U.S. patent application number 14/987156 was filed with the patent office on 2016-04-28 for compositions with ph responsive copolymer containing maep and/or mahp and methods for using same.
This patent application is currently assigned to RHODIA OPERATIONS. The applicant listed for this patent is RHODIA OPERATIONS. Invention is credited to Herve ADAM, Nemesio MARTINEZ-CASTRO, Jennie MCGUIRE, James WOODS.
Application Number | 20160113856 14/987156 |
Document ID | / |
Family ID | 50974890 |
Filed Date | 2016-04-28 |
United States Patent
Application |
20160113856 |
Kind Code |
A1 |
MARTINEZ-CASTRO; Nemesio ;
et al. |
April 28, 2016 |
COMPOSITIONS WITH PH RESPONSIVE COPOLYMER CONTAINING MAEP AND/OR
MAHP AND METHODS FOR USING SAME
Abstract
Disclosed is a pH responsive polymer made with
mono-[2-(methacryloyloxy)ethyl]phthalate and/or
mono-[2-(methacryloyloxy)ethyl hexahydro]phthalate. Also disclosed
is an aqueous coating composition including at least one latex
polymer derived from at least one monomer copolymerized or blended
with alkali swellable acrylate copolymer. Also provided is an
aqueous coating composition including at least one latex polymer
derived from at least one monomer blended with alkali swellable
acrylate copolymer, at least one pigment, and water. Also provided
is a method of preparing an aqueous coating composition such as a
latex paint including the above components. Also provided are
methods of preparing mono-[2-(methacryloyloxy)ethyl]phthalate. Also
provided are compositions and methods using the polymer in
hydraulic fracturing, personal care and or home and industrial
cleaners.
Inventors: |
MARTINEZ-CASTRO; Nemesio;
(Bristol, PA) ; MCGUIRE; Jennie; (Lansdale,
PA) ; ADAM; Herve; (Vadodara, IN) ; WOODS;
James; (Wilmington, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
RHODIA OPERATIONS |
Paris |
|
FR |
|
|
Assignee: |
; RHODIA OPERATIONS
Paris
FR
|
Family ID: |
50974890 |
Appl. No.: |
14/987156 |
Filed: |
January 4, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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14132685 |
Dec 18, 2013 |
9228041 |
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14987156 |
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Current U.S.
Class: |
166/308.3 ;
424/70.16; 507/224; 510/475; 514/772.6; 523/122; 524/502; 524/558;
560/95 |
Current CPC
Class: |
C08F 220/06 20130101;
C09K 8/685 20130101; C08F 220/06 20130101; C08F 220/283 20200201;
C08F 220/303 20200201; C07C 69/80 20130101; C08F 220/285 20200201;
C08F 20/64 20130101; C08F 220/285 20200201; A61K 8/8194 20130101;
C09D 5/024 20130101; C08F 220/28 20130101; A61Q 5/00 20130101; A61Q
19/00 20130101; C09K 8/74 20130101; C07C 67/08 20130101; C09K 8/70
20130101; C09K 2208/08 20130101; A61K 8/86 20130101; C08F 220/64
20130101; A61K 2800/48 20130101; C09K 8/882 20130101; C08F 220/18
20130101; C08F 220/18 20130101; C09D 5/04 20130101; C11D 17/003
20130101; A61K 2800/10 20130101; C09K 8/588 20130101; C08F 20/06
20130101; E21B 43/26 20130101; C09K 8/68 20130101; C07C 67/08
20130101; A61K 8/8152 20130101; C08F 220/18 20130101; C11D 3/3757
20130101; C11D 3/3765 20130101; C08F 220/06 20130101; C09D 7/43
20180101; C08L 33/08 20130101 |
International
Class: |
A61K 8/81 20060101
A61K008/81; C09K 8/68 20060101 C09K008/68; C09K 8/88 20060101
C09K008/88; E21B 43/26 20060101 E21B043/26; C09D 7/00 20060101
C09D007/00; C09D 5/04 20060101 C09D005/04; A61Q 19/00 20060101
A61Q019/00; A61Q 5/00 20060101 A61Q005/00; C11D 3/37 20060101
C11D003/37; C07C 67/08 20060101 C07C067/08 |
Claims
1-13. (canceled)
14. An aqueous composition, comprising water and a pH responsive
copolymer of unsaturated copolymerizable monomers, said unsaturated
copolymerizable monomers comprising, based on total weight of
monomers: A. about 0.1-70 weight percent first acidic monomer
selected from at least one member of the group consisting of
mono-[2-(methacryloyloxy)ethyl]phthalate and
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate, B. about 0-45
weight percent of at least one C3-C8 alpha beta-ethylenically
unsaturated second acidic monomer, preferably a C3-C8 alpha
beta-ethylenically unsaturated carboxylic acid monomer; C. about
15-70 weight percent of at least one nonionic, copolymerizable
C2-C12 alpha, beta-ethylenically unsaturated monomer; and D. about
0 to 30 weight percent of at least one nonionic ethylenically
unsaturated hydrophobic monomer.
15. The aqueous composition of claim 14, further comprising an
emulsifier, wherein the aqueous composition is a pH responsive
composition.
16. The aqueous composition of claim 15, having an average particle
size of about 500 to about 3000 angstroms and a Brookfield
viscosity of about 100 to about 500,000, cps as a 1 percent aqueous
solution in ammonium salt at pH 9.0 and 25 degrees C.
17. The aqueous composition of claim 14, wherein the composition
comprises, based on 100 parts by weight of the composition, from
about 0.05 parts by weight to about 20 parts by weight of the pH
responsive polymer.
18. The aqueous composition of claim 14, wherein the composition is
an emulsion comprising an effective amount of the pH responsive
compound, and further comprises an emulsifier and a film forming
polymer latex, wherein the pH responsive copolymer is present in an
amount effective for modifying the rheological properties of the
emulsion.
19. The composition of claim 16, further comprising one or more of
a pigment, a filler, or an extender.
20. The aqueous composition of claim 18, wherein the emulsion is
selected from the group consisting of a latex paint, a latex
coating, a cosmetic, a detergent/cleanser, and an oilfield drilling
fluid.
21. The aqueous composition of claim 20, wherein the emulsion is a
latex paint, further comprising at least one additive selected from
the group consisting of dispersants, surfactants, rheology
modifiers, defoamers, thickeners, biocides, mildewcides, colorants,
waxes, perfumes and co-solvents to a mixture comprising the latex
polymer and water.
22-23. (canceled)
24. The aqueous composition of claim 14, wherein the composition is
a personal care composition and further comprises one or more
surfactants.
25. The aqueous composition of claim 14, wherein the one or more
surfactants comprise at least one anionic surfactant and the
composition further comprises a structuring agent for the anionic
surfactant.
26. The aqueous composition of claim 14, further comprising a
personal care benefit agent.
27. The aqueous composition of claim 14, wherein the composition is
a particle dispersion and further comprises particles dispersed in
the composition.
28. A method for handling particles, comprising dispersing the
particles in a composition according to claim 27, to form an
aqueous particle dispersion.
29. The method of claim 28, further comprising transporting the
aqueous particle dispersion by pumping the aqueous particle
dispersion through a conduit.
30. The method of claim 29, comprising directing a stream of the
composition into a subterranean formation, wherein the composition
is a hydraulic fracturing composition and further comprises a
proppant.
31. The aqueous composition of claim 14, wherein the composition is
a hydraulic fracturing composition and further comprises a
proppant.
32. A method for fracturing a geologic formation, comprising
directing a stream of the composition of claim 31 at a surface of
the formation at a pressure and flow rate at least sufficient to
initiate, extend, or initiate and extend one or more fractures in
the formation.
33. A method for thickening an aqueous emulsion, comprising:
forming a blend by blending with the aqueous emulsion an amount of
the pH-responsive composition of claim 12 effective to thicken the
aqueous emulsion when pH of the blend is adjusted to a pH in the
range of about 6.5 to about 11.
34. A process comprising the steps of: mixing 100 parts by weight
2-hydroxyethy methacrylate (HEMA) and 0.1 to 0.5 parts by weight
4-methoxyphenol (MEHQ) to form a mixture; heating the mixture to a
set point of 70-100.degree. C. with NOx sparge and then adding
25-50 parts by weight phthalic anhydride as a first dose of
phthalic anhydride to the heated mixture; after adding the first
dose of phthalic anhydride then adding 1-3 parts by weight
imidazole to the mixture; after adding the imidazole then adding 50
to 90 parts by weight phthalic anhydride as a second dose of
phthalic anhydride; after adding the second dose of phthalic
anhydride then heating the reaction mixture at 70-90.degree. C. to
form mono-[2-(methacryloyloxy)ethyl]phthalate; and recovering the
mono-[2-(methacryloyloxy)ethyl]phthalate.
35. A process comprising the steps of: mixing 15-25 parts by weight
2-hydroxyethy methacrylate (HEMA) and at least one member of the
group consisting of 1-3 parts by weight
2,6-di-tert-butyl-4-((dimethylamino)methyl)phenol or 0.2-2 parts by
weight 2,4,6-tris((dimethylamino)methyl)phenol; heating the mixture
to a set point of 70-100.degree. C. with NOx sparge and then adding
10-30 parts by weight phthalic anhydride to the heated mixture;
after adding the phthalic anhydride then heating the reaction
mixture at 70-90.degree. C. to form
mono-[2-(methacryloyloxy)ethyl]phthalate; and recovering the
mono-[2-(methacryloyloxy)ethyl]phthalate.
36. The process of claim 35 wherein the process is performed with
an absence of MEHQ and an absence of base catalyst.
37. The process of claim 35 wherein the process is performed with
an absence of base catalyst.
38. A method for promoting personal care comprising applying the
copolymer of claim 1 to skin or hair of a user.
39. A home care or industrial cleaning composition for cleaning
fabrics or hard surfaces comprising, the copolymer of claim 1 and a
surfactant and a home care or industrial cleaner benefit agent.
40. A method for cleaning a substrate selected from the group
consisting of a hard surface and a fabric, comprising applying the
composition of claim 39 to the substrate.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This claims the benefit of U.S. provisional patent
application No. 61/740,837, filed 21 Dec. 2012, incorporated herein
by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to compositions and methods
using a HASE copolymer or ASE copolymer as a thickener for making
paints and coatings. In particular one of the monomers from which
the HASE and/or ASE copolymer is made is
mono-[2-(methacryloyloxy)ethyl]phthalate (MAEP) (also known as
2-(2-carboxybenzoyloxy)ethyl methacrylate) and/or
mono-[2-(methacryloyloxy)ethyl hexahydro]phthalate (MAHP) (also
known as Monoacryloyloxyethy Hexahydrophthalate).
BACKGROUND OF THE INVENTION
[0003] Rheological additives are chemical compositions, which,
added even in small amounts, modify a liquid system's rheological
properties, such as viscosity and response to shear. Such additives
or thickeners may be used in a variety of liquid systems including
aqueous systems such as paints, aqueous inks, and personal care
products and compositions for treating subterranean formations. The
additives improve the rheological properties by also affecting the
dispersion, suspension and emulsification of pigments, binders and
other solids within a vehicle.
[0004] Thixotropic promoters are a category of rheology additives
widely used in the coating industry. They can be categorized as
organic clay, polyethylene waxes and titanium derivatives. These
thixotropic promoters have been used for a long time in latex
paints and other architectural coatings. Many types of thixotropic
promoters are used because each of them has its own limitations.
Some, such as the organic clay, are very effective but they have
disadvantages such as decreasing the gloss of the paint
significantly. Thixotropic promoters are also used in hydraulic
fracturing of subterranean formations, such as oil and natural gas
wells, and other methods of secondary oil recovery.
[0005] Hydrophobically modified alkali swellable emulsion (HASE,
also known as Hydrophobically modified alkali soluble) polymer
systems and alkali soluble emulsion (ASE) polymer systems are
commonly employed to modify the rheological properties of aqueous
emulsion systems. These polymers are substantially insoluble in
water at a low pH. However, at higher pH they become swellable or
soluble in water and thus exhibit thickening behavior. Under the
influence of a base, organic or inorganic, the HASE particles
gradually swell and expand to form a three-dimensional network by
intermolecular hydrophobic aggregation between HASE copolymer
chains and/or with components of the emulsion. This network,
combined with the hydrodynamic exclusion volume created by the
expanded HASE chains, produces a thickening effect. This network is
sensitive to applied stress so it breaks down under shear and
recovers when the stress is relieved. Such rheological properties
are particularly desirable for paints and coatings because they
make the formulation easy to apply onto a surface while providing
the thickness needed for uniform coverage and avoid spattering.
[0006] These alkali-swellable and alkali-soluble polymers are
carboxyl functional polymers synthesized by free radical
polymerization. HASE copolymer systems can be prepared from the
following monomers: (a) an ethylenically unsaturated carboxylic
acid, (b) a nonionic ethylenically unsaturated monomer, and (c) an
ethylenically unsaturated hydrophobic monomer. Representative HASE
copolymer systems include those shown in EP 226097 B1, EP 705852
B1, U.S. Pat. No. 4,384,096, U.S. Pat. No. 5,874,495, U.S. Pat. No.
7,217,752 B2, and US patent application publication 2006/0270563
A1, now U.S. Pat. Nos. 7,772,421 and 8,071,674, all incorporated
herein by reference.
[0007] Three categories of polymers produced by emulsion
polymerization are: (1) Synthetic rubber: some grades of
styrene-butadiene (SBR), some grades of polybutadiene,
polychloroprene (Neoprene), nitrile rubber, acrylic rubber,
fluoroelastomer (FKM); (2) Plastic: some grades of PVC, some grades
of polystyrene, some grades of PMMA (polymethylmethacrylate),
acrylonitrile-butadiene-styrene terpolymer (ABS), polyvinylidene
fluoride, polytertrafluoroethylene (PTFE); and (3) Dispersions
(i.e., polymers sold as aqueous dispersions).
[0008] Latex is an example of an emulsion polymer which is a water
based polymer dispersion. Latex paints are used for a variety of
applications including interior and exterior, and flat, semi-gloss
and gloss applications. Latex is a stable dispersion (colloidal
emulsion) of rubber or plastic polymer microparticles in an aqueous
medium. Latexes may be natural or synthetic.
[0009] It would be desirable to have a as a thixotropic promoter
that provides improved viscosity control, sagging, and leveling,
while maintaining gloss in latex paints and coatings.
[0010] Hydraulic fracturing of the subterranean formation is
conducted to increase oil and/or gas production. Fracturing is
caused by injecting a viscous fracturing fluid or a foam at a high
pressure (hereinafter injection pressure) into the well to form a
fracture. As the fracture is formed, the particulate material,
referred to as a "propping agent" or "proppant" is placed in the
formation to maintain the fracture in a propped condition when the
injection pressure is released. Coated and/or uncoated particles
are often used as proppants to keep open fractures imposed by
hydraulic fracturing upon a subterranean formation, e.g., an oil or
gas bearing strata. Particles typically used to prop fractures
generally comprise sand or sintered ceramic particles as the
fracture forms, the proppants are carried into the fracture by
suspending them in additional fluid or foam to fill the fracture
with slurry of proppant in the fluid or foam. Upon release of the
pressure, the proppants form a pack that serves to hold open the
fractures. Thus, the proppants increase production of oil and/or
gas by providing a conductive channel in the formation. There is a
need for a proppant carrier that can prevent settling of proppants
or sand being positioned in the fractures.
[0011] During primary recovery a subterranean formation produces
the oil by pressure depletion. In pressure depletion, the pressure
difference between the formation and a production well or wells
forces the oil contained within the formation toward a production
well where it can be recovered. Typically, up to 35 percent of the
oil initially contained in a formation can be recovered using
pressure depletion. Methods have been developed to recover oil
which could not be recovered using only pressure depletion
techniques or secondary recovery techniques. These methods are
typically referred to as "enhanced oil recovery techniques"
(EOR).
[0012] One enhanced oil recovery process is referred to as
surfactant flooding. This generally covers the use of an aqueous
fluid containing surfactant injected into an oil rich formation to
displace oil from the formation and the displaced oil is then
recovered.
[0013] Another enhanced oil recovery process is referred to as
chemical flooding. This generally covers the use of polymer and/or
surfactant slugs. In polymer flooding, a polymer solution is
injected to displace oil toward producing wells. The polymer
solution is designed to develop a favorable mobility ratio between
the injected polymer solution and the oil/water bank being
displaced ahead of the polymer. In surfactant flooding, an aqueous
solution containing surfactant is injected into the oil rich
formation. Residual oil drops are deformed as a result of low
interfacial tension provided by surfactant solution and drops are
displaced through the pore throats and displaced oil is then
recovered.
[0014] U.S. Pat. No. 4,432,881, incorporated herein by reference in
its entirety, discloses an aqueous liquid medium having increased
low shear viscosity as provided by dispersing into the aqueous
medium (1) a water-soluble polymer having pendant hydrophobic
groups, e.g., an acrylamide dodecyl acrylate copolymer, and (2) a
water-dispersible surfactant, e.g., sodium oleate, or dodecyl
polyethyleneoxy glycol monoether.
[0015] U.S. Pat. No. 4,541,935, incorporated herein by reference in
its entirety, discloses fracturing processes which use aqueous
hydraulic fracturing fluids. The fluids comprise: (a) an aqueous
medium, and (b) a thickening amount of a thickener composition
comprising (i) a water-soluble or water-dispersible interpolymer
having pendant hydrophobic groups chemically bonded thereto, (ii) a
nonionic surfactant having a hydrophobic group(s) capable of
associating with the hydrophobic groups on said organic polymer,
and (iii) a water-soluble electrolyte.
[0016] U.S. Pat. No. 5,566,760, incorporated herein by reference in
its entirety, discloses a fracturing fluid comprising surfactants
and hydrophobically-modified polymers.
[0017] U.S. Pat. No. 7,084,095, incorporated herein by reference in
its entirety, discloses addition of polymers to a viscoelastic
surfactant base system allows adjusting the rheological properties
of the base fluid.
[0018] U.S. Pat. No. 7,427,583, incorporated herein by reference in
its entirety, describes an aqueous viscoelastic fracturing fluid
for use in the recovery of hydrocarbons. The fluid comprises a
viscoelastic surfactant and a hydrophobically modified polymer.
[0019] U.S. Pat. No. 7,727,937 to Pauls et al, incorporated herein
by reference in its entirety, discloses acidic treatment fluids
used in industrial and/or subterranean operations, and more
particularly, acidic treatment fluids comprising clarified xanthan
gelling agents, and methods of use in industrial and/or
subterranean operations.
[0020] U.S. Pat. No. 7,772,421 to Yang et al, incorporated herein
by reference in its entirety, discloses a hydraulic fracturing
composition comprising water, a pH responsive polymer and a
proppant.
[0021] U.S. Pat. No. 7,789,160 to Hough et al, incorporated herein
by reference in its entirety discloses an aqueous fluid useful for
the recovery of crude oil from a subterranean formation, which
includes a composition including a mixture of water, a water
soluble block copolymer, an inorganic salt and at least one member
of the group of a nonionic surfactant having an HLB of less than
12, and methods for using same.
[0022] U.S. Pat. No. 7,857,055 to Li et al, incorporated herein by
reference in its entirety, discloses a fluid for treating a
subterranean formation comprising an aqueous solution of a
polysaccharide, a polyacrylamide, a crosslinking agent, and less
than 0.1% by weight of any clay component, wherein the
polyacrylamide is present in an amount of from about 0.01 percent
to about 1 percent by weight of the fluid.
[0023] It would be desirable to provide stable fracturing fluids
and EOR fluids for subterranean formations, such as natural gas
and/or oil field.
[0024] Also, there is a need to enhance viscosity to improve
personal care compositions. In personal care applications,
consumers are increasingly demanding formulations that provide
multiple benefits such as, but not limited to, unique sensory
experience, enhanced moisturization, increased conditioning,
improved delivery of active ingredients and compatibility.
Synthetic rheology modifier polymers can be employed to assist in
achieving one or more of these properties.
[0025] Also there is a need to enhance viscosity to improve
cleaning compositions for home and industry.
SUMMARY OF THE INVENTION
[0026] The invention is directed to pH responsive copolymer of a
mixture of unsaturated copolymerizable monomers, the unsaturated
copolymerizable monomers comprising, based on total weight of
monomers:
[0027] A. about 0.1-70 weight percent, typically 0.5-50, 0.7-40,
1-40, 5-40, 5-30 or 10 to 40 weight percent of at least one alpha
beta-ethylenically unsaturated first acid monomer selected from the
group consisting of mono-[2-(methacryloyloxy)ethyl]phthalate (also
known as 2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) and
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP),
[0028] B. about 0-45 weight percent, preferably 5 to 30 weight
percent, of at least one C3-C8 alpha beta-ethylenically unsaturated
acidic monomer, preferably a C3-C8 alpha beta-ethylenically
unsaturated carboxylic acid monomer;
[0029] C. about 15-70 weight percent, typically 20 to 50 weight
percent, of at least one non-ionic, copolymerizable C2-C12 alpha,
beta-ethylenically unsaturated monomer; and
[0030] D. about 0 to 30 weight percent, preferably 0.05 to 30
weight percent or typically 5 to 20 weight percent, of at least one
non-ionic ethylenically unsaturated hydrophobic monomer.
[0031] The pH responsive copolymer is also known as a HASE or ASE
copolymer. The HASE copolymer includes component D and the ASE
copolymer does not include component D.
[0032] The present invention also includes compositions such as
aqueous dispersions comprising this pH responsive copolymer. In
particular the invention is also directed using the pH responsive
copolymer as an additive for latex binders, paints and aqueous
coatings. This pH responsive copolymer additive is a thickener used
as a thixotropic promoter during formulation of the latex binders,
paints and aqueous coatings, compositions for treating subterranean
formations, home care and personal care.
[0033] The invention is also directed to a homogeneous, pourable
liquid which improves sagging properties in coatings without a
significant decrease in gloss. The improved sagging property is due
to the thixotropic behavior of the HASE and/or ASE copolymer
thickener synthesized with the above mentioned monomer. In addition
the new thixotropic promoter only needs low shear for
incorporation.
[0034] The aqueous coating compositions of the invention typically
include at least one latex polymer derived from at least one
monomer, for example acrylic monomers. The at least one latex
polymer in the aqueous coating composition can be a pure acrylic, a
styrene acrylic, a vinyl acrylic or an acrylated ethylene vinyl
acetate copolymer and is more preferably a pure acrylic. The at
least one latex polymer is preferably derived from at least one
acrylic monomer selected from the group consisting of acrylic acid,
acrylic acid esters, methacrylic acid, and methacrylic acid esters.
For example, the at least one latex polymer can be a butyl
acrylate/methyl methacrylate copolymer or a 2-ethylhexyl
acrylate/methyl methacrylate copolymer. Typically, the at least one
latex polymer is further derived from one or more monomers selected
from the group consisting of styrene, alpha-methyl styrene, vinyl
chloride, acrylonitrile, methacrylonitrile, ureido methacrylate,
vinyl acetate, vinyl esters of branched tertiary monocarboxylic
acids, itaconic acid, crotonic acid, maleic acid, fumaric acid,
ethylene, and C4-C8 conjugated dienes.
[0035] Latex paint formulations typically comprise additives, e.g.,
at least one pigment. In a preferred embodiment of the invention
the latex paint formulation includes at least one pigment selected
from the group consisting of TiO2, CaCO3, clay, aluminum oxide,
silicon dioxide, magnesium oxide, sodium oxide, potassium oxide,
talc, barytes, zinc oxide, zinc sulfite and mixtures thereof. More
preferably the at least one pigment includes TiO2, calcium
carbonate or clay.
[0036] In addition to the above components, the aqueous coating
composition can include one or more additives selected from the
group consisting of dispersants, surfactants, rheology modifiers,
defoamers, thickeners, biocides, mildewcides, colorants, waxes,
perfumes and co-solvents.
[0037] The present invention is also directed to new processes for
making mono-[2-(methacryloyloxy)ethyl]phthalate (also known as
2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP).
[0038] Compositions of the present invention may have an absence of
one or more of anionic surfactant, cationic surfactant, nonionic
surfactant, zwitterionic surfactant, and/or amphoteric
surfactant.
[0039] These and other features and advantages of the present
invention will become more readily apparent to those skilled in the
art upon consideration of the following detailed description, which
describe both the preferred and alternative embodiments of the
present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] FIG. 1 shows Viscosity Profiles of formulations prepared
with HASE thickeners containing MAEP and MAHP (in RHOPLEX
SG30).
[0041] FIG. 2 shows Yield Stress of formulations prepared with HASE
thickeners containing MAEP and MAHP (in RHOPLEX SG30).
[0042] FIG. 3 shows thixotropic measurement of Binder and HASE
Polymer System K of HASE polymer 12 in RHOPLEX SG30 (couette).
[0043] FIG. 4 shows the measurement of Binder and HASE Polymer
System J of HASE polymer 11 in RHOPLEX SG30 (couette).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0044] The present invention relates to the use of a particular
family of HASE and/or ASE copolymers for latex dispersions,
binders, paints and coatings. The present invention provides
aqueous compositions, for example, aqueous coating compositions.
The aqueous compositions of the invention are aqueous polymer
dispersions which include at least one latex polymer. Paints or
other aqueous coatings of the present invention typically further
include at least one pigment. Typically the latex has a Tg of less
than 10.degree. C., more typically less than 5.degree. C., still
more typically in the range from 5 to -10.degree. C., e.g.,
0.degree. C.
[0045] As used herein, the term "alkyl" means a monovalent straight
or branched saturated hydrocarbon radical, more typically, a
monovalent straight or branched saturated (C.sub.1-C.sub.40)
hydrocarbon radical, such as, for example, methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, octyl, hexadecyl,
octadecyl, eicosyl, behenyl, tricontyl, and tetracontyl.
[0046] As used herein, the term "alkenyl" means an unsaturated
straight or branched hydrocarbon radical, more typically an
unsaturated straight, branched, (C.sub.2-C.sub.22) hydrocarbon
radical, that contains one or more carbon-carbon double bonds, such
as, for example, ethenyl, n-propenyl, iso-propenyl.
[0047] As used herein, the term "alkoxyl" means an oxy radical that
is substituted with an alkyl group, such as for example, methoxyl,
ethoxyl, propoxyl, isopropoxyl, or butoxyl, which may optionally be
further substituted on one or more of the carbon atoms of the
radical.
[0048] As used herein, the term "alkoxyalkyl" means an alkyl
radical that is substituted with one or more alkoxy substituents,
more typically a (C.sub.1-C.sub.22)alkyloxy-(C.sub.1-C.sub.6)alkyl
radical, such as methoxymethyl, and ethoxybutyl.
[0049] As used herein, terms "aqueous medium" and "aqueous media"
are used herein to refer to any liquid medium of which water is a
major component. Thus, the term includes water per se as well as
aqueous solutions and dispersions.
[0050] As used herein, the term "aryl" means a monovalent
unsaturated hydrocarbon radical containing one or more six-membered
carbon rings in which the unsaturation may be represented by three
conjugated double bonds, which may be substituted one or more of
carbons of the ring with hydroxy, alkyl, alkoxyl, alkenyl, halo,
haloalkyl, monocyclic aryl, or amino, such as, for example, phenyl,
methylphenyl, methoxyphenyl, dimethylphenyl, trimethylphenyl,
chlorophenyl, trichloromethylphenyl, triisobutyl phenyl,
tristyrylphenyl, and aminophenyl.
[0051] As used herein, the term "arylalkyl" means an alkyl group
substituted with one or more aryl groups, more typically a
(C.sub.1-C.sub.18)alkyl substituted with one or more
(C.sub.6-C.sub.14)aryl substituents, such as, for example,
phenylmethyl, phenylethyl, and triphenylmethyl.
[0052] As used herein, the term "aryloxy" means an oxy radical
substituted with an aryl group, such as for example, phenyloxy,
methylphenyl oxy, isopropylmethylphenyloxy.
[0053] The "bicyclo[d.e.f]" notation is used herein in reference to
bicycloheptyl and bicycloheptenyl ring systems in accordance with
the von Baeyer system for naming polycyclic compounds, wherein a
bicyclic system is named by the prefix "bicyclo-" to indicate
number of rings in the system, followed by a series of three arabic
numbers, listed in descending numerical order, separated by full
stops, and enclosed in square brackets, to indicate the respective
number of skeletal atoms in each acyclic chain connecting the two
common atoms (the "bridgehead atoms"), excluding the bridgehead
atoms.
A bridgehead atom is any skeletal atom of the ring system bonded to
three or more skeletal atoms (excluding hydrogen). A bicyclic
system (which comprises the main ring and main bridge only) is
named by: the prefix bicyclo- (indicating the number of rings);
numbers indicating the bridge lengths (i.e. number of skeletal
atoms excluding the bridgehead atoms) separated by full stops and
placed in square brackets. The three numbers are cited in
decreasing order of size (e.g.[3.2.1]); the name of the hydrocarbon
indicating the total number of skeletal atoms. For example,
bicyclo[3.2.1]octane is the name for the structure of Formula
I.
##STR00001##
[0054] As used herein, the terminology "(C.sub.x-C.sub.y)" in
reference to an organic group, wherein x and y are each integers,
indicates that the group may contain from x carbon atoms to y
carbon atoms per group.
[0055] As used herein, the term "cycloalkenyl" means an unsaturated
hydrocarbon radical, typically an unsaturated (C.sub.5-C.sub.22)
hydrocarbon radical, that contains one or more cyclic alkenyl rings
and which may optionally be substituted on one or more carbon atoms
of the ring with one or two (C.sub.1-C.sub.6)alkyl groups per
carbon atom, such as cyclohexenyl, cycloheptenyl, and
"bicycloalkenyl" means a cycloalkenyl ring system that comprises
two condensed rings, such as bicycloheptenyl.
[0056] As used herein, the term "cycloalkyl" means a saturated
hydrocarbon radical, more typically a saturated (C.sub.5-C.sub.22)
hydrocarbon radical, that includes one or more cyclic alkyl rings,
which may optionally be substituted on one or more carbon atoms of
the ring with one or two (C.sub.1-C.sub.6)alkyl groups per carbon
atom, such as, for example, cyclopentyl, cycloheptyl, cyclooctyl,
and "bicyloalkyl" means a cycloalkyl ring system that comprises two
condensed rings, such as bicycloheptyl.
[0057] As used herein, an indication that a composition is "free"
of a specific material means the composition contains no measurable
amount of that material.
[0058] As used herein, the term "heterocyclic" means a saturated or
unsaturated organic radical that comprises a ring or condensed ring
system, typically comprising from 4 to 16 ring atoms per ring or
ring system, wherein such ring atoms comprise carbon atoms and at
least one heteroatom, such as for example, O, N, S, or P per ring
or ring system, which may optionally be substituted on one or more
of the ring atoms, such as, for example, thiophenyl,
benzothiphenyl, thianthrenyl, pyranyl, benzofuranyl, xanthenyl,
pyrolidinyl, pyrrolyl, pyradinyl, pyrazinyl, pyrimadinyl,
pyridazinyl, indolyl, quinonyl, carbazolyl, phenathrolinyl,
thiazolyl, oxazolyl, phenoxazinyl, or phosphabenzenyl.
[0059] As used herein, the term "hydroxyalkyl" means an alkyl
radical, more typically a (C.sub.1-C.sub.22)alkyl radical, that is
substituted with one or more hydroxyl groups, such as for example,
hydroxymethyl, hydroxyethyl, hydroxypropyl, and hydroxydecyl.
[0060] As used herein the term "(meth)acrylate" refers collectively
and alternatively to the acrylate and methacrylate and the term
"(meth)acrylamide" refers collectively and alternatively to the
acrylamide and methacrylamide, so that, for example, "butyl
(meth)acrylate" means butyl acrylate and/or butyl methacrylate.
[0061] As used herein, "molecular weight" in reference to a polymer
or any portion thereof, means to the weight-average molecular
weight ("M.sub.w") of the polymer or portion. M.sub.w of a polymer
is a value measured by gel permeation chromatography (GPC) with an
aqueous eluent or an organic eluent (for example dimethylacetamide,
dimethylformamide, and the like), depending on the composition of
the polymer, light scattering (DLS or alternatively MALLS),
viscometry, or a number of other standard techniques. M.sub.w of a
portion of a polymer is a value calculated according to known
techniques from the amounts of monomers, polymers, initiators
and/or transfer agents used to make the portion.
[0062] In one embodiment, the copolymers for use in the present
invention exhibit a weight average molecular weight, as determined
by gel permeation chromatography (GPC) and light scattering of a
solution of the polymer in tetrahydrofuran and compared to a
polystyrene standard, of greater than or equal to 30,000 grams per
mole ("g/mole"). HASE thickeners may not fully dissolve in THF but
after hydrolysis they can dissolve in water and measurement can be
run in a water gel permeation chromatography (GPC). Reference:
Macromolecules 2000, 33, 2480. For example in a range of 30,000 to
2,000,000 g/mole.
[0063] As used herein, the indication that a radical may be
"optionally substituted" or "optionally further substituted" means,
in general, unless further limited either explicitly or by the
context of such reference, such radical may be substituted with one
or more inorganic or organic substituent groups, for example,
alkyl, alkenyl, aryl, arylalkyl, alkaryl, a hetero atom, or
heterocyclyl, or with one or more functional groups capable of
coordinating to metal ions, such as hydroxyl, carbonyl, carboxyl,
amino, imino, amido, phosphonic acid, sulphonic acid, or arsenate,
or inorganic and organic esters thereof, such as, for example,
sulphate or phosphate, or salts thereof.
[0064] As used herein, "parts by weight" or "pbw" in reference to a
named compound refers to the amount of the named compound,
exclusive, for example, of any associated solvent. In some
instances, the trade name of the commercial source of the compound
is also given, typically in parentheses. For example, a reference
to "10 pbw cocoamidopropylbetaine ("CAPB", as MIRATAINE BET C-30)"
means 10 pbw of the actual betaine compound, added in the form of a
commercially available aqueous solution of the betaine compound
having the trade name "MIRATAINE BET C-30", and exclusive of the
water contained in the aqueous solution.
[0065] As used herein, an indication that a composition is
"substantially free" of a specific material, means the composition
contains no more than an insubstantial amount of that material, and
an "insubstantial amount" means an amount that does not measurably
affect the desired properties of the composition.
[0066] As used herein, the term "surfactant" means a compound that
reduces surface tension when dissolved in water.
[0067] "Surfactant effective amount" means the amount of the
surfactant that provides a surfactant effect to enhance the
stability of emulsions of the polymers.
[0068] I. pH Responsive Copolymer
[0069] The invention is directed to a pH responsive copolymer of a
mixture of unsaturated copolymerizable monomers. These pH
responsive copolymers are substantially insoluble in water at a low
pH. However, at higher pH they become swellable or soluble in water
and thus exhibit thickening behavior. Thus, the pH responsive
copolymer is interchangeably termed alkali swellable copolymer or
alkali soluble copolymer. Typically the pH responsive copolymer is
termed an alkali-soluble emulsion (ASE) copolymer and/or a
hydrophobically modified alkali-soluble emulsion (HASE) copolymer.
Although this copolymer is described as ASE and/or HASE copolymer
it is not necessary to make a copolymer of this structure by
emulsion polymerization. The copolymer may also be made by solution
polymerization and comes within the invention whether made by
emulsion polymerization or solution polymerization.
[0070] The pH responsive copolymer is made from a mixture of
unsaturated copolymerizable monomers, the unsaturated
copolymerizable monomers comprising, based on total weight of
monomers:
[0071] A. about 0.1-70 weight percent, typically 0.5-50, 0.7-40,
1-40, 5-40, 5-30 or 10 to 40 weight percent, of at least one alpha
beta-ethylenically unsaturated first acid monomer selected from the
group consisting of mono-[2-(methacryloyloxy)ethyl]phthalate (MAEP)
(also known as 2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP)
having the structure A.I:
##STR00002##
[0072] CAS No. 27697-00-3; Chemical FormulaC14H14O6, molecular
weight 278.08; and
[0073] mono-[2-(methacryloyloxy)ethyl hexahydro]phthalate (MAHP)
(also known as Monoacryloyloxyethy Hexahydrophthalate) having the
structure A.II
##STR00003##
[0074] CAS No. 51252-88-1, molecular formula 014H20O6, molecular
weight 284.31.
[0075] B. about 0-45 weight percent, preferably 5 to 30 weight
percent, of at least one C3-C8 alpha, beta-ethylenically
unsaturated first acidic monomer, preferably a C3-C8 alpha
beta-ethylenically unsaturated carboxylic acid monomer;
[0076] C. about 15-70 weight percent, typically 20 to 50 weight
percent, of at least one nonionic monomer, each comprising a
nonionic substituent group, copolymerizable C2-C12 alpha,
beta-ethylenically unsaturated monomer; and
[0077] D. about 0 to 30 weight percent, preferably 0.05 to 30
weight percent or typically 5 to 20 weight percent, of at least one
non-ionic ethylenically unsaturated hydrophobic monomer.
[0078] In terms of monomeric units of the resulting pH responsive
copolymer, rather than monomers from which the pH responsive
copolymer is made, the pH responsive copolymer comprises:
[0079] A. about 0.1-70 weight percent, typically 0.5-50, 0.7-40,
1-40, 5-40, 5-30 or 10 to 40 weight percent first acidic monomeric
units derived by opening the alpha beta-ethylenic unsaturated bond
of at least one member of the group consisting of
mono-[2-(methacryloyloxy)ethyl]phthalate (also known as
2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP)
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP);
[0080] B. about 0-45 weight percent, preferably 5 to 30 weight
percent, second acidic monomeric units, preferably each second
acidic monomeric unit independently comprises a carboxylic
acid-functional substituent group;
[0081] C. about 15-70 weight percent, typically 20 to 50 weight
percent, nonionic monomeric units, each comprising a nonionic
substituent group. The non-ionic monomeric units, each
independently comprising a nonionic substituent group, for example
Ethyl Acrylate (EA) monomer; and
[0082] D. about 0 to 30 weight percent, preferably 0.05 to 30
weight percent or typically 5 to 20 weight percent, of at least one
non-ionic ethylenically unsaturated hydrophobic monomeric unit.
[0083] The ASE copolymer lacks the non-ionic ethylenically
unsaturated hydrophobic monomeric units. In contrast, the HASE
copolymer includes the hydrophobic monomeric units in an amount of
about 0.05-30 weight percent hydrophobic monomer units based on
total weight of monomers.
[0084] The first acidic monomeric units assist to prevent
sagging.
[0085] The second acidic monomeric units provide solubility and
sagging. Typical second acidic monomeric units each independently
comprise at least one acid group per monomeric unit, for example, a
sulfonic acid group, a phosphonic acid group, a phosphoric acid
group, or a carboxylic acid-functional substituent group. Typically
the second acidic monomeric units, each independently comprise a
carboxylic acid-functional substituent group, for example,
methacrylic acid (MAA).
[0086] The nonionic monomeric units, for example slightly insoluble
ethyl acrylate (EA) or butyl acrylate (BA), segments enhance the
thickening performance by promoting hydrophobic aggregations.
[0087] The hydrophobic macro monomers are responsible for
intra-/intermolecular associations. For example, they are specialty
monomers which typically include a polymerizable group, a
hydrophobic macro group and a bivalent polyether group of a poly
(ethylene oxide) chain, usually 5-100 ethylene oxide units
(typically 6-10 EO groups) and optionally 0-5 propylene oxide units
to favor the intermolecular aggregation. The bivalent polyether
group typically links the hydrophobic macro groups to the
polymerizable group. The polymerizable group typically becomes part
of the backbone of the pH responsive copolymer and the bivalent
polyether group linking group and macro group becomes a side chain
of the pH responsive copolymer. Examples of this side chain
comprising the bivalent polyether group linking group and macro
group are a bicycloheptyl-polyether group, a
bicycloheptenyl-polyether group or a branched
(C.sub.5-C.sub.50)alkyl-polyether group, wherein the
bicycloheptyl-polyether or bicycloheptenyl-polyether group may
optionally be substituted on one or more ring carbon atoms by one
or two (C.sub.1-C6)alkyl groups per carbon atom.
[0088] Formula III shows an idealized diagram of the structure of
an embodiment of this HASE copolymer made from alpha beta-ethylenic
unsaturated bond of mono-[2-(methacryloyloxy)ethyl]phthalate (also
known as 2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) as the
first acidic monomer, methacrylic acid as the second acidic
monomer, ethyl acrylate as the nonionic monomer and a hydrophobic
polymer. The hydrophobic polymer having a polyethylene oxide chain
as a bivalent polyether group linking a polymerizable functional
group and a C18H37 macro hydrophobic group.
##STR00004##
[0089] Formula IV shows an idealized diagram of the structure of an
ASE copolymer made from alpha beta-ethylenic unsaturated bond of
mono-[2-(methacryloyloxy)ethyl]phthalate (also known as
2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) as the first
acidic monomer, methacrylic acid as the second acidic monomer,
ethyl acrylate as the nonionic monomer, and a hydrophobic polymer
having a polymerizable functional group, a C18H37 macro hydrophobic
group and an ethylene oxide chain as a bivalent polyether group
linking the polymerizable functional group and a C18H37 macro
hydrophobic group.
##STR00005##
[0090] Formula V shows an idealized diagram of the structure of
this HASE copolymer made from alpha beta-ethylenic unsaturated bond
of mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP) as the
first acidic monomer, methacrylic acid as the second acidic
monomer, ethyl acrylate as the nonionic monomer, and a hydrophobic
polymer having a polymerizable functional group, a C18H37 macro
hydrophobic group and an ethylene oxide chain as a bivalent
polyether group linking the polymerizable functional group and a
C18H37 macro hydrophobic group.
##STR00006##
[0091] Formula VI shows an idealized diagram of the structure of an
ASE copolymer made from mono-[2-(Methacryloyloxy)ethyl
hexahydro]phthalate (MAHP) as the first acidic monomer, methacrylic
acid as the second acidic monomer, ethyl acrylate as the nonionic
monomer, and a hydrophobic polymer having a polymerizable
functional group, a C18H37 macro hydrophobic group and an ethylene
oxide chain as a bivalent polyether group linking the polymerizable
functional group and a C18H37 macro hydrophobic group.
##STR00007##
[0092] The ASE and/or HASE copolymer comprises a chain of monomeric
units. The polymer is a macromolecule having a relatively high
molecular mass that comprises chains of multiple repetitions of the
monomeric units, which are derived, actually or conceptually, from
molecules of relatively low molecular mass and are connected to
form a linear, branched, or network structure. The copolymer
typically has a linear or branched structure, more typically single
strand linear or branched structure. In one embodiment, a polymer
having a predominantly single strand linear or branched structure
is lightly crosslinked to form a polymer network having a low
density of crosslinks. As used herein the term "single strand" in
regard to a polymer means monomeric units of the polymer are
connected such that adjacent monomeric units are joined to each
other through two atoms, one on each of the adjacent monomeric
units.
[0093] The copolymer may typically be regarded as having a
"backbone", or main polymer chain, from which all branches and
substituent groups of the polymer may be regarded as being pendant.
Where two or more chains of the copolymer could equally be
considered to be the main chain of the polymer, that chain is
selected as the main chain which leads to the simplest
representation of the polymer molecule. The monomeric units of the
copolymer may be arranged in random, alternating, tapered, or block
sequence along the copolymer chain.
[0094] The ASE and/or HASE copolymer typically has a weight average
molecular weight of greater than or equal to about 30,000 grams per
mole, typically the copolymer has a weight average molecular weight
of greater than or equal to about 30,000 to 1,000,000 grams per
mole or 30,000 to 500,000 grams per mole or 50,000 to 500,000 grams
per mole.
[0095] A. First Acidic Monomers for pH Responsive Copolymer
[0096] The alpha beta-ethylenically unsaturated first acid monomer
is selected from the group consisting of
mono-[2-(methacryloyloxy)ethyl]phthalate (also known as
2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) and
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP).
[0097] Mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP)
has the structure A.II:
##STR00008##
[0098] It is commercially available from Wako Pure Chemical
Industries.
[0099] It has the CAS No. 51252-88-1, the molecular formula
C14H20O6, and a molecular weight of 284.31 g/mol.
[0100] Mono-[2-(methacryloyloxy)ethyl]phthalate has the structure
A.I:
##STR00009##
[0101] MAEP has the chemical formula 014H14O6 and a molecular
weight of 278.08 g/mol.
[0102] There are a number of routes to making
mono-[2-(methacryloyloxy)ethyl]phthalate. For example it can be
made by method AA:
##STR00010##
[0103] MEHQ is mono methyl ether of hydroquinone (also known as
4-methoxy phenol). It is an inhibitor to prevent
Hydroxyethylmethacrylate (HEMA) and HEMA Phthalate monomer from
self reacting.
[0104] There are various methods to make
mono-[2-(methacryloyloxy)ethyl]phthalate while using a catalyst to
lower reaction temperatures. For example, U.S. Pat. No. 3,689,427
(Aug. 27, 1969) discloses synthesis using catalytic
N,N-dimethylbenzylamine and no solvent. JP48089947 (1973) discloses
synthesis using catalytic triethylamine and no solvent. CN10110880
(Jun. 21, 2007) discloses synthesis using organic solvent and
several catalysts including pyridine, ethylenediamine and
triethylenediamine. Sedlakova et al., Synthesis of
2-(2-carboxybenzoyloxy)ethyl methacrylate and its radical
polymerizatin and copolymerization with butyl methacrylate, Die
Angewandte Makromolekulare Chemie, 201, 33-48 (1992) discloses
synthesis using organic solvent, and several catalysts including
pyridine, triethylamine and p-toluenesulfonic acid. All of these
patents, patent applications and non-patent literature are
incorporated herein by reference.
[0105] 1. Processes Using Imidazole
[0106] A novel process of the present invention for making
mono-[2-(methacryloyloxy)ethyl]phthalate employs imidazole to serve
as a nucleophile catalyst to activate phthalic anhydride and then
as a leaving group on acylated intermediate. This process employing
imidazole also employs MEHQ as an inhibitor to prevent HEMA from
self reacting.
[0107] The use of imidazole in activation of anhydrides within
analytical procedures is documented by Evtushenko et al, Chemistry
of Heterocyclic Compounds 2000, 36, 1054 and Carey et al, Journal
of Cellular Plastics 1984, Jan.-Feb. This reference describes
imidazole as a useful catalyst in activating anhydrides. However,
this reference does not reveal the use of imidazole to synthesize
mono-[2-(methacryloyloxy)ethyl]phthalate.
[0108] This process comprises the steps of:
[0109] mixing 100 parts by weight 2-hydroxyethy methacrylate (HEMA)
and 0.1 to 0.5 parts by weight 4-methoxyphenol (MEHQ) to form a
mixture;
[0110] heating the mixture to a set point of 70-100.degree. C. and
then adding 25-50 parts by weight phthalic anhydride as a first
dose of phthalic anhydride to the heated mixture;
[0111] after adding the first dose of phthalic anhydride then
adding 1-3 parts by weight imidazole to the mixture during which an
exotherm was noted;
[0112] after adding the imidazole then adding 50 to 90 parts by
weight phthalic anhydride as a second dose of phthalic
anhydride;
[0113] after adding the second dose of phthalic anhydride then
heating the reaction mixture at 70-90.degree. C. for several hours
to form mono-[2-(methacryloyloxy)ethyl]phthalate; and
[0114] recovering the mono-[2-(methacryloyloxy)ethyl]phthalate.
[0115] The reaction mixture was sparged with 8% oxygen in nitrogen
throughout the process However, the reaction also works without NOx
(92/2 N.sub.2/O.sub.2).
[0116] 2. Process Using 2,6-Di-Tert-Butyl-4-(Dimethylaminomethyl)
Phenol or 2,4,6-Tris(Dimethylaminomethyl)Phenol with an Absence of
MEHQ and an Absence of Base Catalyst
[0117] Another preferred novel process of the present invention for
making mono-[2-(methacryloyloxy)ethyl]phthalate uses
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol without MEHQ or base
catalyst. In this role they serve as both catalyst and
inhibitor.
[0118] This process comprises using
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol as a catalyst to activate
phthalic anhydride and as an inhibitor to prevent HEMA from
self-reacting in the absence of additional catalyst. Thus, in this
process there is an absence of MEHQ and an absence of base
catalyst. The 2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol each have dual functionality
in this process. In particular they each act as a catalyst for the
desired reaction of phthalic anhydride and HEMA and an inhibitor to
prevent HEMA from self reacting. As sterically hindered phenols,
both have the recognized ability to serve as radical inhibitors,
inhibiting HEMA from self-reacting.
[0119] 2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol has formula
A.III:
##STR00011##
[0120] 2,4,6-tris(dimethylaminomethyl)phenol has the following
formula A.IV:
##STR00012##
[0121] This process comprises the steps of:
[0122] mixing 15-25 parts by weight 2-hydroxyethy methacrylate
(HEMA) and at least one member of the group consisting of 1-3 parts
by weight 2,6-di-tert-butyl-4-((dimethylamino)methyl)phenol or
0.2-2 parts by weight 2,4,6-tris((dimethylamino)methyl)phenol;
[0123] heating the mixture to a set point of 70-100.degree. C. and
then adding 10-30 parts by weight phthalic anhydride to the heated
mixture;
[0124] after adding the phthalic anhydride then heating the
reaction mixture at 70-90.degree. C. for several hours to form
mono-[2-(methacryloyloxy)ethyl]phthalate; and
[0125] recovering the mono-[2-(methacryloyloxy)ethyl]phthalate.
[0126] The reaction mixture was sparged with 8% oxygen in nitrogen
(NOx) throughout the process.
[0127] 3. Process Using 2,6-Di-Tert-Butyl-4-(Dimethylaminomethyl)
Phenol or 2,4,6-Tris(Dimethylaminomethyl)Phenol with MEHQ in the
Absence of Base Catalyst
[0128] In another inventive process of the present invention, both
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol could be used in the presence
of MEHQ and in an absence of organic base catalyst to make MAEP. In
this role they serve as catalyst only.
[0129] This process for making
mono-[2-(methacryloyloxy)ethyl]phthalate comprises using
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol as a catalyst to activate
phthalic anhydride with MEHQ but without organic base (catalyst) on
commercially available reagents. In this process MEHQ is employed
as a polymerization inhibitor to prevent HEMA from self
reacting.
[0130] The process comprises the steps of:
[0131] mixing 15-25 parts by weight 2-hydroxyethy methacrylate
(HEMA) and at least one member of the group consisting of 1-3 parts
by weight 2,6-di-tert-butyl-4-((dimethylamino)methyl)phenol or
0.2-2 parts by weight 2,4,6-tris((dimethylamino)methyl)phenol;
[0132] heating the mixture to a set point of 70-100.degree. C. with
NOx sparge and then adding 10-30 parts by weight phthalic anhydride
to the heated mixture;
[0133] after adding the phthalic anhydride then heating the
reaction mixture at 70-90.degree. C. to form
mono-[2-(methacryloyloxy)ethyl]phthalate; and
[0134] recovering the mono-[2-(methacryloyloxy)ethyl]phthalate,
wherein the process steps are performed in the absence of a base
catalyst.
[0135] Thus, a) these two molecules
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol have the following two
functions:
[0136] 1. polymerization inhibitor (due to phenyl ring and OH)
[0137] 2. monomer reaction catalyst (due to amino groups) to make
MAEP
[0138] b) Either 2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol can be used to synthesize the
monomer MAEP and no additional base catalyst is needed.
[0139] c) However, as explained below, monomer could be also
synthesized by using the
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol molecules and an additional
base catalyst.
[0140] 4. Process Using 2,6-Di-Tert-Butyl-4-(Dimethylaminomethyl)
Phenol or 2,4,6-Tris(Dimethylaminomethyl)Phenol with Base
Catalyst
[0141] In another alternative both
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol could be used in the presence
of base catalyst to make MAEP. In this role they serve as an
inhibitor. Being an inhibitor is a known literature established
role for these reagents.
[0142] The base catalyst promotes the formation of product at a
lower temperature or in shorter time frame than in an uncatalyzed
system. When added to our system, lower reaction temp provided
higher quality product than uncatalyzed system. The base catalyst
is a Lewis base catalyst. A Lewis base is any species that donates
a pair of electrons to a Lewis acid to form a Lewis adduct. For
example, OH.sup.- and NH.sub.3 are Lewis bases, because they can
donate a lone pair of electrons. Lewis base catalysis is the
process by which an electron pair donor increases the rate of a
given chemical reaction by interacting with an acceptor atom in one
of the reagents or substrates. The binding event may enhance either
the electrophilic or nucleophilic character of the bound species.
Furthermore, the Lewis base should not be consumed or altered
during the course of the reaction. A Lewis base is an atomic or
molecular species where the highest occupied molecular orbital is
highly localized. Typical Lewis bases are amines such as ammonia
and alkyl amines. Other common Lewis bases include pyridine and its
derivatives. Some of the main classes of Lewis bases are amines of
the formula NH.sub.3-xR.sub.x where R=alkyl or aryl, for example
C1-C12 alkyl or C1-C12 aryl. Related to these are pyridine and its
derivatives; phosphines of the formula PR.sub.3-xA.sub.x, where
R=alkyl, A=aryl; and compounds of O, S, Se and Te in oxidation
state 2, including water, ethers, ketones. The following amines are
typical base catalysts: triethylamine and imidazole.
[0143] This process for making
mono-[2-(methacryloyloxy)ethyl]phthalate comprises using
2,6-di-tert-butyl-4-(dimethylaminomethyl)phenol or
2,4,6-tris(dimethylaminomethyl)phenol as a catalyst to activate
phthalic anhydride with MEHQ (polymerization inhibitor) and organic
base (catalyst) on commercially available reagents. In this process
MEHQ is employed as an inhibitor to prevent HEMA from
self-reacting.
[0144] B. Second Acidic Monomeric Units for ASE or HASE
Copolymer
[0145] The polymer of the present invention optionally further
comprises second acidic monomeric units, each independently
comprising at least one acid group per second acidic monomeric
unit.
[0146] In one embodiment, the second acidic monomeric units each
independently comprise, per monomeric unit, at least one group
according to structure (B.I):
--R.sup.32-R.sup.31 (B.I)
wherein R.sup.31 is a moiety that comprises at least one carboxylic
acid, sulfonic acid, or phosphoric acid group, and R.sup.32 is
absent or is a bivalent linking group.
[0147] In one embodiment, R.sup.32 is O, --(CH.sub.2).sub.n--O--,
or is according to structure (structure (B.II):
##STR00013##
wherein: n is an integer of from 1 to 6,
A is O or NR.sup.17, and
[0148] R.sup.17 is H or (C.sub.1-C.sub.4)alkyl.
[0149] In one embodiment, the second acidic monomeric units each
independently comprise one or two carboxy groups per monomeric unit
and may, if the second acidic monomeric unit comprises a single
carboxy group, further comprise an ester group according to
--CH.sub.2COOR.sup.33, wherein R.sup.33 is alkyl, more typically,
(C.sub.1-C.sub.6)alkyl.
[0150] The second acidic monomeric units may be made by known
synthetic techniques, such as, for example, by grafting of one or
more groups according to structure (B.I) onto a polymer backbone,
such as a hydrocarbon polymer backbone, a polyester polymer
backbone, or a polysaccharide polymer backbone. In the alternative,
they may be made by polymerizing a monomer that comprises a
reactive functional group and at least one group according to
structure (B.I) per molecule.
[0151] In one embodiment, the second acidic monomeric units are
derived from polymerizing a monomer comprising a reactive
functional group and a group according to structure (B.XXI) per
molecule.
[0152] In one embodiment, the reactive functional group is an
ethylenically unsaturated group so the monomer comprising a
reactive functional group is an ethylenically unsaturated monomer.
As a result the second acidic monomer comprises at least one site
of ethylenic unsaturation, more typically, an .alpha.-,
.beta.-unsaturated carbonyl moiety, and at least one group
according to structure (B.XXI) per molecule and is copolymerizable
with the first acidic monomer and the nonionic monomer and the
hydrophobic monomer.
[0153] In one embodiment the second acidic monomer comprises one or
more ethylenically unsaturated monocarboxylic acid monomers
according to structure (B.III):
R.sup.34-R.sup.32-R.sup.31 (B.III)
[0154] wherein:
R.sup.31 and R.sup.32 are each as described above, and R.sup.34 is
a moiety having a site of ethylenic unsaturation.
[0155] In one embodiment, the compound according to structure
(B.XXII) is an .alpha.-, .beta.-unsaturated carbonyl compound. In
one embodiment, R.sup.34 is according to structure (B.IV):
##STR00014##
wherein R.sup.19 is H or (C.sub.1-C.sub.4)alkyl.
[0156] Suitable second acidic monomers include, for example,
ethylenically unsaturated carboxylic acid monomers, such as acrylic
acid and methacrylic acid, ethylenically unsaturated dicarboxylic
acid monomers, such as maleic acid and fumaric acid, ethylenically
unsaturated alkyl monoesters of dicarboxylic acid monomers, such as
butyl methyl maleate, ethylenically unsaturated sulphonic acid
monomers, such as vinyl sulfonic acid 2-acrylamido-2-methylpropane
sulfonic acid, and styrene sulfonic acid, and ethylenically
unsaturated phosphonic acid monomers, such as vinyl phosphonic acid
and allyl phosphonic acid, salts of any thereof, and mixtures of
any thereof. Alternatively, corresponding ethylenically unsaturated
anhydride or acid chloride monomers, such as maleic anhydride, may
be used and subsequently hydrolyzed to give a pendant moiety having
two acid groups. The preferred second acidic monomeric units are
derived from one or more monomers selected from acrylic acid,
methacrylic acid, and mixtures thereof. Methacrylic acid has the
following formula B.V:
##STR00015##
[0157] C. Nonionic Monomeric Units for ASE and/or HASE
Copolymer
[0158] In one embodiment, the polymer of the present invention
further comprises one or more nonionic monomeric units.
[0159] In one embodiment, the nonionic monomeric units each
independently comprise, per monomeric unit, at least one group
according to structure (C.I):
--R.sup.42-R.sup.41 (C.I)
wherein R.sup.41 is alkyl, hydroxyalkyl, alkoxyalkyl, cycloalkyl,
aryl, arylalkyl, or aryloxy, and R.sup.42 is absent or is a
bivalent linking group.
[0160] In one embodiment, R.sup.41 is (C.sub.1-C.sub.22)alkyl,
(C.sub.1-C.sub.22)hydroxyalkyl, (C.sub.2-C.sub.22)alkoxyalkyl,
(C.sub.6-C.sub.24)cycloalkyl, (C.sub.6-C.sub.40)aryl, or
(C.sub.7-C.sub.40)arylalkyl, more typically
(C.sub.2-C.sub.12)alkyl.
[0161] In one embodiment, R.sup.41 is (C.sub.1-C.sub.22)alkyl, more
typically, (C.sub.1-C.sub.12)alkyl.
[0162] In one embodiment, R.sup.42 is O, --(CH.sub.2).sub.n--O--,
wherein n is an integer of from 1 to 6, or is according to
structure (C.II):
##STR00016##
wherein: n is an integer of from 1 to 6,
A is O or NR.sup.17, and
[0163] R.sup.17 is H or (C.sub.1-C.sub.4)alkyl.
[0164] The nonionic monomeric units may be made by known synthetic
techniques, such as, for example, by grafting of one or more groups
according to structure (C.XXIII) onto a polymer backbone, such as a
hydrocarbon polymer backbone, a polyester polymer backbone, or a
polysaccharide polymer backbone, or a backbone made by
polymerization, with, for example, the above described first
acidic, second acidic, and hydrophobic monomers, of at least one
other monomer selected from monomers that comprise a reactive
functional group and at least one group according to structure
(C.XXIII) per molecule and copolymerizable with the first, second,
and third monomers. Alternatively, the nonionic monomeric units may
simply be non-grafted portions of a polymer backbone.
[0165] In one embodiment, the nonionic monomeric units are derived
from a nonionic monomer, for example, ethyl acrylate, that
comprises a reactive functional group and a group according to
structure (C.XXIII), and is copolymerizable with the first acidic
monomers, second acidic monomers and hydrophobic monomers.
[0166] In one embodiment, the reactive functional group of the
nonionic monomer is an ethylenically unsaturated group and the
nonionic monomer is an ethylenically unsaturated monomer comprising
at least one site of ethylenic unsaturation, more typically, an
.alpha.-, .beta.-unsaturated carbonyl moiety and at least one group
according to structure (C.XXIII) per molecule.
[0167] In one embodiment, the nonionic monomer comprises one or
more compounds according to structure (C.III):
R.sup.43-R.sup.42-R.sup.41 (C.III)
[0168] wherein:
R.sup.41 and R.sup.42 are each as described above, and R.sup.43 is
a moiety having a site of ethylenic unsaturation.
[0169] In one embodiment, the compound according to structure
(C.III) is an .alpha.-, .beta.-unsaturated carbonyl compound. In
one embodiment, R.sup.43 is according to structure (C.IV):
##STR00017##
wherein R.sup.19 is H or (C.sub.1-C.sub.4)alkyl.
[0170] Suitable nonionic monomers include unsaturated monomers
containing at least one group according to structure C.XXIII per
molecule, including (meth)acrylic esters such as: methyl
(meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate,
isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate
isobornyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl
(meth)acrylate, hydroxypropyl (meth)acrylate, methoxyethyl
(meth)acrylate, ethoxyethyl (meth)acrylate, phenoxyethyl
(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl
(meth)acrylate, dimethylaminoethyl (meth)acrylate,
diethylaminoethyl (meth)acrylate, tert-butylaminoethyl
(meth)acrylate, and acetoxyethyl (meth)acrylate, (meth)acrylamides
such as, (meth)acrylamide, N-methylol (meth)acrylamide,
N-butoxyethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide,
N-isopropyl (meth)acrylamide, N-tert-butyl (meth)acrylamide,
N-tert-octyl (meth)acrylamide, and diacetone (meth)acrylamide,
vinyl esters such as vinyl acetate, vinyl propionate, vinyl
2-ethylhexanoate, N-vinylamides such as: N-vinylpyrrolidione,
N-vinylcaprolactam, N-vinylformamide, and N-vinylacetamide, and
vinyl ethers such as, methyl vinyl ether, ethyl vinyl ether, butyl
vinyl ether, and hydroxybutyl vinyl ether, and ethylenically
unsaturated aryl compounds, such as styrene.
[0171] In one embodiment, the HASE copolymer of the present
invention is crosslinked. A crosslinked polymer can be made by, for
example, reacting a mixture of hydrophobic, first acidic, and
second acidic monomers with a nonionic monomer having more than one
reactive functional group, such as for example, more than one site
of ethylenic unsaturation per molecule. In one embodiment, the
nonionic monomer comprises least one monomeric compound having more
than one (meth)acrylic group per molecule, such as, for example,
allyl methacrylate, ethylene glycol dimethacrylate, butylene glycol
dimethacrylate, diallyl pentaerythritol, methylenebisacrylamide,
pentaerythritol di-, tri- and tetra-acrylates, divinyl benzene,
polyethylene glycol diacrylates, bisphenol A diacrylates,
butanediol dimethacrylate, 2,2-dimethylpropanediol dimethacrylate,
ethylene glycol dimethacrylate, phenylene diacrylate, or a mixture
thereof.
[0172] Ethylene glycol dimethylacrylate has the following formula
C.IV.
##STR00018##
[0173] In one embodiment, the polymer of the present invention
comprises nonionic units derived from one or more
(C.sub.1-C.sub.22)alkyl (meth)acrylic esters, more typically
(C.sub.1-C.sub.12)alkyl (meth)acrylic esters, such as ethyl
acrylate, butyl methacrylate, or ethylhexyl acrylate.
[0174] D. Hydrophobic Monomers for HASE Copolymer
[0175] In contrast to the ASE copolymers, the HASE copolymers
further comprise hydrophobic monomeric units derived from a
hydrophobic monomer. These hydrophobic monomers are ethylenically
unsaturated hydrophobic monomers.
[0176] Preferably, the hydrophobic monomeric units each
independently comprise, per monomeric unit, at least one branched
(C.sub.5-C.sub.50)alkyl or bicycloheptyl-polyether or
bicycloheptenyl-polyether group according to structure (D.I):
--R.sup.14-R.sup.13-R.sup.12-R.sup.11 (D.I).
[0177] In one embodiment, R.sup.11 is bicyclo[d.e.f]heptyl or
bicyclo[d.e.f]heptenyl, wherein d is 2, 3, or 4, e is 1 or 2, f is
0 or 1, and the sum of d+e+f=5, and wherein the
bicyclo[d.e.f]heptyl or bicyclo[d.e.f]heptenyl may, optionally, be
substituted on one or more of the ring carbon atoms by one or more
(C.sub.1-C.sub.6)alkyl groups,
R.sup.12 is absent or is a bivalent linking group, R.sup.13 is
bivalent polyether group, and R.sup.14 is absent or is a bivalent
linking group.
[0178] Suitable bicycloheptyl- and bicycloheptenyl-moieties may be
derived from, for example, terpenic compounds having core
(non-substituted) 7 carbon atom bicyclic ring systems according to
structures (D.II)-(D.VI):
##STR00019##
[0179] More typically, R.sup.11 is:
[0180] a bicyclo[2.2.1]heptyl or bicyclo[2.2.1]heptenyl group
bonded to R.sup.2, if present, or to R.sup.3, if R.sup.2 is not
present, via its carbon atom at the 2-position or 3-position and is
typically substituted on its carbon atom at the 7 position by one
or two (C.sub.1-C.sub.6)alkyl radicals, more typically by two
methyl radicals, or
[0181] a bicyclo[3.1.1]heptyl or bicyclo[3.1.1]heptenyl group
bonded to R.sup.2, if present, or to R.sup.3, if R.sup.2 is not
present, via its carbon atom at the 2-position or 3-position and is
typically substituted on its carbon atom at the 6-position or
7-position by one or two (C.sub.1-C.sub.6)alkyl radicals, more
typically by two methyl radicals.
[0182] In another embodiment, R.sup.11 is branched
(C.sub.5-C.sub.50)alkyl group, more typically a branched alkyl
group according to structure (D.VIII):
##STR00020##
[0183] wherein:
R.sup.15 and R.sup.16 are each independently
(C.sub.1-C.sub.48)alkyl, and a is an integer of from 0 to 40,
provided that R.sup.11, that is, R.sup.15, R.sup.16 and the
--(CH.sub.2).sub.a-- radical taken together, comprises a total of
from about 5 to about 50, more typically about 12 to about 50,
carbon atoms; R.sup.12 is absent or is a bivalent linking group,
R.sup.13 is bivalent polyether group, and R.sup.14 is absent or is
a bivalent linking group.
[0184] More typically, R.sup.12 is O, a bivalent hydrocarbon group,
even more typically a methylene group or chain of from 2 to 6
methylene units, or a bivalent alkyleneoxyl group, such as
ethyleneoxy. In one embodiment, R.sup.12 is according to structure
(D.VIII):
--(CH.sub.2).sub.b-A- (D.IX)
wherein A is O or absent, and b is an integer of from 1 to 6.
[0185] More typically, R.sup.13 is a bivalent polyether group
comprising a linear chain of from 2 to 100 units, each of which may
independently be (C.sub.2-C.sub.4)oxyalkylene, more typically,
(C.sub.2-C.sub.3)oxyalkylene. In one embodiment, R.sup.13 is a
bivalent polyether group comprising a chain of from 2 to 100
polymerized oxyethylene units and oxypropylene units, which may be
arranged alternately, randomly, or in blocks. In one embodiment,
R.sup.13 is a bivalent polyether group comprising a block of
polyoxyethylene units and a block of oxypropylene units, more
typically, a block of polyoxyethylene units and a block of
oxypropylene units, wherein the block of oxypropylene units is
disposed between and links the block of oxyethylene units and the
R.sup.12 substituent, if present, or the R.sup.11 substituent, if
R.sup.12 is not present.
[0186] In one embodiment, R.sup.13 is according to structure
(D.X):
##STR00021##
wherein: g and h are independently integers of from 2 to 5, more
typically 2 or 3, each i is independently an integer of from 1 to
about 80, more typically from 1 to about 50, each j is
independently an integer of from 0 to about 80, more typically from
1 to about 50, k is an integer of from 1 to about 50, provided that
the product obtained by multiplying the integer k times the sum of
i+j is from 2 to about 100.
[0187] If i.noteq.0, j.noteq.0, and g.noteq. h, the respective
--(C.sub.pH.sub.2pO)-- and (--(C.sub.qH.sub.2qO)-- oxyalkylene
units may be arranged randomly, in blocks, or in alternating
order.
[0188] In one embodiment,
[0189] g=2,
[0190] h=3,
[0191] i is an integer of from 1 to 50, more typically 10 to 40,
and even more typically from 15 to about 30,
[0192] j is an integer of from 1 to 30, more typically from 2 to
20, and even more typically from about 2 to about 10, and
[0193] k=1.
[0194] In one embodiment, R.sup.14 is O, --(CH.sub.2).sub.n--O--,
or is according to structure (D.XI):
##STR00022##
wherein: n is an integer of from 1 to 6,
A is O or NR.sup.17, and
[0195] R.sup.17 is H or (C.sub.1-C.sub.4)alkyl.
[0196] In another embodiment of structure (D.I) R.sup.11 is a
tri-styryl group according to the following structure D.XII.
##STR00023##
[0197] wherein R1, R2 and R3 are independently selected from the
following structures D.XIIa, D.XIIb, D.XIIc, D.XIId.
##STR00024##
[0198] The hydrophobic monomeric units may be made by known
synthetic techniques, such as, for example, by grafting of one or
more groups according to structure (D.I) onto a polymer backbone,
such as a hydrocarbon polymer backbone, a polyester polymer
backbone, or a polysaccharide polymer backbone, or by
copolymerization, with, for example, the first acidic monomer,
second acidic monomer and nonionic monomer monomer described above,
of at least one other monomer selected from monomers that comprise
a reactive functional group and at least one group according to
structure (D.I) per molecule.
[0199] In one embodiment, the hydrophobic monomeric units are
derived from at least one hydrophobic monomer selected from
monomers that comprise a reactive functional group and at least one
group according to structure (D.I) per molecule.
[0200] In one embodiment, the reactive functional group of the
first monomer is an ethylenically unsaturated group. Thus, the
hydrophobic monomer is selected from ethylenically unsaturated
monomers that comprise at least one site of ethylenic unsaturation,
more typically, an .alpha.-, .beta.-unsaturated carbonyl moiety,
and least one group according to structure (I) per molecule.
[0201] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XIV):
R.sup.18-R.sup.14-R.sup.13-R.sup.12-R.sup.11 (D.XIV)
wherein:
[0202] R.sup.11, R.sup.12, R.sup.13, and R.sup.14 are each as
described above, and
[0203] R.sup.18 is a moiety having a site of ethylenic
unsaturation.
[0204] In one embodiment, the compound according to structure
(D.XI) is an .alpha.-, .beta.-unsaturated carbonyl compound.
[0205] In one embodiment, R.sup.18 is according to structure
(D.XV):
##STR00025##
wherein R.sup.19 is H or (C.sub.1-C.sub.4)alkyl.
[0206] In one embodiment, the hydrophobic monomer is selected from
monomers according to structure (D.XVI):
##STR00026##
wherein:
[0207] R.sup.11 is bicyclo[d.e.f]heptyl or bicyclo[d.e.f]heptenyl
wherein d is 2, 3, or 4, e is 1 or 2, f is 0 or 1, and the sum of
d+e+f=5, and which may, optionally, be substituted on one or more
of the ring carbon atoms by one or more (C.sub.1-C.sub.6)alkyl
groups, or R.sup.11 is a tri-styryl group according to the
above-discussed structure D.XII.
and R.sup.19, b, g, h, i, j, and k are each as defined above,
namely: R.sup.19 is H or (C.sub.1-C.sub.4)alkyl, b is an integer of
from 1 to 6, g and h are independently integers of from 2 to 5,
more typically 2 or 3, each i is independently an integer of from 1
to about 80, more typically from 1 to about 50, each j is
independently an integer of from 0 to about 80, more typically from
1 to about 50, k is an integer of from 1 to about 50, provided that
the product obtained by multiplying the integer k times the sum of
i+j is from 2 to about 100.
[0208] Preferably R.sup.11 is the bicyclo[d.e.f]heptyl or
bicyclo[d.e.f]heptenyl group.
[0209] In another embodiment of monomers according to structure
(D.XVI) R.sup.11 is a tri-styryl group according to the following
structure D.XII and R.sup.19, b, g, h, j, and k are each as defined
above. An example of a suitable monomer has structure D.XVia:
##STR00027##
[0210] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XVII):
##STR00028##
wherein i, j, and R.sup.19 are each as described above, and, more
typically, i is an integer of from 10 to 40, and even more
typically from 15 to about 30, or from about 20 to about 30, and j
is an integer of from 1 to 20, and even more typically from about 2
to about 10. A preferred version of this structure has the
structure D.XVIIa:
##STR00029##
[0211] In another embodiment, the hydrophobic monomer comprises one
or more compounds according to structure (D.XVIII):
##STR00030##
wherein a, i, j, and R.sup.15, R.sup.16, and R.sup.19 are each as
described above.
[0212] Suitable hydrophobic monomer may be made by known synthetic
methods. For example, a bicycloheptenyl intermediate compound
(D.XIX), known as "Nopol":
##STR00031##
is made by reacting .beta.-pinene with formaldehyde, and
[0213] a bicycloheptyl intermediate compound (D.XX), known as
"Arbanol":
##STR00032##
is made by isomerization of .alpha.-pinene to camphene and
ethoxyhydroxylation of the camphene.
[0214] The bicycloheptyl- or bicycloheptenyl-intermediate may then
be alkoxylated by reacting the bicycloheptyl- or bicycloheptenyl
intermediate with one or more alkylene oxide compounds, such as
ethylene oxide or propylene oxide, to form a bicycloheptyl-, or
bicycloheptenyl-polyether intermediate. The alkoxylation may be
conducted according to well known methods, typically at a
temperature in the range of about 100.degree. to about 250.degree.
C. and at a pressure in the range of from about 1 to about 4 bars,
in the presence of a catalyst, such as a strong base, an aliphatic
amine, or a Lewis acid, and an inert gas, such as nitrogen or
argon.
[0215] The bicycloheptyl-, or bicycloheptenyl-polyether monomer may
then be formed from the bicycloheptyl- or bicycloheptenyl-polyether
intermediate by addition of a moiety containing an ethylenically
unsaturated group to the bicycloheptyl- or
bicycloheptenyl-polyether intermediate, by, for example,
esterification, under suitable reaction conditions, of the
bicycloheptyl- or bicycloheptenyl-polyether intermediate with, for
example, methacrylic anhydride.
[0216] Alternatively, a monomer comprising a ethylenically
unsaturated group, such as for example, a polyethylene glycol
monomethacrylate, which may optionally be further alkoxylated, may
be reacted with the bicycloheptyl- or bicycloheptenyl-intermediate
to form the bicycloheptyl-, or bicycloheptenyl-polyether
monomer.
[0217] In another embodiment, the hydrophobic monomeric units each
independently comprise, per monomeric unit, at least one group
according to structure (D.XXI):
--R.sup.23-R.sup.22-R.sup.21 (D.XXI)
wherein: R.sup.21 is linear or branched (C.sub.5-C.sub.50)alkyl,
hydroxyalkyl, alkoxyalkyl, aryl, or aryalkyl, R.sup.22 is a
bivalent polyether group, R.sup.23 is absent or is a bivalent
linking group.
[0218] In one embodiment, R.sup.21 is linear or branched
(C.sub.5-C.sub.40)alkyl, more typically linear or branched
(C.sub.10-C.sub.40)alkyl, even more typically, linear or branched
(C.sub.16-C.sub.40)alkyl, and still more typically linear or
branched (C.sub.16-C.sub.30)alkyl. In one embodiment, R.sup.21 is
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
nonadecyl, eicosyl, heneicosyl, behenyl, tricosyl, tetracosyl,
pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl,
triacontyl, dotriacontyl, tritriacontyl, tetratriacontyl,
pentatriacontyl, hexatriacontyl, heptatriacontyl, octatriacontyl,
nonatriacontyl, or tetracontyl, more typically, hexadecyl,
heptadecyl, octadecyl, nonadecyl, eicosyl, or behenyl.
[0219] In embodiment R.sup.21 is hydroxyalkyl, such as, for
example, hydroxyhexadecyl, hydroxyoctadecyl, or hydroxyeicosyl, or
alkoxyalkyl, such as for example, methoxyhexadecyl,
methoxyoctadecyl, or methoxyeicosyl.
[0220] In embodiment R.sup.21 is aryl, such as, for example,
phenyl, methylphenyl, methoxyphenyl, dibutylphenyl,
triisobutylphenyl, or tristyrylphenyl, or arylalkyl, such as
phenylmethyl, phenylethyl, or triphenylmethyl.
[0221] In one embodiment, the hydrophobic monomeric units each
independently comprise at least one group according to structure
(D.XVIII) above wherein R.sup.21 is a linear
(C.sub.5-C.sub.50)alkyl group.
[0222] In one embodiment, the hydrophobic monomeric units each
independently comprise at least one group according to structure
(D.XXI) above wherein R.sup.21 is a branched
(C.sub.5-C.sub.50)alkyl group, more typically a branched
(C.sub.5-C.sub.50)alkyl group according to structure (D.IX).
[0223] In one embodiment, the hydrophobic monomeric units comprise
a mixture of hydrophobic monomeric units that each independently
comprise at least one group according to structure (D.XXI) above
wherein R.sup.21 is a linear (C.sub.5-C.sub.50)alkyl group and
other hydrophobic monomeric units that each independently comprise
at least one group according to structure (D.XXI) above wherein
R.sup.21 is a branched (C.sub.5-C.sub.50)alkyl group, more
typically a branched (C.sub.5-C.sub.50)alkyl group according to
structure (D.VIII) above.
[0224] In one embodiment, R.sup.22 is a bivalent polyether group
comprising a linear chain of from 2 to 100 units, each of which may
independently be (C.sub.2-C.sub.4)oxyalkylene, more typically,
(C.sub.2-C.sub.3)oxyalkylene. In one embodiment, R.sup.22 is a
bivalent polyether group comprising a chain of from 2 to 100
polymerized oxyethylene units.
[0225] In one embodiment, R.sup.22 is according to structure
(D.XXII):
##STR00033##
wherein: p and q are independently integers of from 2 to 5, more
typically 2 or 3, each r is independently an integer of from 1 to
about 80, more typically from 1 to about 50, each s is
independently an integer of from 0 to about 80, more typically from
0 to about 50, t is an integer of from 1 to about 50, provided that
the product obtained by multiplying the integer t times the sum of
r+s is from 2 to about 100.
[0226] If r.noteq.0, s.noteq.0, and p.noteq. q, the respective
--(C.sub.pH.sub.2pO)-- and --(C.sub.qH.sub.2qO)-oxyalkylene units
may be arranged randomly, in blocks, or in alternating order.
[0227] In one embodiment,
[0228] p=2,
[0229] q=3,
[0230] r is an integer of from 1 to 50, more typically 5 to 45, and
even more typically from 10 to about 40,
[0231] s is an integer of from 1 to 30, more typically from 2 to
20, and even more typically from about 2 to about 10, and
[0232] t=1
[0233] In another embodiment,
[0234] p=2,
[0235] r is an integer of from 1 to 50, more typically 5 to 45, and
even more typically from 10 to about 40,
[0236] s is 0, and
[0237] t=1.
[0238] In one embodiment, R.sup.23 is O, --(CH.sub.2).sub.n--O--
wherein n is an integer of from 1 to 6, or is according to
structure (D.X) above, wherein A is O or NR.sup.17, and R.sup.17 is
H or (C.sub.1-C.sub.4)alkyl.
[0239] The hydrophobic monomeric units may be made by known
synthetic techniques, for example, by grafting of one or more
groups according to structure D.XVII onto a polymer backbone, such
as a hydrocarbon polymer backbone, a polyester polymer backbone, or
a polysaccharide polymer backbone, or by copolymerization, with,
for example, the above-described first acidic monomer, second
acidic monomer and the nonionic monomer described above.
[0240] In one embodiment, the hydrophobic monomeric units are
derived from copolymerizing at least one monomer that comprises a
reactive functional group and at least one group according to
structure (D.XXI) per molecule.
[0241] In one embodiment, the reactive group of the hydrophobic
monomer is an ethylenically unsaturated group and the second
monomer is an ethylenically unsaturated monomer comprises at least
one site of ethylenic unsaturation, more typically, an .alpha.-,
.beta.-unsaturated carbonyl moiety, and at least one group
according to structure (D.XXI) per molecule and copolymerizable
with the first monomer.
[0242] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XXIII):
R.sup.24-R.sup.23-R.sup.22-R.sup.21 (D.XXIII)
wherein:
[0243] R.sup.21, R.sup.22, and R.sup.23 are each as described
above, and
[0244] R.sup.24 is a moiety having a site of ethylenic
unsaturation. Thus the resulting hydrophobic monomeric unit has the
structure (D.XXIV):
##STR00034##
[0245] In one embodiment, the compound according to structure
(D.XIX) is an .alpha.-, .beta.-unsaturated carbonyl compound. In
one embodiment, R.sup.23 is according to structure (D.X).
[0246] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XXV):
##STR00035##
[0247] wherein
[0248] R.sup.21 is linear or branched (C.sub.5-C.sub.50)alkyl,
hydroxyalkyl, alkoxyalkyl, aryl, or arylalkyl, [0249] R.sup.25 is
methyl or ethyl, and p and q are independently integers of from 2
to 5, more typically 2 or 3, each r is independently an integer of
from 1 to about 80, more typically from 1 to about 50, each s is
independently an integer of from 0 to about 80, more typically from
0 to about 50, t is an integer of from 1 to about 50, provided that
the product obtained by multiplying the integer t times the sum of
r+s is from 2 to about 100; or p, q, r, s, and t are each as
otherwise described above.
[0250] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XXV) wherein R.sup.21 is
linear (C.sub.16-C.sub.22)alkyl.
[0251] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XXV) wherein R.sup.21 is a
branched (C.sub.5-C.sub.50)alkyl group, more typically a branched
(C.sub.5-C.sub.50)alkyl group according to structure (D.VII) above.
For example R.sup.21 may have the structure D.XXVI
##STR00036##
wherein m and n each, independently, are positive integers from 1
to 39 and m+n represents an integer from 4 to 40, as disclosed by
US Patent Application Publication 2006/02700563 A1 to Yang et al,
incorporated herein by reference.
[0252] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XX) wherein p=2, s=0, and
t=1.
[0253] In one embodiment, the hydrophobic monomer comprises one or
more compounds according to structure (D.XX) wherein R.sup.21 is
linear (C.sub.16-C.sub.22)alkyl, R.sup.25 is methyl or ethyl, p=2,
s=0, and t=1.
[0254] Suitable ethylenically unsaturated hydrophobic monomers
include:
[0255] alkyl-polyether (meth)acrylates that comprise at least one
linear or branched (C.sub.5-C.sub.40)alkyl-polyether group per
molecule, such as hexyl polyalkoxylated (meth)acrylates, tridecyl
polyalkoxylated (meth)acrylates, myristyl polyalkoxylated
(meth)acrylates, cetyl polyalkoxylated (meth)acrylates, stearyl
polyalkoxylated (methyl)acrylates, eicosyl polyalkoxylated
(meth)acrylates, behenyl polyalkoxylated (meth)acrylates, melissyl
polyalkoxylated (meth)acrylates, tristyrylphenoxyl polyalkoxylated
(meth)acrylates, and mixtures thereof,
[0256] alkyl-polyether (meth)acrylamides that comprise at least one
(C.sub.5-C.sub.40)alkyl-polyether substituent group per molecule,
such as hexyl polyalkoxylated (meth)acrylamides, tridecyl
polyalkoxylated (meth)acrylamides, myristyl polyalkoxylated
(meth)acrylamides, cetyl polyalkoxylated (meth)acrylamides, stearyl
polyalkoxylated (methyl)acrylamides, eicosyl polyalkoxylated
(meth)acrylamides, behenyl polyalkoxylated (meth)acrylamides,
melissyl polyalkoxylated (meth)acrylamides and mixtures
thereof,
[0257] alkyl-polyether vinyl esters, alkyl-polyether vinyl ethers,
or alkyl-polyether vinyl amides that comprise at least one
(C.sub.5-C.sub.40)alkyl-polyether substituent group per molecule
such as vinyl stearate polyalkoxylate, myristyl polyalkoxylated
vinyl ether, and mixtures thereof,
[0258] as well as mixtures of any of the above alkyl-polyether
acrylates, alkyl-polyether methacrylates, alkyl-polyether
acrylamides, alkyl-polyether methacrylamides, alkyl-polyether vinyl
esters, alkyl-polyether vinyl ethers, and/or alkyl-polyether vinyl
amides.
[0259] In one embodiment, the hydrophobic monomer comprises one or
more alkyl-polyalkoxylated (meth)acrylates that comprise one linear
or branched (C.sub.5-C.sub.40)alkyl-polyethoxylated group, more
typically (C.sub.10-C.sub.22)alkyl-polyethoxylated group per
molecule, such as decyl-polyethoxylated (meth)acrylates,
tridecyl-polyethoxylated (meth)acrylates, myristyl-polyethoxylated
(meth)acrylates, cetyl-polyethoxylated (meth)acrylates,
stearyl-polyethoxylated (methyl)acrylates, eicosyl-polyethoxylated
(meth)acrylates, behenyl-polyethoxylated (meth)acrylates, even more
typically decyl-polyethoxylated methacrylates,
tridecyl-polyethoxylated methacrylates, myristyl-polyethoxylated
methacrylates, cetyl-polyethoxylated methacrylates,
stearyl-polyethoxylated methylacrylates, eicosyl-polyethoxylated
methacrylates, behenyl-polyethoxylated methacrylates, and mixtures
thereof.
[0260] In one embodiment wherein the nonionic ethylenically
unsaturated hydrophobic monomer comprises a compound according to
structure a structure selected from the group consisting of
structure D.XXVIIa and structure D.XXVIIb:
##STR00037##
[0261] wherein R.sub.3 is H or CH.sub.3, R.sub.4 is independently
an alkyl chain containing 1 to about 4 carbon atoms; R.sub.5 is an
alkyl chain containing 1 to about 6 carbon atoms (preferably
methyl); R.sub.6 is an alkyl chain containing 1 to about 4 carbon
atoms; M is an integer from 0 to about 50 (preferably about 1 to
50, more preferably about 5 to 30); N is an integer from 0 to 20
(preferably 1 to 20, more preferably 5 to 15); P is an integer from
0 to about 50 (preferably 0 to 30); wherein P+M is greater than or
equal to 1; wherein Q is an integer from 1 to 4 (typically 1 to
2).
[0262] Some typical hydrophobic monomers have any of the structures
D.XXVIII, D.XXIX, D.XXX, or D.XXXI,
##STR00038##
[0263] III. Making the ASE and/or HASE Copolymer
[0264] The pH responsive ASE copolymer is the product of
copolymerization of a mixture of monomers, comprising:
[0265] A. about 0.1-70 weight percent, typically 0.5-50, 0.7-40,
1-40, 5-40, 5-30 or 10 to 40 weight percent of at least one alpha
beta-ethylenically unsaturated first acid monomer selected from the
group consisting of mono-[2-(methacryloyloxy)ethyl]phthalate (also
known as 2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) and
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP),
[0266] B. about 0-45 weight percent, preferably 5 to 30 weight
percent, of at least one C3-C8 alpha beta-ethylenically unsaturated
acidic monomer, preferably a C3-C8 alpha beta-ethylenically
unsaturated carboxylic acid monomer;
[0267] C. about 15-70 weight percent, typically 20 to 50 weight
percent, of at least one non-ionic, copolymerizable C2-C12 alpha,
beta-ethylenically unsaturated monomer.
[0268] The pH responsive HASE copolymer is the product of
copolymerization of a mixture of monomers, comprising:
[0269] A. about 0.1-70 weight percent, typically 0.5-50, 0.7-40,
1-40, 5-40, 5-30 or 10 to 40 weight percent of at least one alpha
beta-ethylenically unsaturated first acid monomer selected from the
group consisting of mono-[2-(methacryloyloxy)ethyl]phthalate (also
known as 2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) and
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP),
[0270] B. about 0-45 weight percent, preferably 5 to 30 weight
percent, of at least one C3-C8 alpha beta-ethylenically unsaturated
acidic monomer, preferably a C3-C8 alpha beta-ethylenically
unsaturated carboxylic acid monomer;
[0271] C. about 15-70 weight percent, typically 20 to 50 weight
percent, of at least one non-ionic, copolymerizable C2-C12 alpha,
beta-ethylenically unsaturated monomer; and
[0272] D. about 0 to 30 weight percent, preferably 0.05 to 30
weight percent or typically 5 to 20 weight percent, of at least one
non-ionic ethylenically unsaturated hydrophobic monomer.
[0273] In one embodiment, the pH responsive copolymer of the
present invention is the product of polymerization of a mixture of
monomers comprising, based on the 100 pbw of the total amount of
the monomers: [0274] (a) from about 0.1, more typically from about
1 or 5 pbw of the first acidic monomers, to about 70, more
typically to about 40 pbw, of the one or more first acidic
monomers, [0275] (b) from about 0, more typically from about 1, and
even more typically from about 5, pbw of the second acidic
monomers, to about 45, more typically to about 35, and even more
typically to about 30, pbw of the one or more second acidic
monomers, and [0276] (c) from about 15, more typically from about
20 pbw of the one or more nonionic acidic monomers, to about 70,
more typically to about 50 pbw, of the one or more nonionic
monomers, and [0277] (d) from about 0, more typically from about
0.05, even more typically from about 1, and still more typically
from about 5, pbw of the one or more hydrophobic monomers, to about
30, more typically to about 25, and even more typically to about
20, pbw of the one or more hydrophobic monomers.
[0278] The pH responsive copolymer of the present invention can be
conveniently prepared from the above-described monomers by known
aqueous emulsion polymerization techniques using free-radical
producing initiators, typically in an amount from 0.01 percent to 3
percent, based on the weight of the monomers.
[0279] In one embodiment, the polymerization is conducted at a pH
of about 5.0 or less. Polymerization at an acid pH of about 5.0 or
less permits direct preparation of an aqueous colloidal dispersion
having relatively high solids content without the problem of
excessive viscosity.
[0280] In one embodiment, the polymerization is conducted in the
presence of one or more free-radical producing initiators selected
from peroxygen compounds. Useful peroxygen compounds include
inorganic persulfate compounds such as ammonium persulfate,
potassium persulfate, sodium persulfate, peroxides such as hydrogen
peroxide, organic hydroperoxides, for example, cumene
hydroperoxide, and t-butyl hydroperoxide, organic peroxides, for
example, benzoyl peroxide, acetyl peroxide, lauroyl peroxide,
peracetic acid, and perbenzoic acid (sometimes activated by a
water-soluble reducing agent such as ferrous compound or sodium
bisulfite), and other free-radical producing materials or
techniques such as 2,2'-azobisisobutyronitrile and high energy
radiation sources.
[0281] In one embodiment, the polymerization is conducted in the
presence of one or more emulsifiers. Useful emulsifiers include
anionic surfactants, nonionic surfactants, amphoteric surfactants,
and zwitterionic surfactants. In one embodiment, the emulsion
polymerization is conducted in the presence of one or more anionic
surfactants. Examples of anionic emulsifiers are the alkali metal
alkyl aryl sulfonates, the alkali metal alkyl sulfates and the
sulfonated alkyl esters. Specific examples of these well-known
emulsifiers are sodium dodecyl benzene sulfonate, sodium dodecyl
butylnaphthalene sulfonate, sodium lauryl sulfate, disodium dodecyl
diphenyl ether disulfonate, disodium n-octadecyl sulfosuccinamate
and sodium dioctyl sulfosuccinate. Known nonionic emulsifiers
include, for example, fatty alcohols, alkoxylated fatty alcohols,
and alkylpolyglucosides.
[0282] The emulsion polymerization may, optionally, be conducted in
the presence, in an amount up to about 10 parts per 100 parts of
polymerizable monomers, of one or more chain transfer agents.
Representative chain transfer agents are carbon tetrachloride,
bromoform, bromotrichloromethane, and long-chain alkyl mercaptans
and thioesters, such as n-dodecyl mercaptan, t-dodecyl mercaptan,
octyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, butyl
thioglycolate, isooctyl thioglycolate, and dodecyl
thioglycolate.
[0283] Optionally, other ingredients well known in the emulsion
polymerization art may be included, such as chelating agents,
buffering agents, inorganic salts and pH adjusting agents.
[0284] In one embodiment, the polymerization is carried out at a
temperature between about 60.degree. C. and 90.degree. C., but
higher or lower temperatures may be used. The polymerization can be
conducted batchwise, stepwise, or continuously with batch and/or
continuous addition of the monomers, in a conventional manner.
[0285] The monomers can be copolymerized in such proportions, and
the resulting emulsion polymers can be physically blended, to give
products with the desired balance of properties for specific
applications. For example, for analogous polymers of a given
molecular weight, increasing the amount of first monomer tends to
increase the yield strength exhibited by the polymer, increasing
the relative amount of second monomer tends to increase the
viscosity of the polymer. One or more fourth monomers may be added
to adjust the properties of the polymer.
[0286] These polymeric products prepared by emulsion polymerization
at an acid pH are in the form of stable aqueous colloidal
dispersions containing the polymer dispersed as discrete particles
having average particle diameters of about 400 to about 3000 .ANG.
(40 to 300 nanometers) and preferably about 600 to about 1750 .ANG.
(60 to 175 nanometers), as measured by light scattering.
Dispersions containing polymer particles smaller than about 400
.ANG. (40 nanometers) are difficult to stabilize, while particles
larger than about 3000 .ANG. (300 nanometers) reduce the ease of
dispersion in the aqueous products to be thickened.
[0287] In one embodiment, the polymer composition is in the form of
an aqueous polymer dispersion, typically having a solids content
including the polymer and any surfactants that may be present and
based on the total weight of the polymer dispersion, of up to about
60 wt % and, more typically about 20 to about 50 wt %.
[0288] Alternatively this (co)polymerization may also be conducted
by different methods or in different solvents. The scope of methods
and solvents is well known to those skilled in the art.
[0289] Thus, these polymers for use in the present invention can be
made using known solution polymerization techniques, wherein the
reactant monomers and initiator are dissolved in an appropriate
solvent such as toluene, xylene, tetrahydrofuran, or mixtures
thereof. Polymerization can be accomplished in the time and at the
temperature necessary, e.g., 60.degree. C. to 80.degree. C. and
about 2 to 24 hours. The polymer product can be isolated through
normal separation techniques, including solvent stripping.
[0290] In one embodiment, these polymers for use in the present
invention exhibit a weight average molecular weight, as determined
by gel permeation chromatography and light scattering of a solution
of the polymer in tetrahydrofuran and compared to a polystyrene
standard, of greater than or equal to 30,000 grams per mole
("g/mole"). HASE thickeners may not fully dissolve in THF but after
hydrolysis they can dissolve in water and measurement can be run in
a water gel permeation chromatography (GPC). Reference:
Macromolecules 2000, 33, 2480. For example in a range of 30,000 to
5,000,000 g/mole. More typically the polymer of the present
invention exhibits a weight average molecular weight of from about
100,000 g/mole, and even more typically from about 150,000 g/mole,
to about 1,500,000 g/mole, more typically to about 1,000,000
g/mole, and even more typically to about 800,000 g/mole.
[0291] In one embodiment, these pH responsive copolymers for use in
the present invention are in the form of an aqueous colloidal
polymer dispersion. When the polymer composition is in the form of
an aqueous colloidal polymer dispersion, the composition is
maintained at a pH of about 5 or less to maintain stability. More
typically, the aqueous colloidal polymer dispersion composition has
a pH of about 1.5 to about 3. When thickening of the composition is
desired, the pH of the composition can be increased to a value
above about 5 by addition of a base to solubilize the polymer.
[0292] These ASE and HASE copolymers and compositions for use as
thickeners in the present invention are pH-responsive. At the lower
pH levels at which the emulsion polymerization takes place, i.e.,
pH levels of 5 or less, the composition is relatively thin or
non-viscous. When the pH of the copolymer dispersion is neutralized
or adjusted by addition of a base to a pH of about 5.5 or more,
preferably about 6 to about 11, the composition thickens
substantially. The composition turns from semi-opaque or opaque to
translucent or transparent as viscosity increases. Viscosity
increases as copolymer dissolves partially or completely in the
aqueous phase of the composition. Neutralization can occur in situ
when the emulsion copolymer is blended with the base and added to
the aqueous phase. Or, if desired for a given application,
neutralization can be carried out when blending with an aqueous
product. Useful bases include, but are not limited to, ammonium
hydroxide, an amine, sodium hydroxide, potassium carbonate or the
like.
[0293] For example, the HASE copolymer having a polymer backbone
including MAA and EA is a pH-sensitive thickener. Typically the
copolymer is a latex at pH=2.3. When neutralized with a suitable
base to a pH above about 5.5, the carboxyl groups on the
methacrylic acid ionize to carboxylate ions. The charge on the
polymer induces a conformational change, and the white latex
becomes water-soluble, thus increasing the hydrodynamic volume of
the polymer. When the HASE copolymers swell, the pendant
hydrophobic groups are free to build associations with one another
and with other hydrophobes available in the formulation, such as
surfactants, particulates, emulsion droplets and dyes. This
phenomenon creates a network structure that results in a
significant viscosity build.
[0294] IV. Uses of the pH Responsive Polymer
[0295] The polymers and polymer compositions according to the
present invention are useful as water-soluble thickeners for a wide
variety of applications ranging from home care, personal care and
oilfield drilling fluids. They are particularly useful for aqueous
paints and coatings. Solution-polymerized polymers can be used in
solvent systems or emulsified by known techniques for use in
aqueous systems. Other uses include latexes and detergents. Useful
cosmetic compositions will typically have an aqueous carrier, a
pigment and/or cosmetic active, a HASE emulsion polymer, and
optional adjuvants. Useful detergents and cleansers will typically
have aqueous carrier, a HASE emulsion polymer, and optional
adjuvants. Oilfield drilling fluids will typically have an aqueous
carrier, HASE emulsion polymer as a thickener/viscosity modifier,
and optional adjuvants. The oilfield drilling fluids are injected
into the oilfield formation. Useful latex coatings will typically
have an aqueous carrier, a HASE emulsion polymer, and optional
adjuvants.
[0296] The HASE emulsion polymers according to the present
invention as described herein are particularly useful as thickeners
for a wide variety of water-based compositions. Such compositions
include brine, slurries, and colloidal dispersions of
water-insoluble inorganic and organic materials, such as natural
rubber, synthetic or artificial latexes. The emulsion polymers of
the invention are especially useful in areas requiring thickening
at neutral pHs, such as in cosmetics.
[0297] In one embodiment, the aqueous composition comprising the pH
responsive polymer of the present invention exhibits viscoelastic
properties at neutral to alkaline pH values, typically at pH values
greater than or equal to about 5, more typically greater than or
equal to about 5.5, even more typically from about 6 to about
9.
[0298] V. Use of the pH Responsive Polymer with Binders which are
Latex Polymers
[0299] Embodiments of the invention, such as latex paint, may
contain more than one category of latex. There can be a first latex
namely, the HASE copolymer, as a thickener. There can also be a
second latex, for example RHOPLEX SG30 or REVACRYL synthetic latex
emulsion resins, as a binder for latex paint.
[0300] Synthetic latexes take the form of aqueous
dispersions/suspensions of particles of latex polymers. Synthetic
latexes include aqueous colloidal dispersions of water-insoluble
polymers prepared by emulsion polymerization of one or more
ethylenically unsaturated monomers. Typical of such synthetic
latexes are emulsion copolymers of monoethylenically unsaturated
compounds, such as styrene, methyl methacrylate, acrylonitrile with
a conjugated diolefin, such as butadiene or isoprene; copolymers of
styrene, acrylic and methacrylic esters, copolymers of vinyl
halide, vinylidene halide, vinyl acetate and the like. Many other
ethylenically unsaturated monomers or combinations thereof can be
emulsion polymerized to form synthetic latexes. Such latexes are
commonly employed in paints (latex paints) and coatings. The
composition of the present invention may be added to latexes to
modify/increase viscosity.
[0301] The polymeric thickeners of this invention are advantageous
for use with the water-based compositions according to the
foregoing description and with compositions containing those
materials, especially coating compositions of various types.
Mixtures or combinations of two or more thickeners may be used, if
desired. Of course the latex polymers used in coating compositions
are preferably film-forming at temperatures about 25 degrees C. or
less, either inherently or through the use of plasticizers. Such
coating compositions include water-based consumer and industrial
paints; sizing, adhesives and other coatings for paper, paperboard,
textiles; and the like.
[0302] Latex paints and coatings may contain various adjuvants,
such as pigments, fillers and extenders. Useful pigments include,
but are not limited to, titanium dioxide, mica, and iron oxides.
Useful fillers and extenders include, but are not limited to,
barium sulfate, calcium carbonate, clays, talc, and silica. The
compositions of the present invention described herein are
compatible with most latex paint systems and provide highly
effective and efficient thickening.
[0303] The polymer compositions of the present invention may be
added to aqueous product systems at a wide range of amounts
depending on the desired system properties and end use
applications. In latex paints, the composition is added such that
the emulsion (HASE) polymer according to the present invention is
present at about 0.05 to about 5.0 weight percent and preferably
about 0.1 to about 3.0 weight percent based on total weight of the
latex paint, including all of its components, such as water, HASE
polymer, latex polymer, pigment, and any adjuvants.
[0304] The present invention also includes a method of preparing an
aqueous coating composition by mixing together at least one latex
polymer derived from at least one monomer and blended with at least
one pH responsive copolymer as described above, and at least one
pigment. Preferably, the latex polymer is in the form of latex
polymer dispersion. The additives discussed above can be added in
any suitable order to the latex polymer, the pigment, or
combinations thereof, to provide these additives in the aqueous
coating composition. In the case of paint formulations, the aqueous
coating composition preferably has a pH of from 7 to 10.
[0305] In formulating latexes and latex paints/coatings, physical
properties that may be considered include, but are not limited to,
viscosity versus shear rate, ease of application to surface,
spreadability, and shear thinning.
[0306] VI. Emulsion Polymerization to Make Latex Binder for Latex
Paint
[0307] Emulsion polymerization is discussed in G. Pohlein,
"Emulsion Polymerization", Encyclopedia of Polymer Science and
Engineering, vol. 6, pp. 1-51 (John Wiley & Sons, Inc., NY,
N.Y., 1986), the disclosure of which is incorporated herein by
reference. Emulsion polymerization is a heterogeneous reaction
process in which unsaturated monomers or monomer solutions are
dispersed in a continuous phase with the aid of an emulsifier
system and polymerized with free-radical or redox initiators. The
product, a colloidal dispersion of the polymer or polymer solution,
is called a latex.
[0308] The monomers typically employed in emulsion polymerization
to make latex for latex paint include such monomers as methyl
acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate,
2-ethyl hexyl acrylate, other acrylates, methacrylates and their
blends, acrylic acid, methacrylic acid, styrene, vinyl toluene,
vinyl acetate, vinyl esters of higher carboxylic acids than acetic
acid, e.g. vinyl versatate, acrylonitrile, acrylamide, butadiene,
ethylene, vinyl chloride and the like, and mixtures thereof. This
is further discussed below in the section entitled "Latex
Monomers".
[0309] In the above process, suitable initiators, reducing agents,
catalysts and surfactants are well known in the art of emulsion
polymerization. Typical initiators include ammonium persulfate
(APS), hydrogen peroxide, sodium, potassium or ammonium
peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, ditertiary
butyl peroxide, 2,2'-azobisisobutyronitrile, t-butyl hydroperoxide,
benzoyl peroxide, and the like. Commonly used redox initiation
systems are described e.g., by A. S. Sarac in Progress in Polymer
Science 24(1999), 1149-1204.
[0310] Suitable reducing agents are those which increase the rate
of polymerization and include for example, sodium bisulfite, sodium
hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid,
isoascorbic acid, and mixtures thereof.
[0311] Suitable catalysts are those compounds which increase the
rate of polymerization and which, in combination with the
above-described reducing agents, promote decomposition of the
polymerization initiator under the reaction conditions. Suitable
catalysts include transition metal compounds such as, for example,
ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate,
cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures
thereof.
[0312] Emulsion polymerization occurs in the presence of an
emulsifier. Typically the mixture contains 0.5 to 6 wt % emulsifier
based on weight of latex monomers
[0313] Typical emulsifiers are ionic or non-ionic surfactants
polymerizable or non-polymerizable in the aqueous coating
composition including latex polymer. Suitable ionic and nonionic
surfactants are alkyl polyglycol ethers such as ethoxylation
products of lauryl, tridecyl, oleyl, and stearyl alcohols; alkyl
phenol polyglycol ethers such as ethoxylation products of octyl- or
nonylphenol, diisopropyl phenol, triisopropyl phenol; alkali metal
or ammonium salts of alkyl, aryl or alkylaryl sulfonates, sulfates,
phosphates, and the like, including sodium lauryl sulfate, sodium
octylphenol glycolether sulfate, sodium dodecylbenzene sulfonate,
sodium lauryldiglycol sulfate, and ammonium tritertiarybutyl phenol
and penta- and octa-glycol sulfonates, sulfosuccinate salts such as
disodium ethoxylated nonylphenol half ester of sulfosuccinic acid,
disodium n-octyldecyl sulfosuccinate, sodium dioctyl
sulfosuccinate, and the like.
[0314] The polymer latex binder can be produced by first preparing
an initiator solution comprising the initiator and water. A monomer
pre-emulsion is also prepared comprising one or more surfactants
(emulsifiers), and other latex monomers to be used to form the
latex polymer, water, and additional additives such as NaOH.
[0315] Thus, a typical process of emulsion polymerization
preferably involves charging water to a reactor and feeding as
separate streams a pre-emulsion of the monomer and a solution of
the initiator. In particular, the polymer latex binder can be
prepared using emulsion polymerization by feeding the monomers used
to form the latex binder to a reactor in the presence of at least
one initiator and at least one surfactant and polymerizing the
monomers to produce the latex binder. Typically the initiator
solution and monomer pre-emulsion are continuously added to the
reactor over a predetermined period of time (e.g. 1.5-5 hours) to
cause polymerization of latex monomers to produce the latex
polymer.
[0316] Prior to the addition of the initiator solution and the
monomer pre-emulsion, a seed latex such as a polystyrene seed latex
can be added to the reactor. For example, a small amount of the
pre-emulsion and a portion of the initiator may be charged
initially at the reaction temperature to produce "seed" latex. The
"seed" latex procedure results in better particle-size
reproducibility.
[0317] Under "normal" initiation conditions, that is initiation
conditions under which the initiator is activated by heat, the
polymerization is normally carried out at about 60-90.degree. C. A
typical "normal" initiated process, for example, could employ
ammonium persulfate as initiator at a reaction temperature of
80+/-2.degree. C. Under "redox" initiation conditions, namely
initiation conditions under which the initiator is activated by a
reducing agent, the polymerization is normally carried out at
60-70.degree. C. Normally, the reducing agent is added as a
separate solution. A typical "redox" initiated process, for
example, could employ potassium persulfate as the initiator and
sodium metabisulfite as the reducing agent at a reaction
temperature of 65+/-2.degree. C.
[0318] The reactor is operated at desired reaction temperature at
least until all the monomers are fed to produce the polymer latex
binder. Once the polymer latex binder is prepared, it is preferably
chemically stripped thereby decreasing its residual monomer
content. Preferably, it is chemically stripped by continuously
adding an oxidant such as a peroxide (e.g. t-butylhydroperoxide)
and a reducing agent (e.g. sodium acetone bisulfite), or another
redox pair such as those described by A. S. Sarac in Progress in
Polymer Science 24(1999), 1149-1204, to the latex binder at an
elevated temperature and for a predetermined period of time (e.g.
0.5 hours). The pH of the latex binder can then be adjusted and
other additives added after the chemical stripping step.
[0319] In the above emulsions, the polymer preferably exists as a
generally spherical particle, dispersed in water, with a diameter
of about 50 nanometers to about 500 nanometers.
[0320] For purposes of this description, monomers from which latex
polymers may be derived are termed "latex monomers".
[0321] The latex monomers fed to a reactor to prepare the polymer
latex binder preferably include at least one acrylic monomer
selected from the group consisting of acrylic acid, acrylic acid
esters, methacrylic acid, and methacrylic acid esters. In addition,
the monomers can include styrene, vinyl acetate, or ethylene. The
monomers can also include one or more monomers selected from the
group consisting of styrene, (alpha)-methyl styrene, vinyl
chloride, acrylonitrile, methacrylonitrile, ureido methacrylate,
vinyl acetate, vinyl esters of branched tertiary monocarboxylic
acids (e.g. vinyl esters commercially available under the mark
VEOVA from Shell Chemical Company or sold as EXXAR neo vinyl esters
by ExxonMobil Chemical Company), itaconic acid, crotonic acid,
maleic acid, fumaric acid, and ethylene. It is also possible to
include C4-C8 conjugated dienes such as 1,3-butadiene, isoprene or
chloroprene. Commonly used monomers in making acrylic paints are
butyl acrylate, methyl methacrylate, ethyl acrylate and the like.
Preferably, the monomers include one or more monomers selected from
the group consisting of n-butyl acrylate, methyl methacrylate,
styrene and 2-ethylhexyl acrylate.
[0322] The latex polymer is typically selected from the group
consisting of pure acrylics (comprising acrylic acid, methacrylic
acid, an acrylate ester, and/or a methacrylate ester as the main
monomers); styrene acrylics (comprising styrene and acrylic acid,
methacrylic acid, an acrylate ester, and/or a methacrylate ester as
the main monomers); vinyl acrylics (comprising vinyl acetate and
acrylic acid, methacrylic acid, an acrylate ester, and/or a
methacrylate ester as the main monomers); and acrylated ethylene
vinyl acetate copolymers (comprising ethylene, vinyl acetate and
acrylic acid, methacrylic acid, an acrylate ester, and/or a
methacrylate ester as the main monomers). The monomers can also
include other main monomers such as acrylamide and acrylonitrile,
and one or more functional monomers such as itaconic acid and
ureido methacrylate, as would be readily understood by those
skilled in the art. In a particularly preferred embodiment, the
latex polymer is a pure acrylic such as a butyl acrylate/methyl
methacrylate copolymer derived from monomers including butyl
acrylate and methyl methacrylate.
[0323] In typical acrylic paint compositions the polymer is
comprised of one or more esters of acrylic or methacrylic acid,
typically a mixture, e.g. about 50/50 by weight, of a high T.sub.g
monomer (e.g. methyl methacrylate) and a low T.sub.g monomer (e.g.
butyl acrylate), with small proportions, e.g. about 0.5% to about
2% by weight, of acrylic or methacrylic acid. The vinyl-acrylic
paints usually include vinyl acetate and butyl acrylate and/or
2-ethyl hexyl acrylate and/or vinyl versatate. In vinyl-acrylic
paint compositions, at least 50% of the polymer formed is comprised
of vinyl acetate, with the remainder being selected from the esters
of acrylic or methacrylic acid. The styrene/acrylic polymers are
typically similar to the acrylic polymers, with styrene substituted
for all or a portion of the methacrylate monomer thereof.
[0324] The latex polymer dispersion preferably includes from about
30 to about 75% solids and a mean latex particle size of from about
70 to about 650 nm. The latex polymer is preferably present in the
aqueous coating composition in an amount from about 5 to about 60
percent by weight, and more preferably from about 8 to about 40
percent by weight (i.e. the weight percentage of the dry latex
polymer based on the total weight of the coating composition).
[0325] The aqueous coating composition is a stable fluid that can
be applied to a wide variety of materials such as, for example,
paper, wood, concrete, metal, glass, ceramics, plastics, plaster,
and roofing substrates such as asphaltic coatings, roofing felts,
foamed polyurethane insulation; or to previously painted, primed,
undercoated, worn, or weathered substrates. The aqueous coating
composition of the invention can be applied to the materials by a
variety of techniques well known in the art such as, for example,
brush, rollers, mops, air-assisted or airless spray, electrostatic
spray, and the like.
[0326] VII. Liquid Carrier
[0327] In one embodiment, the composition of the present invention
comprises the selected polymer and a liquid carrier.
[0328] In one embodiment, the liquid carrier is an aqueous carrier
comprising water and the treatment solution is in the form of a
solution, emulsion, or dispersion of the material and additives. In
one embodiment, the liquid carrier comprises water and a water
miscible organic liquid. Suitable water miscible organic liquids
include saturated or unsaturated monohydric alcohols and polyhydric
alcohols, such as, for example, methanol, ethanol, isopropanol,
cetyl alcohol, benzyl alcohol, oleyl alcohol, 2-butoxyethanol, and
ethylene glycol, as well as alkylether diols, such as, for example,
ethylene glycol monoethyl ether, propylene glycol monoethyl ether
and diethylene glycol monomethyl ether.
[0329] As used herein, terms "aqueous medium" and "aqueous media"
are used herein to refer to any liquid medium of which water is a
major component. Thus, the term includes water per se as well as
aqueous solutions and dispersions.
[0330] VIII. Other Additives
[0331] As described above, latex paints and coatings may contain
various adjuvants.
[0332] The aqueous coating compositions of the invention include
less than 2% by weight and preferably less than 1.0% by weight of
anti-freeze agents based on the total weight of the aqueous coating
composition. For example, the aqueous coating compositions may be
substantially free of anti-freeze agents.
[0333] The aqueous coating composition typically includes at least
one pigment. The term "pigment" as used herein includes
non-film-forming solids such as pigments, extenders, and fillers.
The at least one pigment is preferably selected from the group
consisting of TiO2 (in both anastase and rutile forms), clay
(aluminum silicate), CaCO3 (in both ground and precipitated forms),
aluminum oxide, silicon dioxide, magnesium oxide, talc (magnesium
silicate), barytes (barium sulfate), zinc oxide, zinc sulfite,
sodium oxide, potassium oxide and mixtures thereof. Suitable
mixtures include blends of metal oxides such as those sold under
the marks MINEX (oxides of silicon, aluminum, sodium and potassium
commercially available from Unimin Specialty Minerals), CELITES
(aluminum oxide and silicon dioxide commercially available from
Celite Company), ATOMITES (commercially available from English
China Clay International), and ATTAGELS (commercially available
from Engelhard). More preferably, the at least one pigment includes
TiO2, CaCO3 or clay. Generally, the mean particle sizes of the
pigments range from about 0.01 to about 50 microns. For example,
the TiO2 particles used in the aqueous coating composition
typically have a mean particle size of from about 0.15 to about
0.40 microns. The pigment can be added to the aqueous coating
composition as a powder or in slurry form. The pigment is
preferably present in the aqueous coating composition in an amount
from about 5 to about 50 percent by weight, more preferably from
about 10 to about 40 percent by weight.
[0334] The coating composition can optionally contain additives
such as one or more film-forming aids or coalescing agents.
Suitable firm-forming aids or coalescing agents include
plasticizers and drying retarders such as high boiling point polar
solvents. Other conventional coating additives such as, for
example, dispersants, additional surfactants (i.e. wetting agents),
rheology modifiers, defoamers, thickeners, additional biocides,
additional mildewcides, colorants such as colored pigments and
dyes, waxes, perfumes, co-solvents, and the like, can also be used
in accordance with the invention. For example, non-ionic and/or
ionic (e.g. anionic or cationic) surfactants can be used to produce
the polymer latex. These additives are typically present in the
aqueous coating composition in an amount from 0 to about 15% by
weight, more preferably from about 1 to about 10% by weight based
on the total weight of the coating composition.
[0335] The aqueous coating composition typically includes less than
10.0% of anti-freeze agents based on the total weight of the
aqueous coating composition. Exemplary anti-freeze agents include
ethylene glycol, diethylene glycol, propylene glycol, glycerol
(1,2,3-trihydroxypropane), ethanol, methanol, 1-methoxy-2-propanol,
2-amino-2-methyl-1-propanol, and FTS-365 (a freeze-thaw stabilizer
from Inovachem Specialty Chemicals). More preferably, the aqueous
coating composition includes less than 5.0% or is substantially
free (e.g. includes less than 0.1%) of anti-freeze agents.
Accordingly, the aqueous coating composition of the invention
preferably has a VOC level of less than about 100 g/L and more
preferably less than or equal to about 50 g/L.
[0336] The balance of the aqueous coating composition of the
invention is water. Although much of the water is present in the
polymer latex dispersion and in other components of the aqueous
coating composition, water is generally also added separately to
the aqueous coating composition. Typically, the aqueous coating
composition includes from about 10% to about 85% by weight and more
preferably from about 35% to about 80% by weight water. Stated
differently, the total solids content of the aqueous coating
composition is typically from about 15% to about 90%, more
preferably, from about 20% to about 65%.
[0337] The coating compositions are typically formulated such that
the dried coatings comprise at least 10% by volume of dry polymer
solids, and additionally 5 to 90% by volume of non-polymeric solids
in the form of pigments. The dried coatings can also include
additives such as plasticizers, dispersants, surfactants, rheology
modifiers, defoamers, thickeners, additional biocides, additional
mildewcides, colorants, waxes, and the like, that do not evaporate
upon drying of the coating composition.
[0338] Biocides are substances that kill or inhibit the growth of
microorganisms such as bacteria, fungi and algae. Biocides include
chlorinated hydrocarbons, organometallics, halogen-releasing
compounds, metallic salts, quaternary ammonium compounds, phenolics
and organic sulfur compounds.
[0339] Exemplary of organic sulfur compounds are compounds based on
an isothiazolinone or isothiazolothione structure. The biocidal
activity of these compounds is effected by inactivation of
essential enzymes of microbial metabolism which require sulfhydryl
groups for activity. These enzymes include phosphoenolpyruvate
transphosphorase and a number of dehydrogenases. The thio moiety of
the isothiazolinone or isothiazolothione compounds reacts with the
free sulfhydryl groups of an enzyme to form a disulfide bond
between the enzyme molecule and the isothiazolinone or
isothiazolothione molecule rendering the sulfhydryl unavailable for
interaction with substrate or effector molecules.
[0340] Isothiazolinone and isothiazolothione biocides have found
widespread use as latex preservatives. Most latex emulsions are
water based and are prone to microbial attack. Biocides are
typically added to the finished latex after all processing is
completed to protect the latex from microbial attack. The present
compositions and methods may also include Isothiazolinone biocides.
Biocides which are widely used as latex preservatives include
PROXEL GXL, having an active ingredient of
1,2-benzisothiazolin-3-one (BIT), PROMEXAL W50, having an active
ingredient of 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and
KATHON LX, a blend of 5-chloro-2-methyl-4-isothiazolin-3-one and
2-methyl-4-isothiazolin-3-one active ingredients.
[0341] Typical isothiazolinones or isothiazolothiones are
represented by the general formula (I):
##STR00039##
[0342] or a salt or a complex thereof;
[0343] wherein X is oxygen or sulfur; R is hydrogen, a substituted
or unsubstituted hydrocarbyl group, a substituted or unsubstituted
hydrocarbylthio group, a substituted or unsubstituted
hydrocarbyloxy group or a carbamoyl group; and each of A and D is
independently hydrogen, a halogen atom, a cyano group, a
substituted or unsubstituted hydrocarbyl group or a direct bond to
the other of A or D.
[0344] When R, A and D are, or contain, substituted hydrocarbyl
groups, the substituents are preferably independently halogen,
alkoxy or alkylthio where the alkyl groups contain 1 to 4 carbon
atoms. If R is a carbamoyl group, preferably it is of the general
type --CON(H)(R.sup.1) where R.sup.1 is a hydrogen atom or a
hydrocarbyl group, which may be substituted with halogen, alkoxy or
alkylthio substituents. It is generally preferred that R is a
hydrogen atom or a lower alkyl group of 1 to 4 carbon atoms. Most
preferably, R is hydrogen or a methyl group.
[0345] Preferably, A and D, together with the carbon atoms to which
they are attached, form a five- or six-membered substituted or
unsubstituted ring. The ring substituents are preferably halogen,
alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or
alkylthio of 1 to 4 carbon atoms. The ring may contain a heteroatom
such as a nitrogen atom replacing a carbon atom. Most preferably, A
and D form a hydrocarbon ring such as benzene, cyclopentene or
cyclohexene.
[0346] Alternatively, A and D are separate groups. Preferably, at
least one of A and D is not a hydrogen atom and most preferably, at
least one of A and D is a halogen atom or an alkyl group of 1 to 4
carbon atoms.
[0347] The biocidal isothiazolinone compounds include
5-chloro-2-methyl-4-isothiazolin-3-one (where R is methyl, A is
hydrogen and D is chlorine); 2-methyl-4-isothiazolin-3-one (where R
is methyl and A and D are both hydrogen);
4,5-dichloro-2-methylisothiazolin-3-one (where R is methyl and A
and D are both chlorine); 2-n-octylisothiazolin-3-one (where R is
n-octyl and A and D are both hydrogen; 1,2-benzisothiazolin-3-one
(where R is hydrogen and A and D, together with the carbon atoms to
which they are attached, form a benzene ring);
4,5-trimethylene-4-isothiazolin-3-one (where R is hydrogen and A
and D, together with the carbon atoms to which they are attached,
form a cyclopentene ring) and
2-methyl-4,5-trimethylene-4-isothiazolin-3-one (where R is methyl
and A and D, together with the carbon atoms to which they are
attached, form a cyclopentene ring).
[0348] A typical the biocidal compound of this family which may be
used as the additional biocidal compound in the present invention
is one where R is hydrogen and A and D together form an
unsubstituted 5- or 6-membered hydrocarbon ring as in the compounds
1,2-benzisothiazolin-3-one and
4,5-trimethylene-4-isothiazolin-3-one.
[0349] Certain of the isothiazolinone or isothiazolothione
compounds which may be used as the additional biocidal compound can
have improved solubility in water when ill the form of a salt or
complex. The salt or complex may be with any suitable cation such
as an amine (including an alkanolamine) or a metal. Preferably, any
metal salt or complex contains a monovalent metal such as an alkali
metal. The alkali metal may be lithium, sodium or potassium. Most
preferably, the alkali metal salt is a sodium salt in view of the
ready availability of suitable sodium compounds from which to
prepare the salt.
[0350] Certain isothiazolinone or isothiazolothione compounds
useful as the biocidal compounds decompose in the presence of
alkali. Exemplary of alkali-sensitive compounds are
5-chloro-2-methyl-4-isothiazolin-3-one and
2-methyl-4-isothiazolin-3-one. Accordingly, the pH of the
compositions of the present invention which are alkali sensitive
should be maintained at a value no greater than about 8.
[0351] IX. Personal Care
[0352] The pH responsive polymer of the present invention is
suitable in the preparation of personal care (cosmetics,
toiletries, health and beauty aids, cosmeceuticals) and topical
health care products, including without limitation, hair care
products, such as shampoos (including combination shampoos, such as
"two-in-one" conditioning shampoos); post-shampoo rinses; setting
and style maintenance agents including setting aids, such as gels
and sprays, grooming aids, such as pomades, conditioners, perms,
relaxers, hair smoothing products, and the like; skin care products
(facial, body, hands, scalp and feet), such as creams, lotions,
conditioners, and cleansing products; anti-acne products;
anti-aging products (exfoliant, keratolytic, anticellulite,
antiwrinkle, and the like); skin protectants such as sunscreens,
sunblock, barrier creams, oils, silicones, and the like; skin color
products (whiteners, lighteners, sunless tanning accelerators, and
the like); hair colorants (hair dyes, hair color rinses,
highlighters, bleaches and the like); pigmented skin colorants
(face and body makeups, foundation creams, mascara, rouge, lip
products, and the like); bath and shower products (body cleansers,
body wash, shower gel, liquid soap, soap bars, syndet bars,
conditioning liquid bath oil, bubble bath, bath powders, and the
like); nail care products (polishes, polish removers,
strengtheners, lengtheners, hardeners, cuticle removers, softeners,
and the like); and any aqueous acidic to basic composition to which
an effective amount of the hydrophobic polymer can be incorporated
for achieving a beneficial or desirable, physical or chemical,
effect therein during storage and/or usage.
[0353] In one embodiment, the present invention is directed to a
personal care composition comprising water, one or more
surfactants, and a pH responsive polymer according to the present
invention.
[0354] In one embodiment, the personal care composition comprises,
based on 100 parts by weight ("pbw") of the personal care
composition, from about 10 to about 80 pbw, more typically from
about 20 to about 70 pbw, water, from about 1 to about 50 pbw of
one or more surfactants and from about 0.05 to about 20 pbw of the
pH responsive polymer of the present invention.
[0355] Suitable surfactants include anionic surfactants, cationic
surfactants, non-ionic surfactants, zwitterionic surfactants, and
mixtures thereof.
[0356] Suitable anionic surfactants are known compounds and
include, for example, linear alkylbenzene sulfonates, alpha olefin
sulfonates, paraffin sulfonates, alkyl ester sulfonates, alkyl
sulfates, alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy
carboxylates, alkyl alkoxylated sulfates, monoalkyl phosphates,
dialkyl phosphates, sarcosinates, isethionates, and taurates, as
well as mixtures thereof, such as for example, ammonium lauryl
sulfate, ammonium laureth sulfate, triethanolamine laureth sulfate,
monoethanolamine lauryl sulfate, monoethanolamine laureth sulfate,
diethanolamine lauryl sulfate, diethanolamine laureth sulfate,
lauric monoglyceride sodium sulfate, sodium lauryl sulfate, sodium
laureth sulfate, potassium lauryl sulfate, potassium laureth
sulfate, sodium trideceth sulfate, sodium tridecyl sulfate,
ammonium trideceth sulfate, ammonium tridecyl sulfate, sodium
cocoyl isethionate, disodium laureth sulfosuccinate, sodium methyl
oleoyl taurate, sodium laureth carboxylate, sodium trideceth
carboxylate, sodium monoalkyl phosphate, sodium dialkyl phosphate,
sodium lauryl sarcosinate, lauroyl sarcosine, cocoyl sarcosinate,
ammonium cocyl sulfate, sodium cocyl sulfate, potassium cocyl
sulfate, monoethanolamine cocyl sulfate, sodium tridecyl benzene
sulfonate, sodium dodecyl benzene sulfonate, and mixtures
thereof.
[0357] The cationic counterion of the anionic surfactant is
typically a sodium cation but may alternatively be a potassium,
lithium, calcium, magnesium, ammonium cation, or an alkyl ammonium
anion having up to 6 aliphatic carbon atoms, such as
anisopropylammonium, monoethanolammonium, diethanolammonium, or
triethanolammonium cation. Ammonium and ethanolammonium salts are
generally more soluble than the sodium salts. Mixtures of the above
cations may be used.
[0358] Suitable cationic surfactants are known compounds and
include, for example, mono-cationic surfactants according to
structure (XX) below:
##STR00040##
[0359] wherein:
[0360] R31, R32, R33 and R34 are independently hydrogen or an
organic group, provided that at least one of R31, R32, R33 and R34
is not hydrogen, and
[0361] X.sup.- is an anion, as well as mixtures of such
compounds
[0362] If one to three of the R31, R32, R33 and R34 groups are each
hydrogen, then the compound may be referred to as an amine salt.
Some examples of cationic amine salts include polyethoxylated (2)
oleyl/stearyl amine, ethoxylated tallow amine, cocoalkylamine,
oleylamine, and tallow alkyl amine.
[0363] For quaternary ammonium compounds (generally referred to as
quats) R31, R32, R33 and R34 may be the same or different organic
group, but may not be hydrogen. In one embodiment, R31, R32, R33
and R34 are each C8-C24 branched or linear hydrocarbon groups which
may comprise additional functionality such as, for example, fatty
acids or derivatives thereof, including esters of fatty acids and
fatty acids with alkoxylated groups; alkyl amido groups; aromatic
rings; heterocyclic rings; phosphate groups; epoxy groups; and
hydroxyl groups. The nitrogen atom may also be part of a
heterocyclic or aromatic ring system, e.g., cetethyl morpholinium
ethosulfate or steapyrium chloride.
[0364] Examples of quaternary ammonium compounds of the monoalkyl
amine derivative type include: cetyl trimethyl ammonium bromide
(also known as CETAB or cetrimonium bromide), cetyl trimethyl
ammonium chloride (also known as cetrimonium chloride), myristyl
trimethyl ammonium bromide (also known as myrtrimonium bromide or
Quaternium-13), stearyl dimethyl benzyl ammonium chloride (also
known as stearalkonium chloride), oleyl dimethyl benzyl ammonium
chloride, (also known as olealkonium chloride), lauryl/myristryl
trimethyl ammonium methosulfate (also known as cocotrimonium
methosulfate), cetyl dimethyl (2)hydroxyethyl ammonium dihydrogen
phosphate (also known as hydroxyethyl cetyldimonium phosphate),
babassuamidopropalkonium chloride, cocotrimonium chloride,
distearyldimonium chloride, wheat germ-amidopropalkonium chloride,
stearyl octyldimonium methosulfate, isostearaminopropalkonium
chloride, dihydroxypropyl PEG-5 linoleaminium chloride, PEG-2
stearmonium chloride, Quaternium 18, Quaternium 80, Quaternium 82,
Quaternium 84, behentrimonium chloride, dicetyl dimonium chloride,
behentrimonium methosulfate, tallow trimonium chloride and
behenamidopropyl ethyl dimonium ethosulfate.
[0365] Quaternary ammonium compounds of the dialkyl amine
derivative type include, for example, distearyldimonium chloride,
dicetyl dimonium chloride, stearyl octyldimonium methosulfate,
dihydrogenated palmoylethyl hydroxyethylmonium methosulfate,
dipalmitoylethyl hydroxyethylmonium methosulfate, dioleoylethyl
hydroxyethylmonium methosulfate, hydroxypropyl bisstearyldimonium
chloride, and mixtures thereof.
[0366] Quaternary ammonium compounds of the imidazoline derivative
type include, for example, isostearyl benzylimidonium chloride,
cocoyl benzyl hydroxyethyl imidazolinium chloride, cocoyl
hydroxyethylimidazolinium PG-chloride phosphate, Quaternium 32, and
stearyl hydroxyethylimidonium chloride, and mixtures thereof.
[0367] Typical cationic surfactants comprise dialkyl derivatives
such as dicetyl dimonium chloride and distearyldimonium chloride;
branched and/or unsaturated cationic surfactants such as
isostearylaminopropalkonium chloride or olealkonium chloride; long
chain cationic surfactants such as stearalkonium chloride and
behentrimonium chloride; as well as mixtures thereof.
[0368] Suitable anionic counterions for the cationic surfactant
include, for example, chloride, bromide, methosulfate, ethosulfate,
lactate, saccharinate, acetate and phosphate anions.
[0369] Suitable nonionic surfactants are known compounds and
include amine oxides, fatty alcohols, alkoxylated alcohols, fatty
acids, fatty acid esters, and alkanolamides. Suitable amine oxides
comprise, (C10-C24) saturated or unsaturated branched or straight
chain alkyl dimethyl oxides or alkyl amidopropyl amine oxides, such
as for example, lauramine oxide, cocamine oxide, stearamine oxide,
stearamidopropylamine oxide, palmitamidopropylamine oxide,
decylamine oxide as well as mixtures thereof. Suitable fatty
alcohols include, for example, (C10-C24) saturated or unsaturated
branched or straight chain alcohols, more typically (C10-C20)
saturated or unsaturated branched or straight chain alcohols, such
as for example, decyl alcohol, lauryl alcohol, myristyl alcohol,
cetyl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol and
linolenyl alcohol, and mixtures thereof. Suitable alkoxylated
alcohols include alkoxylated, typically ethoxylated, derivatives of
(C10-C24) saturated or unsaturated branched or straight chain
alcohols, more typically (C10-C20) saturated or unsaturated
branched or straight chain alcohols, which may include, on average,
from 1 to 22 alkoxyl units per molecule of alkoxylated alcohol,
such as, for example, ethoxylated lauryl alcohol having an average
of 5 ethylene oxide units per molecule. Mixtures of these
alkoxylated alcohols may be used. Suitable fatty acids include
(C10-C24) saturated or unsaturated carboxylic acids, more typically
(C10-C22) saturated or unsaturated carboxylic acids, such as, for
example, lauric acid, oleic acid, stearic acid, myristic acid,
cetearic acid, isostearic acid, linoleic acid, linolenic acid,
ricinoleic acid, elaidic acid, arichidonic acid, myristoleic acid,
and palmitoleic acid, as well as neutralized versions thereof.
Suitable fatty acid esters include esters of (C10-C24) saturated or
unsaturated carboxylic acids, more typically (C10-C22) saturated or
unsaturated carboxylic acids, for example, propylene glycol
isostearate, propylene glycol oleate, glyceryl isostearate, and
glyceryl oleate, and mixtures thereof. Suitable alkanolamides
include aliphatic acid alkanolamides, such as cocamide MEA (coco
monoethanolamide) and cocamide MIPA (coco monoisopropanolamide), as
well as alkoxylated alkanolamides, and mixtures thereof.
[0370] Suitable amphoteric surfactants are known compounds and
include for example, derivatives of aliphatic secondary and
tertiary amines in which the aliphatic radical can be straight
chain or branched and wherein one of the aliphatic substituents
contains from about 8 to about 18 carbon atoms and one contains an
anionic water-solubilizing group as well as mixtures thereof.
Specific examples of suitable amphoteric surfactants include the
alkali metal, alkaline earth metal, ammonium or substituted
ammonium salts of alkyl amphocarboxy glycinates and alkyl
amphocarboxypropionates, alkyl amphodipropionates, alkyl
amphodiacetates, alkyl amphoglycinates, and alkyl amphopropionates,
as well as alkyl iminopropionates, alkyl iminodipropionates, and
alkyl amphopropylsulfonates, such as for example, cocoamphoacetate
cocoamphopropionate, cocoamphodiacetate, lauroamphoacetate,
lauroamphodiacetate, lauroamphodipropionate, lauroamphodiacetate,
cocoamphopropyl sulfonate caproamphodiacetate, caproamphoacetate,
caproamphodipropionate, and stearoamphoacetate.
[0371] In one embodiment, the amphoteric surfactant comprises
sodium lauroampoacetate, sodium lauroampopropionate, disodium
lauroampodiacetate, sodium cocoamphoacetate, disodium
cocoamphodiacetate or a mixture thereof.
[0372] Suitable Zwitterionic surfactants are known compounds. Any
Zwitterionic surfactant that is acceptable for use in the intended
end use application and is chemically stable at the required
formulation pH is suitable as the optional Zwitterionic surfactant
component of the composition of the present invention, including,
for example, those which can be broadly described as derivatives of
aliphatic quaternary ammonium, phosphonium, and sulfonium compounds
in which the aliphatic radicals can be straight chain or branched
and wherein one of the aliphatic substituents contains from about 8
to about 24 carbon atoms and one contains an anionic
water-solubilizing group such as carboxyl, sulfonate, sulfate,
phosphate or phosphonate. Specific examples of suitable
Zwitterionic surfactants include alkyl betaines, such as
cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl
betaine, lauryl dimethyl alpha-carboxy-ethyl betaine, cetyl
dimethyl carboxymethyl betaine, lauryl bis-(2-hydroxy-ethyl)carboxy
methyl betaine, stearyl bis-(2-hydroxy-propyl)carboxymethyl
betaine, oleyl dimethyl gamma-carboxypropyl betaine, and lauryl
bis-(2-hydroxypropyl)alpha-carboxyethyl betaine, amidopropyl
betaines, and alkyl sultaines, such as cocodimethyl sulfopropyl
betaine, stearyldimethyl sulfopropyl betaine, lauryl dimethyl
sulfoethyl betaine, lauryl bis-(2-hydroxy-ethyl)sulfopropyl betaine
and alkylamidopropylhydroxy sultaines.
[0373] In one embodiment, the personal care composition further
comprises an electrolyte, typically in an amount of up to about 20
pbw per 100 pbw of the personal care composition. Suitable
electrolytes are known compounds and include salts of multivalent
anions, such as potassium pyrophosphate, potassium
tripolyphosphate, and sodium or potassium citrate, salts of
multivalent cations, including alkaline earth metal salts such as
calcium chloride and calcium bromide, as well as zinc halides,
barium chloride and calcium nitrate, salts of monovalent cations
with monovalent anions, including alkali metal or ammonium halides,
such as potassium chloride, sodium chloride, potassium iodide,
sodium bromide, and ammonium bromide, alkali metal or ammonium
nitrates, and polyelectrolytes, such as uncapped polyacrylates,
polymaleates, or polycarboxylates, lignin sulfonates or naphthalene
sulfonate formaldehyde copolymers.
[0374] In one embodiment, the personal care composition comprises
water, an anionic surfactant, a structuring agent for the anionic
surfactant, and a pH responsive polymer according to the present
invention and exhibits one or more lamellar surfactant phases.
"Lamellar surfactant phases" are phases which comprise one or more
surfactant bilayers, typically a plurality of surfactant bilayers
separated by liquid medium. Lamellar phases include spherulite
phases and the typical form of the liquid crystal G-phase, as well
as mixtures thereof. "G-phases", which are sometimes referred to in
the literature as "L, phases", are typically pourable,
non-Newtonian, anisotropic products that are cloudy looking and
exhibit a characteristic "smeary" appearance on flowing. Lamellar
phases can exist in several different forms, including domains of
parallel sheets, which constitute the bulk of the typical G-phases
described above and spherulites formed from a number of concentric
spherical shells, each of which is a bilayer of surfactant. In this
specification the term "G-phase" will be reserved for compositions,
which are at least partly of the former type. The spherulites are
typically between 0.1 and 50 microns in diameter and so differ
fundamentally from micelles. The surfactant phase morphology of the
structured surfactant composition is observed, for example, using
an optical microscope under cross-polarized light at about
40.times. magnification.
[0375] In one embodiment, the personal care composition of the
present invention exhibits structured surfactant properties, that
is, shear-thinning viscosity and a capacity to suspend water
insoluble or partially water soluble components.
[0376] As used herein in reference to viscosity, the terminology
"shear-thinning" means that such viscosity decreases with an
increase in shear rate. Shear-thinning may be characterized as a
"non-Newtonian" behavior, in that it differs from that of a
classical Newtonian fluid, for example, water, in which viscosity
is not dependent on shear rate.
[0377] As used herein in reference to a component of an aqueous
composition, the terminology "water insoluble or partially water
soluble components" means that the component is present in the
aqueous composition at a concentration above the solubility limit
of the component so that, in the case of a water insoluble
component, the component remains substantially non-dissolved in the
aqueous composition and, in the case of a partially water soluble
component, at least a portion of such component remains undissolved
in the aqueous composition.
[0378] As used herein, characterization of an aqueous composition
as "capable of suspending", or as being "able of suspend" water
insoluble or partially water insoluble components means that the
composition substantially resists flotation of such components in
the composition or sinking of such components in such composition
so that such components appear to be neutrally buoyant in such
composition and remain at least substantially suspended in such
composition under the anticipated processing, storage, and use
conditions for such aqueous composition.
[0379] In one embodiment, the personal care composition of the
present invention comprises, based on 100 pbw of the composition
from about 5 to about 40 parts pbw, more typically from about 10 to
about 30 pbw, and still more typically from about 15 to about 25
pbw, of the anionic surfactant and from about 0.1 to about 25 pbw,
more typically, from about 0.5 to about 10 pbw, of a structuring
agent.
[0380] In one embodiment, the pH of the lamellar phase containing
personal care composition is from about 5.0 to about 7.0, more
typically from about 5.5 to about 6.5.
[0381] Suitable anionic surfactants include those described above.
In one embodiment of the lamellar phase containing personal care
composition, the anionic surfactant comprises one or more branched
and/or unsaturated anionic surfactants. Suitable branched anionic
surfactants include, for example, sodium trideceth sulfate, sodium
tridecyl sulfate, ammonium trideceth sulfate, and ammonium tridecyl
sulfate.
[0382] Suitable structuring agents include cationic surfactants,
amphoteric surfactants, fatty alcohols, alkoxylated alcohols, fatty
acids, fatty acid esters, alkanolamides, amine oxides, and
electrolytes, and mixtures thereof. An effective amount of such
structuring agent is one that promotes and/or does not interfere
with the formation of a lamellar surfactant phase. Suitable
cationic surfactants, amphoteric surfactants, fatty alcohols,
alkoxylated alcohols, fatty acids, fatty acid esters,
alkanolamides, amine oxides, and electrolytes are described
above.
[0383] Typically, the greater the amount of surfactant present in
relation to its solubility, the smaller the amount electrolyte that
may be required in order to form a structure capable of supporting
solid materials and/or to cause flocculation of the structured
surfactant. In one embodiment, the composition contains a
sufficient amount of an electrolyte to promote formation lamellar
surfactant phases.
[0384] In one embodiment, the personal care composition of the
present invention further comprises, typically in an amount of from
greater than 0 pbw to about 50 pbw, more typically form about 1 to
about 30 pbw, per 100 pbw of the personal care composition, one or
more "benefit agents" that is, materials that provide a personal
care benefit, such as moisturizing or conditioning, to the user of
the personal care composition, such as, for example, emollients,
moisturizers, conditioners, polymers, vitamins, abrasives, UV
absorbers, antimicrobial agents, anti-dandruff agents, fragrances,
and/or appearance modifying additives, such as, for example,
colored particles or reflective particles, which may be in the form
of a solid, liquid, or gas and may be insoluble or are only partly
soluble in the personal care composition. Mixtures of the benefit
agents may be used.
[0385] In one embodiment, the personal care composition is a hair
styling composition. Suitable hair styling compositions may be in
the form of a gel, mousse, or spray and may be applied to the hair
and/or skin, for example, by hand or by spraying, as appropriate in
view of the form of the composition.
[0386] In one embodiment, the personal care composition is a hair
styling gel that comprises a hair styling polymer, a pH responsive
polymer of the present invention, and a carrier, such as water, a
(C2-C6)alkanol, or a mixture thereof.
[0387] Suitable hair styling polymers typically comprise multiple
cationic sites per molecule and include, for example,
polyquaternium-11, polyquaternium4, polyquaternium-7,
polyquaternium-16, polyquaternium-28, polyquaternium-44,
polyquaternium-46, polyquaternium-55, polyquaternium-68 and
polyquaternium-88. Suitable hair styling polymers also include, but
are not limited to copolymers of polyvinylpyrrolidone, vinyl
acetate, polyvinylcaprolactam, methylether maleic acid,
acrylamides, octylacrylamide, butylaminoethyl, crotonic acid,
dimethylaminopropyl methacrylate and dimethylaminoethyl
methacrylate, and mixtures thereof.
[0388] As used herein, the term "mousse" means a composition that
is in the form of a foam when applied. In one embodiment, the
personal care composition is a hair styling mousse is packaged in a
pressurized container and comprises a hair styling polymer, a pH
responsive polymer of the present invention, a carrier, such as
water, a (C2-C6)alkanol, a propellant suitable for foaming the
composition when the composition is dispensed from the container.
Suitable propellants are liquefiable gases, such as, for example,
propane, butane, isobutane, nitrogen, carbon dioxide, nitrous
oxide, 1,2-difluoroethane.
[0389] In one embodiment, the personal care composition is a hair
spray composition suitable for spray application from a container
that is equipped with a mechanical sprayer, comprising a hair
styling polymer, a pH responsive polymer of the present invention,
and a carrier, such as water, a (C2-C6)alkanol, or a mixture
thereof.
[0390] In one embodiment, the personal care composition is an
aerosol hair spray composition suitable for spray application from
a pressurized container and comprises, a hair styling polymer, a
carrier, typically a (C1-C6)alkanol or a (C7-C10) isoparaffin, a pH
responsive polymer of the present invention, and a propellant
suitable for aerosol delivery of the hair spray composition to the
hair. Suitable propellants are those described above in regard to
the hair styling mousse embodiment of the personal care composition
of the present invention.
[0391] The hair styling gel, mousse, and hair spray may in each
case, optionally further comprise one or more emollients,
conditioning agents, shine enhancers, moisture and heat sensitive
moieties, or a mixture thereof. Suitable emollients include, for
example, PEG-40 castor oil, glycerol, propylene glycol, butylene
glycol. Suitable conditioning and shine agents include, for
example, quaternized and/or hydrolyzed proteins of honey, soy,
wheat, guar or maize, cetyl alcohol, stearyl alcohol, ceteareth-20,
isopropyl palmitate, cyclopentasiloxane, cyclomethicone,
trimethylsilyamodimethicone, phenyltrimethicone,
ethoxylated/propylated dimethicone, dimethiconol, panthenol,
tocopherol acetate, tocopherol, cetrimmonium chloride, hair keratin
and silk amino acids and ethoxylated/propoxylated waxes of fruit
and vegetable origin.
[0392] The personal care composition according to the present
invention may optionally further comprise one or more adjuvants,
such as, for example, preservatives such as benzyl alcohol, methyl
paraben, propyl paraben and imidazolidinyl urea; pH adjusting
agents such as citric acid, succinic acid, phosphoric acid, sodium
hydroxide, sodium carbonate; dyes, and sequestering agents such as
disodium ethylenediamine tetra-acetate.
[0393] In general, personal care compositions may optionally
comprise, based on 100 pbw of the personal care composition and
independently for each such adjuvant, from about 0 to about 10 pbw,
typically from 0.5 pbw to about 5.0 pbw, of such optional
adjuvants, depending on the desired properties of the personal care
composition.
[0394] The pH responsive polymer of the present application is
useful as a component in aqueous fluid compositions used in
oilfield applications.
[0395] In one embodiment, an aqueous fluid composition of the
present invention comprises water and a pH responsive polymer of
the present invention, typically from about 0.05 to about 40 pbw,
more typically 0.1 pbw to 20 pbw, even more typically form about 1
to about 10 pbw of the pH responsive polymer per 100 pbw
composition, wherein the pH of the composition is greater than or
equal to about 6, more typically, from about 6 to about 10.
[0396] X. Use with Materials in Geological Formations
[0397] A. Fracturing Fluids
[0398] In one embodiment, the aqueous fluid composition of the
present invention is used as the fracturing fluid in a method for
hydraulic fracturing of a geologic formation to stimulate the
production of fluids, such as oil and/or natural gas, from the
formation. The fracturing fluid is injected through a wellbore and
against a surface of the formation at a pressure and flow rate at
least sufficient to initiate and/or extend one or more fractures in
the formation. Typically, the fracturing fluid further comprises a
proppant dispersed in the fracturing fluid. Suitable proppants are
inorganic particles, such as sand, bauxite particles, or glass
beads and are typically in the range of from about 20 to about 40
mesh. Such fracturing fluid compositions typically contain, based
on 100 pbw of the liquid component of such composition, from about
90 pbw to about 100 pbw water, from about 0.1 pbw to about 10 pbw
pH responsive polymer, and from about 10 pbw to about 150 pbw
proppant. The proppant particles are transported into fractures in
the geologic formation by the pressurized fracturing fluid stream
and keep the fractures from closing back down when the stream of
fracturing fluid is discontinued. The proppant-filled fractures
provide permeable channels through which the formation fluids can
flow to the wellbore and then be withdrawn. Hydraulic fracturing
fluids are subject to high temperatures and shear rates.
[0399] The polymer and composition of the present invention may be
used in the fracturing fluid in an amount of from 0.01 to 5% by
weight of the fluid.
[0400] A.1. Crosslinking Agent
[0401] A crosslinking agent may be used with the fracturing fluids.
The crosslinking agents used may include aluminum or antimony or
Group 4 transition metal compound crosslinking agents. The
crosslinking agent may include zirconium, titanium and hafnium
crosslinking agents, and combinations of these, and may include
organo-metallic compounds. Examples of suitable zirconium
crosslinking agents include zirconium triethanolamine, L-glutamic
acid-triethanolamine-zirconium, zirconium diethanolamine, zirconium
tripropanolamine, and zirconium lactate complexes, and/or the
related salts, and/or their mixtures. Examples of titanium
crosslinking agents include titanium triethanolamine,
dihydroxybis(ammonium lactato)titanium, and titanium
acetylacetonate. The crosslinking agent may be included in the
fluid in an amount of from about 0.01% to about 1.5% by weight of
the fluid, more particularly, from about 0.02% to about 0.3% by
weight of the fluid.
[0402] A.2. Buffering Agent
[0403] A hydroxyl ion releasing agent or buffering agent may be
employed to adjust the pH or buffer the fluid, i.e., moderate
amounts of either a strong base or acid may be added without
causing any large change in pH value of the fluid. These may useful
in changing the rate of crosslinking. Alkaline amine or polyamine
compounds useful to raise the pH to the desirable level are
outlined in U.S. Pat. No. 4,579,670, and include
tetramethylenediamine, triethylenetetramine, tetraethylenepentamine
(TEPA), diethylenetriamine, triethylenediamine,
triethylenepentamine, ethylenediamen and similar compounds. The
alkali metal hydroxides, e.g., sodium hydroxide, and carbonates can
also be used. Other acceptable materials are Ca(OH).sub.2,
Mg(OH).sub.2, Bi(OH).sub.3, Co(OH).sub.2, Pb(OH).sub.2,
Ni(OH).sub.2, Ba(OH).sub.2, and Sr(OH).sub.2. Acids such as
hydrochloric acid, sulfuric acid, nitric acid, citric acid, acetic
acid, fumaric acid, maleic acid, can be used to lower the pH.
[0404] In various embodiments, the buffering agent is a combination
of a weak acid and a salt of the weak acid; an acid salt with a
normal salt; or two acid salts. Examples of suitable buffering
agents are acetic acid-Na acetate;
NaH.sub.2PO.sub.4--Na.sub.2PO.sub.4; sodium carbonate-sodium
bicarbonate; and sodium bicarbonate, or other like agents. By
employing a buffering agent instead of merely a hydroxyl ion
producing material, a fluid is provided which is more stable to a
wide range of pH values found in local water supplies and to the
influence of acidic materials located in formations and the
like.
[0405] A.3. Gas Component
[0406] The fracturing fluids may contain a gas component, as
discussed above. The gas component may be provided from any
suitable gas that forms an energized fluid or foam when introduced
into the aqueous medium. See, for example, U.S. Pat. No. 3,937,283
(Blauer et al.), hereinafter incorporated by reference. The gas
component may comprise a gas selected from nitrogen, air, argon,
carbon dioxide, and any mixtures thereof. Particularly useful are
the gas components of nitrogen or carbon dioxide, in any quality
readily available. The gas component may assist in the fracturing,
and also the capacity of the fluid to carry solids, such as
proppants. The presence of the gas also enhances the flowback of
the fluid to facilitate cleanup. The fluid may contain from about
10% to about 90% volume gas component based upon total fluid volume
percent, more particularly from about 20% to about 80% volume gas
component based upon total fluid volume percent, and more
particularly from about 30% to about 70% volume gas component based
upon total fluid volume percent.
[0407] A.4. Breaker
[0408] Fracturing fluids based on the invention may also comprise a
breaker. The purpose of this component is to "break" or diminish
the viscosity of the fluid so that this fluid is more easily
recovered from the formation during cleanup. With regard to
breaking down viscosity, oxidizers, enzymes, or acids may be used.
Breakers reduce the polymers molecular weight by the action of an
acid, an oxidizer, an enzyme, or some combination of these on the
polymer itself. The breakers may include persulfates such as
ammonium persulfate, sodium persulfate, and potassium persulfate,
bromates such as sodium bromate and potassium bromate, periodates,
metal peroxides such as calcium peroxide, chlorites, and the like,
and the combinations of these breakers, live or encapsulated.
[0409] A.5. Proppant
[0410] Embodiments of the invention used as fracturing fluids may
also include proppant particles substantially insoluble in the
fluids of the formation. Proppant particles carried by the
treatment fluid remain in the fracture created, thus propping open
the fracture when the fracturing pressure is released and the well
is put into production. Suitable proppant materials include, but
are not limited to, sand, walnut shells, sintered bauxite, glass
beads, ceramic materials, naturally occurring materials, or similar
materials. Mixtures of proppants can be used as well. If sand is
used, it will typically be from about 20 mesh (0.841 mm) to about
100 mesh (0.0059 mm) in size. With synthetic proppants, mesh sizes
of about 8 (0.937 mm) or greater may be used. Naturally occurring
materials may be underived and/or unprocessed naturally occurring
materials, as well as materials based on naturally occurring
materials that have been processed and/or derived. Suitable
examples of naturally occurring particulate materials for use as
proppants include, but are not necessarily limited to: ground or
crushed shells of nuts such as walnut, coconut, pecan, almond,
ivory nut, brazil nut, etc.; ground or crushed seed shells
(including fruit pits) of seeds of fruits such as plum, olive,
peach, cherry, apricot, etc.; ground or crushed seed shells of
other plants such as maize (e.g., corn cobs or corn kernels), etc.;
processed wood materials such as those derived from woods such as
oak, hickory, walnut, poplar, mahogany, etc. including such woods
that have been processed by grinding, chipping, or other form of
particalization, processing, etc. Further information on nuts and
composition thereof may be found in Encyclopedia of Chemical
Technology, Edited by Raymond E. Kirk and Donald F. Othmer, Third
Edition, John Wiley & Sons, Volume 16, pages 248-273 (entitled
"Nuts"), Copyright 1981, which is incorporated herein by
reference.
[0411] The concentration of proppant in the fluid can be any
concentration known in the art, and will preferably be in the range
of from about 0.03 to about 3 kilograms of proppant added per liter
of liquid phase. Also, any of the proppant particles can further be
coated with a resin to potentially improve the strength, clustering
ability, and flow back properties of the proppant.
[0412] A.6. Aqueous Media
[0413] The aqueous medium of the fracturing fluids of the present
invention may be water or brine. In those embodiments of the
invention where the aqueous medium is a brine, the brine is water
comprising an inorganic salt or organic salt. Inorganic salts may
include alkali metal halides, such as potassium chloride. The
carrier brine phase may also comprise an organic salt, such as
sodium or potassium formate. Inorganic divalent salts include
calcium halides, such as calcium chloride or calcium bromide.
Sodium bromide, potassium bromide, or cesium bromide may also be
used. The salt may be chosen for compatibility reasons i.e. where
the reservoir drilling fluid used a particular brine phase and the
completion/clean up fluid brine phase is chosen to have the same
brine phase. Typical salt levels are 2 to 30 wt % salt based on
overall composition of the aqueous brine. The most common level of
salt in brine is 2-10 weight % sodium chloride, potassium chloride
or mixtures thereof based on overall composition of the aqueous
brine.
[0414] A.7. Fiber Component
[0415] A fiber component may be included in the fracturing fluids
of the invention to achieve a variety of properties including
improving particle suspension, and particle transport capabilities,
and gas phase stability. Fibers used may be hydrophilic or
hydrophobic in nature, but hydrophilic fibers may be useful for
some applications. Fibers can be any fibrous material, such as, but
not necessarily limited to, natural organic fibers, comminuted
plant materials, synthetic polymer fibers (by non-limiting example
polyester, polyaramide, polyamide, novoloid or a novoloid-type
polymer), fibrillated synthetic organic fibers, ceramic fibers,
inorganic fibers, metal fibers, metal filaments, carbon fibers,
glass fibers, ceramic fibers, natural polymer fibers, and any
mixtures thereof. Particularly useful fibers are polyester fibers
coated to be highly hydrophilic, such as, but not limited to,
DACRON polyethylene terephthalate (PET) fibers available from
Invista Corp. Wichita, Kans., USA, 67220. Other examples of useful
fibers include, but are not limited to, polylactic acid polyester
fibers, polyglycolic acid polyester fibers, polyvinyl alcohol
fibers, and the like. When used in fluids of the invention, the
fiber component may be include at concentrations from about 1 to
about 15 grams per liter of the liquid phase of the fluid, in
certain applications the concentration of fibers may be from about
2 to about 12 grams per liter of liquid, and in others from about 2
to about 10 grams per liter of liquid.
[0416] A.8. Other Optional Ingredients
[0417] Fluid embodiments of fracturing fluids of the invention may
further contain other additives and chemicals known to be commonly
used in oilfield applications by those skilled in the art. These
include, but are not necessarily limited to, materials such as
surfactants in addition to those mentioned herein, clay stabilizers
such as tetramethyl ammonium chloride and/or potassium chloride,
breaker aids in addition to those mentioned herein, oxygen
scavengers, alcohols, scale inhibitors, corrosion inhibitors,
fluid-loss additives, bactericides, and the like. Also, they may
include a co-surfactant to optimize viscosity or to minimize the
formation of stable emulsions that contain components of crude oil
or a polysaccharide or chemically modified polysaccharide, polymers
such as cellulose, derivatized cellulose, guar gum, derivatized
guar gum, xanthan gum, or synthetic polymers such as
polyacrylamides and polyacrylamide copolymers, oxidizers such as
ammonium persulfate and sodium bromate, and biocides such as
2,2-dibromo-3-nitrilopropionamine. The fluid should be
substantially devoid of hectorite clay or other clay components and
such components may be present in the fluid only in amounts of less
than 0.1% by weight.
[0418] Aqueous fluid embodiments of the invention may also comprise
an organoamino compound. Examples of suitable organoamino compounds
include, but are not necessarily limited to, tetraethylenepentamine
(TEPA), triethylenetetramine, pentaethylenehexamine,
triethanolamine, and the like, or any mixtures thereof. When
organoamino compounds are used in fluids of the invention, they are
incorporated at an amount from about 0.01 wt % to about 2.0 wt %
based on total liquid phase weight. The organoamino compound may be
incorporated in an amount from about 0.05 wt % to about 1.0 wt %
based on total weight of the fluid. A particularly useful
organoamino compound is tetraethylenepentamine (TEPA).
[0419] A.9. Hydraulic Fracturing Techniques
[0420] The fluids of the invention may be used for hydraulically
fracturing a subterranean formation. Techniques for hydraulically
fracturing a subterranean formation are known to persons of
ordinary skill in the art, and involve pumping the fracturing fluid
into the borehole and out into the surrounding formation. The fluid
pressure is above the minimum in situ rock stress, thus creating or
extending fractures in the formation. See Stimulation Engineering
Handbook, John W. Ely, Pennwell Publishing Co., Tulsa, Okla.
(1994), U.S. Pat. No. 5,551,516 (Normal et al.), "Oilfield
Applications", Encyclopedia of Polymer Science and Engineering,
vol. 10, pp. 328-366 (John Wiley & Sons, Inc. New York, N.Y.,
1987) and references cited therein, the disclosures of which are
incorporated herein by reference thereto.
[0421] In the fracturing treatment, fluids of the present invention
may be used in the pad treatment, the proppant stages, or both. The
components of the liquid phase may be mixed on the surface.
Alternatively, the fluid may be prepared on the surface and pumped
down tubing while any gas component could be pumped down the
annulus to mix down hole, or vice versa.
[0422] In hydraulic fracturing the fracturing fluid comprising
water soluble polymer and at least one nonionic surfactant is
pumped into the targeted formation at a rate in excess of what can
be dissipated through the natural permeability of the formation
rock. The fracturing fluids result in a pressure build up until
such pressure exceeds the strength of the formation rock. When this
occurs, the formation rock fails and a so-called "fracture" is
initiated. With continued pumping, the fracture grows in length,
width and height.
[0423] At a predetermined time in the pumping process, solid
particulate is typically added to the fluid that is being pumped.
This particulate is carried down the well, out of the wellbore and
deposited in the created fracture. It is the purpose of this
specially designed particulate to keep the fracture from "healing"
to its initial position (after pumping has ceased). The particulate
is said to be propping open the fracture and is therefore
designated as "proppant". The fracture, which is generated by the
application of this stimulation technique, creates a conductive
path to the wellbore for the hydrocarbon.
[0424] Typical proppant is selected from the group consisting of
gravel, quartz sand grains, sintered bauxite, glass and ceramic
beads, walnut shell fragments, or aluminum pellets. The fracturing
fluid may also include a thermal stabilizer, for example sodium
thiosulfate, methanol, ethylene glycol, isopropanol, thiourea,
and/or sodium thiosulfite. The fracturing fluid may also include
KCl as a clay stabilizer.
[0425] B. Acidizing
[0426] Producing oil and gas wells have long been treated to
stimulate production thereof utilizing a method termed "acidizing"
in which an emulsion of an aqueous mineral acid either alone or in
combination with various surfactants, corrosion inhibiting agents,
and hydrocarbon oils is added to a producer well. Presumably, such
treatments tend to remove deposits from the area of the
subterranean oil or gas formation immediately adjacent to the
production well bore, thus increasing the permeability of the
formation and allowing residual oil or gas to be recovered through
the well bore. Another object of such "acidizing" treatment of oil
or gas producer wells is the removal of water from the interstices
of the formation by the use of a composition which materially
lowers the interfacial forces between the water and the oil or gas.
Various surface-active agents have been recommended for this
use.
[0427] Producing oil and gas wells have long been treated to
stimulate production thereof utilizing a method termed "acidizing"
in which an emulsion of an aqueous mineral acid either alone or in
combination with various surfactants, corrosion inhibiting agents,
and hydrocarbon oils is added to a producer well. Presumably, such
treatments tend to remove deposits from the area of the
subterranean oil or gas formation immediately adjacent to the
production well bore, thus increasing the permeability of the
formation and allowing residual oil or gas to be recovered through
the well bore. Another object of such "acidizing" treatment of oil
or gas producer wells is the removal of water from the interstices
of the formation by the use of a composition which materially
lowers the interfacial forces between the water and the oil or gas.
Various surface-active agents have been recommended for this
use.
[0428] Acidizing, and fracturing procedures using acidic treatment
fluids, are commonly carried out in subterranean well formations to
accomplish a number of purposes including, but not limited to, to
facilitate the recovery of desirable hydrocarbons from the
formation. As used herein, the term "treatment fluid" refers to any
fluid that may be used in a subterranean application in conjunction
with a desired function and/or for a desired purpose. The term
"treatment fluid" does not imply any particular action by the fluid
or any component thereof.
[0429] One commonly used aqueous acidic treatment fluid comprises
hydrochloric acid. Other commonly used acids for acidic treatment
fluids include hydrofluoric acid, acetic acid, formic acid, citric
acid, ethylene diamine tetra acetic acid ("EDTA"), glycolic acid,
sulfamic acid, and derivatives or combinations thereof.
[0430] Acidic treatment fluids are used in various subterranean
operations. For example, formation acidizing or "acidizing" is a
method for, among other purposes, increasing the flow of desirable
hydrocarbons from a subterranean formation. In a matrix acidizing
procedure, an aqueous acidic treatment fluid is introduced into a
subterranean formation via a well bore therein under pressure so
that the acidic treatment fluid flows into the pore spaces of the
formation and reacts with (e.g., dissolves) the acid-soluble
materials therein. As a result, the pore spaces of that portion of
the formation are enlarged, and the permeability of the formation
may increase. The flow of hydrocarbons from the formation therefore
may be increased because of the increase in formation conductivity
caused, inter alia, by dissolution of the formation material. In
fracture acidizing procedures, one or more fractures are produced
in the formation(s) and an acidic treatment fluid is introduced
into the fracture(s) to etch flow channels therein. Acidic
treatment fluids also may be used to clean out well bores to
facilitate the flow of desirable hydrocarbons. Other acidic
treatment fluids may be used in diversion processes and well bore
clean-out processes. A specific example is filter cake removal.
[0431] To increase the viscosity of an aqueous acidic treatment
fluid, a suitable gelling agent may be included in the treatment
fluid (often referred to as "gelling" the fluid). Gelling an
aqueous acidic treatment fluid may be useful, among other purposes,
to prevent the acid from becoming prematurely spent and inactive.
Additionally, gelling an aqueous acidic treatment fluid may enable
the development of wider fractures so that the gelled acidic
treatment fluid may delay the interaction of the acid with an acid
soluble component in the well bore or the formation. Moreover,
gelling an aqueous acidic treatment fluid may permit better fluid
loss control.
[0432] Acidic treatment fluids used in subterranean operations are
predominantly water-based fluids that comprise gelling agents to
increase their viscosities. Common gelling agents include
polysaccharides (such as xanthan), synthetic polymers (such as
polyacrylamide), and surfactant gel systems. To assist the gelling
agents in maintaining these viscosities in the presence of the high
temperatures and slat concentrations experienced downhole the
composition includes the polymer combinations of the present
invention.
[0433] The aqueous base fluids of the acidic treatment fluids of
the present invention generally comprise fresh water, salt water,
sea water, a brine (e.g., a saturated salt water or formation
brine), or a combination thereof. Other water sources may be used,
including those comprising monovalent, divalent, or trivalent
cations (e.g., magnesium, calcium, zinc, or iron) and, where used,
may be of any weight. If a water source is used that contains such
divalent or trivalent cations in concentrations sufficiently high
to be problematic, then such divalent or trivalent salts may be
removed, either by a process such as reverse osmosis, or by raising
the pH of the water in order to precipitate out such divalent salts
to lower the concentration of such salts in the water before the
water is used. Another method would be to include a chelating agent
to chemically bind the problematic ions to prevent their
undesirable interactions with the clarified xanthan. Suitable
chelants include, but are not limited to, citric acid or sodium
citrate, ethylene diamine tetra acetic acid ("EDTA"), hydroxyethyl
ethylenediamine triacetic acid ("HEDTA"), dicarboxymethyl glutamic
acid tetrasodium salt ("GLDA"), diethylenetriaminepentaacetic acid
("DTPA"), propylenediaminetetraacetic acid ("PDTA"),
ethylenediaminedi(o-hydroxyphenylacetic) acid ("EDDHA"),
glucoheptonic acid, gluconic acid, and the like, and
nitrilotriacetic acid ("NTA"). Other chelating agents also may be
suitable. One skilled in the art will readily recognize that an
aqueous base fluid containing a high level of multi-valent ions
should be tested for compatibility prior to use.
[0434] The gelling agents comprising the polymers of the present
invention may be present in an acidic treatment fluid of the
present invention in an amount of from about 1 lb/Mgal to about 200
lb/Mgal. In embodiments wherein the gelling agents comprising
clarified xanthan further comprise scleroglucan, one may include
about 1 lb/Mgal to about 200 lb/Mgal of scleroglucan. In an acidic
treatment fluid that comprises hydrochloric acid, one may include
about 1 to about 200 lb/Mgal of scleroglucan. In embodiments
wherein the gelling agents comprising clarified xanthan further
comprise diutan, one may include about 1 to about 200 lb/Mgal of
diutan. In an acidic treatment fluid that comprises about 15%
hydrochloric acid, one may include about 1 to about 200 lb/Mgal of
diutan. In some embodiments, one may include about 10 to about 150
lb/Mgal of clarified xanthan, scleroglucan, and/or diutan. A person
of skill in the art with the benefit of this disclosure will
recognize that any specific concentration or narrower range of
concentrations of the gelling agents of the present invention
encompassed by the broader concentration ranges specifically
articulated above may be used and/or may be particularly
advantageous for a particular embodiment of the present
invention.
[0435] In certain embodiments, the acidic treatment fluids of the
present invention also may comprise any additional additive that
may be suitable in a particular application of the present
invention, including, but not limited to, any of the following:
hydrate inhibitors, clay stabilizers, bactericides, salt
substitutes (such as tetramethyl ammonium chloride), relative
permeability modifiers (such as HPT-1..TM.. chemical additive
available from Halliburton Energy Services, Duncan, Okla.), sulfide
scavengers, fibers, nanoparticles, consolidating agents (such as
resins and/or tackifiers), corrosion inhibitors, corrosion
inhibitor intensifiers, pH control additives, surfactants,
breakers, fluid loss control additives, scale inhibitors,
asphaltene inhibitors, paraffin inhibitors, salts, bactericides,
crosslinkers, stabilizers, chelants, foamers, defoamers,
emulsifiers, demulsifiers, iron control agents, solvents, mutual
solvents, particulate diverters, gas phase, carbon dioxide,
nitrogen, other biopolymers, synthetic polymers, friction reducers,
combinations thereof, or the like. The acidic treatment fluids of
the present invention also may include other additives that may be
suitable for a given application, as will be recognized by a person
of ordinary skill in the art, with the benefit of this
disclosure.
[0436] While typically not required, the acidic treatment fluids of
the present invention also may comprise breakers capable of
reducing the viscosity of the acidic treatment fluid at a desired
time. Examples of such breakers that may be suitable for the acidic
treatment fluids of the present invention include, but are not
limited to, sodium chlorite, hypochlorites, perborates,
persulfates, peroxides (including organic peroxides), enzymes,
derivatives thereof, and combinations thereof. Other suitable
breakers may include suitable acids. Examples of peroxides that may
be suitable include tert-butyl hydroperoxide and tert-amyl
hydroperoxide. A breaker may be included in an acidic treatment
fluid of the present invention in an amount and form sufficient to
achieve the desired viscosity reduction at a desired time. The
breaker may be formulated to provide a delayed break, if desired.
For example, a suitable breaker may be encapsulated if desired.
Suitable encapsulation methods are known to those skilled in the
art. One suitable encapsulation method that may be used involves
coating the breaker(s) with a material that will degrade when
placed downhole so as to release the breaker at the appropriate
time. Coating materials that may be suitable include, but are not
limited to, polymeric materials that will degrade when downhole.
The terms "degrade," "degradation," or "degradable" refer to both
the two relatively extreme cases of hydrolytic degradation that the
degradable material may undergo, i.e., heterogeneous (or bulk
erosion) and homogeneous (or surface erosion), and any stage of
degradation in between these two. This degradation can be a result
of, inter alia, a chemical or thermal reaction or a reaction
induced by radiation. Suitable examples of materials that can
undergo such degradation include polysaccharides such as dextran or
cellulose; chitins; chitosans; proteins; aliphatic polyesters;
poly(lactides); poly(glycolides); poly(.epsilon.-caprolactones),
poly(hydroxybutyrates); poly(anhydrides); aliphatic polycarbonates;
orthoesters, poly(orthoesters); poly(amino acids); poly(ethylene
oxides); polyphosphazenes; derivatives thereof; and combinations
thereof. If used, a breaker should be included in a composition of
the present invention in an amount sufficient to facilitate the
desired reduction in viscosity in a viscosified treatment fluid.
For instance, peroxide concentrations that may be used vary from
about 0.1 to about 10 gallons of peroxide per 1000 gallons of the
acidic treatment fluid.
[0437] C. Enhanced Oil Recovery
[0438] The present invention may be employed with other techniques
to further improve hydrocarbon recovery from subterranean
formations. Initially, oil is produced from the fractured formation
by pressure depletion (primary recovery). In this method, the
differential pressure between the formation and a production well
or wells forces the oil contained within the formation toward a
production well where it can be recovered. Traditionally secondary
recovery processes through injection of water or gas are used to
displace additional oil toward producing wells. Typically, up to
about 35 percent of the oil which is initially contained in a
formation can be recovered in average through primary and secondary
recovery. This leaves a large quantity of oil within the formation.
Additionally, some formations contain oil which is too viscous to
be efficiently recovered from the formation using primary and
secondary processes. Because of the need to recover a larger
percentage of the oil from a formation, methods have been developed
to recover oil which could not be recovered using only pressure
depletion techniques. These methods are typically referred to as
"enhanced oil recovery techniques" (EOR).
[0439] Thus, the present invention is also directed to a method for
recovering crude oil from a subterranean formation, comprising
introducing to the formation an aqueous medium comprising water or
brine and the composition of the present invention including a
combination of anionic polymer and cationic polymer described
above.
[0440] The global average recovery factor for conventional oil
fields is about 35% and it could be raised up to 50% through
enhanced oil recovery. There are two essentials components to EOR:
improving displacement efficiency and improving macroscopic sweep
efficiency. The present invention enhances oil recovery by
maintaining stable viscosity at high temperatures. The method of
the invention is particularly useful in the stimulation of oil and
gas wells which have failed to respond to acidizing treatment of
the producing well including the use of various acids with various
surfactants.
[0441] C.1. Chemical Flooding
[0442] A promising EOR method is an enhanced oil recovery process
referred to as chemical flooding which generally covers the use of
polymer and/or surfactant slugs. In polymer flooding, a polymer
solution is injected to displace oil toward producing wells. The
polymer solution is designed to develop a favorable mobility ratio
between the injected polymer solution and the oil/water bank being
displaced ahead of the polymer. However, the use of polymer is not
always satisfactory as many polymer solutions are sensitive to
brine type and concentration which can affect the apparent
viscosity of the solution. In surfactant flooding, an aqueous
solution containing surfactant is injected into the oil rich
formation. Residual oil drops are deformed as a result of low
Interfacial Tension provided by surfactant solution and drops are
displaced through the pore throats and displaced oil is the
recovered. See U.S. Pat. No. 7,789,160 to Hough et al. incorporated
herein by reference in its entirety.
[0443] The present compositions advantageously are compatible with
anionic surfactants typically used to decrease interfacial tension
to also assist in enhancing oil recovery from subterranean
formations.
[0444] The present invention proves enhanced oil recovery. For
example, the present invention is also directed to a method for
recovering crude oil from a subterranean formation, comprising
introducing to the formation an aqueous medium comprising water or
brine and the composition of the present invention including a
combination of polyanionic polymer and polycationic polymer
described above.
[0445] There are two important components to EOR: improving
displacement efficiency and improving macroscopic sweep efficiency.
The present invention enhances oil recovery by maintaining stable
viscosity at high temperatures. The method of the invention is
particularly useful in the stimulation of oil and gas wells which
have failed to respond to acidizing treatment of the producing well
including the use of various acids with various surfactants.
[0446] The present compositions advantageously are compatible with
anionic surfactants typically used to decrease interfacial tension
to also assist in enhancing oil recovery from subterranean
formations.
[0447] The aqueous medium of the composition may be soft water,
brackish water or brine. Typically the aqueous medium in
compositions used to treat subterranean formations comprises
brine.
[0448] C.2. Other Ingredients
[0449] Compositions of the invention may contain components in
addition to water, the first cationic or cationaizable polymer, the
second anionic or anionizable polymer and optional surfactants.
Such additional components are, for example, co-solvents, acids,
bases, buffers, chelating agents for the control of multivalent
cations, freezing point depressants, etc.
[0450] For example, a hydrocarbon recovery composition according to
the present invention may be provided to the hydrocarbon containing
formation alone or with other compounds for enhancing oil recovery.
For example, these other compounds may be other nonionic additives
(e.g., alcohols, ethoxylated alcohols and/or sugar based esters).
Some embodiments have less than 0.3 weight percent of one or more
anionic surfactants (e.g. sulfates, sulfonates, ethoxylated
sulfates, and/or phosphates). In some embodiments the composition
has less than 0.3 wt % each of anionic surfactant, amphoteric
surfactant and zwitterionic surfactant. If desired, there may be an
absence of anionic surfactant, an absence of amphoteric surfactant,
and an absence of zwitterionic surfactant.
[0451] C.3. Alcohol
[0452] Alcohol can be used as mutual solvent to reduce water
saturation. The interfacial tension between oil and ethanol is much
lower than between oil and brine.
[0453] Capillary forces of retention for the alcohol are much
reduced compared to those for brine.
[0454] It has been reported that isopropyl or butyl alcohol plus
methyl alcohol could be used in miscible displacement to increase
oil recovery of naphtha and mineral oil.
[0455] Others have investigated enhanced oil recovery by alcohol
flooding. Their process design was strongly guided by the ternary
phase of alcohol/oil/brine. They showed that oil recovery was
highly dependent on the choice of alcohol/oil/brine combinations.
Others have reported that injection of appropriate combinations of
oil-soluble and water-soluble solvents such as alcohols and ketones
could significantly enhance oil recovery.
[0456] In an embodiment, an aliphatic nonionic additive may be used
in a hydrocarbon recovery composition. As used herein, the term
"aliphatic" refers to a straight or branched chain of carbon and
hydrogen atoms. In some embodiments, an aliphatic portion of an
aliphatic nonionic additive may have an average carbon number from
10 to 24. In some embodiments, an aliphatic portion of an aliphatic
nonionic additive may have an average carbon number from 12 to 18.
In some embodiments, the aliphatic nonionic additive may include a
branched aliphatic portion. A branched aliphatic portion of an
aliphatic nonionic additive may have an average carbon number from
16 to 17. In some embodiments, a branched aliphatic group of an
aliphatic nonionic additive may have less than about 0.5 percent
aliphatic quaternary carbon atoms. In an embodiment, an average
number of branches per aliphatic nonionic additive ranges from
about 0.1 to about 2.5. In other embodiments, an average number of
branches per aliphatic nonionic additive ranges from about 0.7 to
about 2.5.
[0457] Methyl branches may represent between about 20 percent to
about 99 percent of the total number of branches present in the
branched nonionic additive. In some embodiments, methyl branches
may represent greater than about 50 percent of the total number of
branches in a branched nonionic additive. The number of ethyl
branches in the alcohol may represent, in certain embodiments, less
than about 30 percent of the total number of branches. In other
embodiments, the number of ethyl branches, if present, may be
between about 0.1 percent and about 2 percent of the total number
of branches. Branches other than methyl or ethyl, if present, may
be less than about 10 percent of the total number of branches. In
some embodiments, less than about 0.5 percent of the total number
of branches are neither ethyl nor methyl groups.
[0458] In an embodiment, an aliphatic nonionic additive may be a
long chain aliphatic alcohol. The term "long chain," as used
herein, refers to a carbon chain having an average carbon number
from 10 to 30. A long chain aliphatic alcohol (e.g., a long chain
primary alcohol) may be purchased commercially (e.g., NEODOL
alcohols manufactured by Shell Chemical Co., Houston, Tex.). In
certain embodiments, a long chain aliphatic alcohol may be prepared
by a variety of generally known methods. A long chain aliphatic
alcohol may have an average carbon number from 10 to 24. In some
embodiments, a long chain aliphatic alcohol may have an average
carbon number from 12 to 18. In other embodiments, a long chain
aliphatic alcohol may have an average carbon number from 16 to
17.
[0459] In an embodiment, a portion of the long chain aliphatic
alcohol may be branched. Branched long chain aliphatic alcohols may
be prepared by hydroformylation of a branched olefin. Preparations
of branched olefins are described in U.S. Pat. No. 5,510,306 to
Murray, entitled "Process for Isomerizing Linear Olefins to
Isoolefins;" U.S. Pat. No. 5,648,584 to Murray, entitled "Process
For Isomerizing Linear Olefins to Isoolefins" and U.S. Pat. No.
5,648,585 to Murray, entitled "Process For Isomerizing Linear
Olefins to Isoolefins," all of which are incorporated by reference
herein. Preparations of branched long chain aliphatic alcohols are
described in U.S. Pat. No. 5,849,960 to Singleton et al., entitled
"Highly Branched Primary Alcohol Compositions, and Biodegradable
Detergents Made Therefrom;" U.S. Pat. No. 6,150,222 to Singleton et
al., entitled "Highly Branched Primary Alcohol Compositions, and
Biodegradable Detergents Made Therefrom;" U.S. Pat. No. 6,222,077
to Singleton et al., entitled "Highly Branched Primary Alcohol
Compositions, and Biodegradable Detergents Made Therefrom," all of
which are incorporated by reference herein.
[0460] In some embodiments, branches of a branched aliphatic group
of a long chain aliphatic alcohol may have less than about 0.5
percent aliphatic quaternary carbon atoms. In an embodiment, an
average number of branches per long chain aliphatic alcohol ranges
from about 0.1 to about 2.5. In other embodiments, an average
number of branches per alcohol ranges from about 0.7 to about
2.5.
[0461] Methyl branches may represent between about 20 percent to
about 99 percent of the total number of branches present in the
branched long chain aliphatic alcohol. In some embodiments, methyl
branches may represent greater than about 50 percent of the total
number of branches in a branched long chain aliphatic alcohol. The
number of ethyl branches in the alcohol may represent, in certain
embodiments, less than about 30 percent of the total number of
branches. In other embodiments, the number of ethyl branches, if
present, may be between about 0.1 percent and about 2 percent of
the total number of branches. Branches other than methyl or ethyl,
if present, may be less than about 10 percent of the total number
of branches. In some embodiments, less than about 0.5 percent of
the total number of branches are neither ethyl nor methyl
groups.
[0462] C.4. Aliphatic Anionic Surfactants
[0463] In an embodiment, an aliphatic anionic surfactant may be
used in a hydrocarbon recovery composition. In certain embodiments,
an aliphatic portion of an aliphatic anionic surfactant may have an
average carbon number from 10 to 24. In some embodiments, an
aliphatic portion of an aliphatic anionic surfactant may have an
average carbon number from 12 to 18. In other embodiments, an
aliphatic portion of an aliphatic anionic surfactant may have an
average carbon number from 16 to 17. In some embodiments, the
aliphatic anionic surfactant may include a branched aliphatic
portion. In some embodiments, a branched aliphatic group of an
aliphatic anionic surfactant may have less than about 0.5 percent
aliphatic quaternary carbon atoms. In an embodiment, an average
number of branches per aliphatic anionic surfactant ranges from
about 0.1 to about 2.5. In other embodiments, an average number of
branches per aliphatic anionic surfactant ranges from about 0.7 to
about 2.5.
[0464] Methyl branches may represent between about 20 percent to
about 99 percent of the total number of branches present in the
branched anionic surfactant. In some embodiments, methyl branches
may represent greater than about 50 percent of the total number of
branches in a branched anionic surfactant. The number of ethyl
branches in the alcohol may represent, in certain embodiments, less
than about 30 percent of the total number of branches. In other
embodiments, the number of ethyl branches, if present, may be
between about 0.1 percent and about 2 percent of the total number
of branches. Branches other than methyl or ethyl, if present, may
be less than about 10 percent of the total number of branches. In
some embodiments, less than about 0.5 percent of the total number
of branches are neither ethyl nor methyl groups.
[0465] In an embodiment which further employs aliphatic anionic
surfactant, a solution may be provided which contains an effective
amount of an aliphatic anionic surfactant selected from the group
of compounds having the general formula:
R.sub.1O(C.sub.3H.sub.6O).sub.m(C.sub.2H.sub.4O).sub.nYX wherein
R.sub.1 is a linear or branched alkyl radical, an alkenyl radical,
or an alkyl or alkenyl substituted benzene radical, the
non-aromatic portion of the radical containing from 6 to 24 carbon
atoms; m has an average value of from 1 to 10; n has an average
value of from 1 to 10; Y is a hydrophilic group; and X is a cation,
preferably monovalent, for example N, K, NH.sub.4.sup.+. Y is a
suitable hydrophilic group or substituted hydrophilic group such
as, for example, the sulfate, sulfonate, phosphonate, phosphate or
carboxylate radical. Preferably, R.sub.1 is a branched alkyl
radical having at least two branching groups and Y is a sulfonate
or phosphate group.
[0466] C.5. Other Optional Additives for Enhanced Oil Recovery
[0467] The aqueous fluid of the present invention may, optionally,
further comprise clay stabilization or sand stabilization material.
During oil recovery processes, sands and other materials may become
entrained in the recovered oil. This may be mitigated by the
addition of a clay stabilization or sand stabilization material.
Suitable clay stabilization or sand stabilization materials include
epoxy resins, polyfunctional cationic polymers, such as
poly(N-acrylamidomethyltnrnethyl ammonium chloride) or
poly(vinylbenzyltrimethyl ammonium chloride).
[0468] Other optional ingredients that may be added to the aqueous
fluid of the present invention include, but are not limited to
polymers such as biopolysaccharides, cellulose ethers,
acrylamide-derived polymers, corrosion inhibitors, oxygen
scavengers, bactericides, and so forth, and any combination
thereof.
[0469] The aqueous fluid of the present invention is introduced
into the crude oil-bearing formation, typically by injecting the
fluid into the formation.
[0470] In the case of a carbonate formation having hydrophobic
surfaces, addition of the organophosphorous material to the aqueous
flooding fluid modifies such surfaces to increase the surface
energy of such surfaces and render such surfaces more readily
wettable by water. The surface modified formation more readily
imbibes the aqueous flooding fluid, thus increasing the amount of
aqueous fluid imbibed by the formation and increasing the amount of
crude oil displaced from the formation by the aqueous fluid.
[0471] The aqueous fluid may be used in secondary or tertiary oil
recovery processes, although the use of such fluids in other
applications is also not excluded.
[0472] C.6. Methods of Use for Enhanced Oil Recovery
[0473] The aqueous medium utilized to form the solution including
the organophosphorous material of the invention can be soft water,
brackish water, or a brine. The aqueous fluid of the present
invention is introduced into the crude oil-bearing formation,
typically by injecting the fluid into the formation.
[0474] Optionally, after injection of the aqueous fluid comprising
the present phosphate esters of the present invention addition to
crude oil having generally the viscosity of the oil-bearing
formation of the oil well to be treated, various hydrocarbon
solvents may be employed to displace the aqueous solution out into
the reservoir. Such hydrocarbon solvents as the low molecular
weight, generally liquid hydrocarbons boiling below the gasoline
range, such as the lower alkanes including butane, propane,
pentane, hexane and heptane, as well as natural gasoline, petroleum
naphtha and kerosene or mixtures of these hydrocarbons, are useful.
Both sweet and sour crude oil is useful as a hydrocarbon to
displace the aqueous solution out into the subterranean reservoir
of oil or gas.
[0475] Optionally, injection of a preflush fluid may be utilized
prior to injection of the aqueous fluid of the present invention.
The preflush may consist of a hydrocarbon fluid, a brine solution,
or simply water.
[0476] Also, injection of the aqueous fluid comprising the present
phosphate esters may optionally be followed by an injection of a
surfactant, a mobility control fluid or a polymeric flush, which is
typically a polymer-thickened aqueous solution, using, for example
the polymers disclosed above, into the formation to further enhance
oil recovery. The polymeric solution is utilized to drive or push
the now oil bearing surfactant flood out of the reservoir, thereby
"sweeping" crude oil out of the reservoir. Further, the polymeric
solution has a very high viscosity which helps to prevent what is
referred to in the industry as channeling or "fingering", thus
improving sweep efficiency.
[0477] This polymeric flush or mobility control fluid may once
again be followed by a water flush which may be brine or saline or
softened water, or fresh water.
[0478] Oil is recovered at a production well to be spaced apart
from the injection well as the drive fluid pushes the mobility
buffer slug which sweeps the oil out of the pores in the formation
and to the production well. Once the water/oil emulsion reaches the
surface, it is put into holding tanks where it is subsequently
demulsified, thereby allowing the oil to separate from the water
through the natural forces of gravity.
[0479] For example, a hydrocarbon recovery composition including
the phosphate esters of the present invention may be added to a
portion of hydrocarbon containing formation that may have an
average temperature of less than 80.degree. C. To facilitate
delivery of an amount of the hydrocarbon recovery composition to
the hydrocarbon containing formation, the hydrocarbon composition
may be combined with water or brine to produce an injectable fluid.
Typically about 0.01 to about 5 wt % of the phosphate ester, based
on the total weight of injectable fluid, may be injected into the
hydrocarbon containing formation through an injection well. In
certain embodiments, the concentration of the hydrocarbon recovery
composition injected through the injection well may be about 0.05%
to about 3 wt. %, based on the total weight of injectable fluid. In
some embodiments, the concentration of the hydrocarbon recovery
composition may be about 0.1% to about 1 wt. % based on the total
weight of injectable fluid.
[0480] In some embodiments, a hydrocarbon recovery composition may
be added to a portion of a hydrocarbon containing formation.
[0481] XI. Home Care or Industrial Care Compositions
[0482] In one embodiment, the present invention is directed to a
home care or industrial cleaning composition, such as a liquid
detergent, a laundry detergent, a hard surface cleanser, a dish
wash liquid, or a toilet bowl cleaner, comprising water, one or
more surfactants, and a polymer of the present invention. Suitable
surfactants include those described above in regard to the personal
care composition embodiments of the present invention. Such
cleaning compositions may optionally further comprise one or more
of water miscible organic solvents, such as alcohols and glycols,
and/or one or more additives.
[0483] Suitable additives are known in the art and include, for
example, organic builders, such as organophosphonates, inorganic
builders, such as ammonium polyphosphates, alkali metal
pyrophosphates, zeolites, silicates, alkali metal borates, and
alkali metal carbonates, bleaching agents, such as perborates,
percarbonates, and hypochlorates, sequestering agents and
anti-scale agents, such as citric acid and
ethylenediaminetetraacetic acid, inorganic acids, such as
phosphoric acid and hydrochloric acid, organic acids, such as
acetic acid, abrasives, such as silica or calcium carbonate,
antibacterial agents or disinfectants, such as triclosan and
cationic biocides, for example (N-alkyl)benzyldimethylammonium
chlorides, fungicides, enzymes, opacifing agents, pH modifiers,
dyes, fragrances, and preservatives.
[0484] In an embodiment the home care or industrial cleaner benefit
agent is selected from the group consisting of soil release agents,
fabric softener, surfactants, builders, binders, bleach and
fragrances.
[0485] In an embodiment the home care or industrial cleaning
composition for cleaning fabrics or hard surfaces comprising, the
composition of the present invention and a surfactant and a home
care or industrial cleaner benefit agent.
[0486] In an embodiment the composition is a detergent composition
and comprises: the polymer, at least one detersive surfactant, and
a builder.
[0487] The invention also encompasses a method for cleaning a
substrate selected from the group consisting of a hard surface and
a fabric, comprising applying the composition of the present
invention to the substrate.
[0488] Examples of the prevent invention are set forth below.
Unless otherwise indicated, all parts, percentages, and proportions
herein are by weight.
EXAMPLES
[0489] Preparation of mono-[2-(methacryloyloxy)ethyl]phthalate
(also known as 2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP)
Example 1
Imidazole as Catalyst
[0490] To a 0.5 liter jacketed reactor equipped with mechanical
stirrer, condenser and addition funnel was added 2-hydroxyethy
methacrylate (100 g, 0.77 mol) and 4-methoxyphenol (MEHQ) (0.16 g).
The mixture was stirred with the initiation of 8% Oxygen in
Nitrogen sub-surface purge. The mixture was heated to a set point
of 80.degree. C. and phthalic anhydride (39 g, 0.26 mol) was added
through an addition funnel. Imidazole (1.57 g, 0.023 mol) was added
to the mixture, resulting in an immediate exotherm. Additional
phthalic anhydride (78 g, 0.53 mol) was added through the addition
funnel over a 10 min. period. The reaction mixture was heated at
76.degree. C. for 5 hours, allowed to cool and the MAEP product was
isolated as a clear colorless viscous liquid (210 g). .sup.1H NMR
(CDCl.sub.3), 400 MHz, ppm; 7.89 (1H, d, J=6.2 Hz), 7.69 (1H, d,
J=7.1 Hz), 7.62-7.55 (2H, m), 6.12 (1H, s), 5.55 (1H, s), 4.58-4.56
(2H, m) 4.46-4.44 (2H, m), 1.91 (3H, s). Only residual quantities
of 2-hydroxyethyl methacrylate and phthalic anhydride were observed
in this isolated product.
Example 2
2,6-Di-Tert-Butyl-4-((Dimethylamino)Methyl)Phenol as Catalyst
[0491] To a 0.25 liter 4-neck round bottom flask equipped with
mechanical stirrer, condenser and heating mantel was added
2-hydroxyethy methacrylate (20 g, 0.153 mol). Stirring was
initiated along with 8% Oxygen in Nitrogen sub-surface purge.
[0492] 2,6-di-tert-butyl-4-((dimethylamino)methyl)phenol (1.2 g,
4.6 mmol) was added and the mixture was heated to a set point of
80.degree. C. Phthalic anhydride (23.6 g, 0.16 mol) was then added
over a ten minute period. The reaction mixture was heated at
82.degree. C. for an additional 5 hours, allowed to cool and the
MAEP product was isolated as a clear viscous liquid (41.3 g).
.sup.1H NMR consistent with that of Example 1.
Example 3
2,4,6-Tris((Dimethylamino)Methylphenol as Catalyst
[0493] To a 0.25 liter 4-neck round bottom flask equipped with
mechanical stirrer, condenser and heating mantel was added
2-hydroxyethy methacrylate (20 g, 0.153 mol). Stirring was
initiated along with 8% Oxygen in Nitrogen sub-surface purge.
2,4,6-tris((dimethylamino)methylphenol (0.41 g, 1.5 mmol) was added
and the mixture was heated to a set point of 82.degree. C. Phthalic
anhydride (23.6 g, 0.16 mol) was then added over a ten minute
period. The reaction mixture was heated at 82.degree. C. for an
additional 5 hours, allowed to cool and the MAEP product was
isolated as a clear viscous liquid (40.5 g). .sup.1H NMR consistent
with that of Example 1.
[0494] The following examples evaluate of
mono-[2-(methacryloyloxy)ethyl]phthalate (also known as
2-(2-carboxybenzoyloxy)ethyl methacrylate, MAEP) and
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate (MAHP)
Example 4
Preparation of HASE Systems
[0495] The typical polymerization ingredients and amounts used to
make experimental HASE polymers for evaluation are summarized in
TABLE 1.
TABLE-US-00001 TABLE 1 Ingredient Active weight ingredient
Ingredients Concentration (grams) weight (grams) KETTLE CHARGE
Deionized water 100% 160.00 160.00 RHODAPEX AB20 29% 1.01 0.29
Ammonium persulfate 100.00% 0.26 0.26 MONOMER EMULSION Deionized
water 100% 107.22 RHODAPEX AB20 29% 1.01 0.29 Methyl acrylic acid
29.20 29.20 Ethyl acrylate 81.76 81.76 Hydrophobic Monomer
50.00%.sup. 11.68 5.84 MAEP or MAHP 82.00%.sup. 29.20 INITIATOR
SOLUTION Deionized water 30.00 30.00 Ammonium persulfate 0.37 0.37
CHASER SOLUTION Part 1 Terbutyl 0.51 0.51 peroxybenzoate Part 2
Isoascorbic acid 0.26 0.26 (araboascorbic acid) Deionized water
8.76 8.76 Total 461.24 Theoretical Solids 30.1% Scale-up factor
1.46 Seed 2.0% ME 5.20 .sup. 25.0% IS 7.59
[0496] The HASE polymers are each made according to the following
procedure. Add heat to kettle charge to about 80.degree. C. while
purging with N.sub.2. Maintain N.sub.2 blanket throughout run. At
about 80.degree. C., add 25% Initiator solution and 2% Monomer
emulsion. Hold at that temperature for about 15 minutes. Feed
remainder of monomer emulsion and initiator solution over 3 hours.
Hold for 30 minutes, and add the chaser solution. Finally, heat to
about 80.degree. C. and hold for 30 minutes, and allow cooling.
[0497] In TABLE 1 RHODAPEX AB20 is a commercially available
sulfated alcohol ethoxylate surfactant from Rhodia. Ammonium
persulfate is an initiator. The initiator and chaser solutions are
provided to convert left over monomers to oligomerize them to
reduce VOCs. If desired to avoid the initiator and chaser solutions
excess monomer could be removed by stripping. ME is an abbreviation
for monomer emulsion. IS is an abbreviation for initiator
solution.
[0498] MAEP is mono-[2-(methacryloyloxy)ethyl]phthalate. MAHP is
mono-[2-(Methacryloyloxy)ethyl hexahydro]phthalate. These are
embodiments of first acidic monomers.
[0499] Methyl acrylic acid is an embodiment of a second acidic
monomer.
[0500] Ethyl acrylate is an embodiment of a nonionic,
copolymerizable C2-C12 alpha, beta-ethylenically unsaturated
monomer.
[0501] The hydrophobic monomer of Example 4 is a Nopol alkoxylate
according to structure (VI):
##STR00041##
[0502] The Nopol alkoxylate is made as follows: Nopol is
alkoxylated with propylene oxide and ethylene oxide charged to a
glass flask equipped with a PTFE blade agitator, temperature
sensor, dry compressed air purge line and a water cooled condenser.
The liquid ethoxylate is warmed, stirred, and MEHQ is added. A
purge of dry air is passed through the liquid and later methacrylic
anhydride is added. The temperature is stabilized and held between
70-74.degree. C. for five and a half hours, and then the liquid is
cooled. Methacrylic acid and water are added and the liquid product
is discharged.
[0503] TABLE 2A and TABLE 2B show results of latex characterization
of HASE polymers as thickeners synthesized from ingredients
generally in accordance with TABLE 1 such as MAEP or MAHP as a
first acidic monomer, methyl acrylic acid as a second acidic
monomer, ethyl acrylate as a nonionic, copolymerizable C2-C12
alpha, beta-ethylenically unsaturated monomer, and a hydrophobic
monomer. However, the hydrophobic monomer is Hydrophobic Monomer 1
having formula VIa:
##STR00042##
[0504] In TABLEs 2A and 2B Particle Size is average particle size.
PDI is polydispersity index. ME is an abbreviation for monomer
emulsion. % Coagulum is % undesired solids.
TABLE-US-00002 TABLE 2A Latex characterization of HASE thickeners
synthesized from methyl acrylic acid, ethyl acrylate, Hydrophobic
Monomer 1, and MAEP HASE Z-Average % Solids Polymer Particle Size
PDI % Coagulum Content 1.sup.a 164.2 0.014 0.0698 30.66 2.sup.b
123.9 0.019 0.109 31.65 3.sup.c 156.1 0.019 0.202 32.09 4.sup.d
173.1 0.012 0.102 31.52 5.sup.e 131.9 0.04 0.0891 33.52 6.sup.f 124
0.047 0.161 33.04 7.sup.g 137 0.029 0.256 33.98 .sup.aPolymer
synthesized using 1:0 MAEP/MAA ratio .sup.bPolymer synthesized
using 1:1 MAEP/MAA ratio .sup.cPolymer synthesized using 1:3
MAEP/MAA ratio .sup.dPolymer synthesized using 1:9 MAEP/MAA ratio
.sup.ePolymer synthesized using 1:1 MAEP/MAA ratio (less initiator
added) .sup.fPolymer synthesized using 1:1 MAEP/MAA ratio (more
Hydrophobic Monomer 1 added) .sup.gPolymer synthesized using 1:1
MAEP/MAA ratio (less initiator and more Hydrophobic Monomer 1
added)
TABLE-US-00003 TABLE 2B Latex characterization of HASE Polymers
8-12 synthesized from methyl acrylic acid, ethyl acrylate,
Hydrophobic Monomer 1, and MAEP or MAHP HASE Z-average % Solids
Polymer Particle Size PDI pH % Coagulum Content 8.sup.h 161.30
0.024 2.06 0.037 31.87 9.sup.i 174.70 0.070 2.11 0.050 32.63
10.sup.j 199.7 0.071 2.60 0.158 31.29 11.sup.k 147.30 0.021 2.38
0.024 30.54 12.sup.l 147.6 0.005 2.70 0.010 30.10 .sup.hPolymer
synthesized using 1:1 MAEP/MAA ratio .sup.iPolymer synthesized
using 1:3 MAEP/MAA ratio .sup.jPolymer synthesized using 0:1
MAEP/MAA ratio (control) .sup.kPolymer synthesized using 1:0
MAEP/MAA ratio .sup.lPolymer synthesized using 1:0 MAHP/MAA
ratio
Example 5
Sample Preparation for Thickening Efficiency (KU)
[0505] Formulation preparation combined 108 grams Binder latex
(RHOPLEX SG30)+61 grams Deionized water+HASE polymer as a
thickener. The binder latex RHOPLEX SG30 is an acrylic emulsion
available from the Dow Chemical Company.
[0506] TABLES 3A and 3B show thickening efficiency in RHOPLEX
SG30.
[0507] TABLE 3A lists Examples A-F which employed HASE Polymers 2-7
of TABLE 2A above.
[0508] TABLE 3B lists Examples G-K which employed HASE Polymers
8-12 of TABLE 2B above.
[0509] The HASE polymer was added as a thickener until a KU
viscosity of 95 +- 2 and pH=9-9.3 was reached.
TABLE-US-00004 TABLE 3A Thickening Efficiency of HASE Polymer in
RHOPLEX SG30 Acrylic Emulsion Binder and KU ICI HASE Polymer HASE
Efficiency Visc. Visc. BV (LV 4 System Polymer (g) pH (KU) (P) @ 60
RPM) A 2.sup.a 3.55 9.02 93.5 2.2 3249 B.sup.b 3.sup.b 3.3 9.174
95.7 1.6 3439 C 4.sup.c 3.16 9.462 96.4 0.50 3339 D 5.sup.d 3.14
9.28 94.2 0.80 3759 E 6.sup.e 3.78 9.004 95.4 0.6 3959 F 7.sup.f
31.0 9.255 93.2 0.60 4209 .sup.aPolymer synthesized using 3:1
MAEP/MAA ratio .sup.bPolymer synthesized using 1:3 MAEP/MAA ratio
.sup.cPolymer synthesized using 1:9 MAEP/MAA ratio .sup.dPolymer
synthesized using 1:1 MAEP/MAA ratio (less initiator added)
.sup.ePolymer synthesized using 1:1 MAEP/MAA ratio .sup.fPolymer
synthesized using 1:1 MAEP/MAA ratio (less initiator and more
Hydrophobic Monomer 1 added)
TABLE-US-00005 TABLE 3B Thickening Efficiency of HASE Polymer in
RHOPLEX SG30 Acrylic Emulsion Binder and KU ICI BV HASE Polymer
HASE Efficiency Visc. Visc. (LV 4 @ System Polymer (g) pH (KU) (P)
60 RPM) G 8.sup.h 3.71 9.02 93.2 0.40 3359 H 9.sup.i 3.04 9.05 95.3
0.40 3299 I 10.sup.j 2.77 9.25 96.4 0.50 3339 J 11.sup.k 21.47 9.15
94.2 0.80 3759 K 12.sup.l 31.0 9.16 93.5 0.60 4209 .sup.hPolymer
synthesized using 1:1 MAEP/MAA ratio .sup.iPolymer synthesized
using 1:3 MAEP/MAA ratio .sup.jPolymer synthesized using 0:1
MAEP/MAA ratio (control) .sup.kPolymer synthesized using 1:0
MAEP/MAA ratio .sup.lPolymer synthesized using 1:0 MAHP/MAA
ratio
[0510] FIG. 1 shows Viscosity Profiles of Formulations prepared
with HASE thickeners containing EGMHPT and MEPHM (in RHOPLEX
SG30).
[0511] FIG. 2 show Yield Stresses of Formulations prepared with
HASE thickeners containing MAEP and MAHP (in RHOPLEX SG30).
[0512] FIG. 3 shows thixotropic measurement of Binder and HASE
Polymer System K of HASE polymer 12 in RHOPLEX SG30 (couette). In
this example: Temperature was 25.0 degrees C. Couette flow refers
to the laminar flow of a viscous fluid in the space between a bob
and cup, one of which is moving relative to the other.
[0513] FIG. 4 shows the measurement of Binder and HASE Polymer
System J of HASE polymer 11 in RHOPLEX SG30 (couette). In this
example Temperature was 25.0 degrees C.
[0514] The data shows HASE thickeners incorporating MAEP and
Methacrylic Acid (MAA) show good thickening efficiency.
[0515] It should be apparent embodiments other than those expressly
described above come within the spirit and scope of the present
invention. Thus, the present invention is not defined by the above
description but by the claims appended hereto.
* * * * *