U.S. patent application number 09/882418 was filed with the patent office on 2002-05-09 for rheology modifier for use in aqueous compositions.
This patent application is currently assigned to ISP INVESTMENTS INC.. Invention is credited to Hood, David K., Kittrick, John Mc, Kopolow, Stephen L., Kwak, Yoon Tae, Patel, Drupesh, Senak, Laurence, Tallon, Michael.
Application Number | 20020055585 09/882418 |
Document ID | / |
Family ID | 46277751 |
Filed Date | 2002-05-09 |
United States Patent
Application |
20020055585 |
Kind Code |
A1 |
Hood, David K. ; et
al. |
May 9, 2002 |
Rheology modifier for use in aqueous compositions
Abstract
A rheology modifier for use in aqueous or alcoholic compositions
includes an aqueous two-phase polymeric composition of by weight,
5-75 % of (a) a water-soluble polymer having (b) in situ-formed,
substantially water-insoluble resinous particles of said polymer
substantially uniformly dispersed therein, and (c) 25-95 % of
water.
Inventors: |
Hood, David K.; (Basking
Ridge, NJ) ; Kopolow, Stephen L.; (Plainsboro,
NJ) ; Tallon, Michael; (Aberdeen, NJ) ; Kwak,
Yoon Tae; (Woodcliff Lake, NJ) ; Senak, Laurence;
(West Orange, NJ) ; Patel, Drupesh; (Jersey City,
NJ) ; Kittrick, John Mc; (Jersey City, NJ) |
Correspondence
Address: |
INTERNATIONAL SPECIALTY PRODUCTS
Att: William J. Davis, Esq.
Legal Department, Building No. 10
1361 Alps Road
Wayne
NJ
07470
US
|
Assignee: |
ISP INVESTMENTS INC.
|
Family ID: |
46277751 |
Appl. No.: |
09/882418 |
Filed: |
June 15, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09882418 |
Jun 15, 2001 |
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09663010 |
Sep 15, 2000 |
|
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09882418 |
Jun 15, 2001 |
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09784268 |
Feb 15, 2001 |
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Current U.S.
Class: |
524/804 |
Current CPC
Class: |
A61K 2800/413 20130101;
C08L 33/00 20130101; B41M 5/5254 20130101; C08F 26/10 20130101;
B41M 5/5272 20130101; B41M 5/52 20130101; C08J 2300/14 20130101;
B41M 5/5227 20130101; C08J 3/03 20130101; B41M 5/529 20130101; A61K
8/817 20130101; B82Y 5/00 20130101; A61K 8/8176 20130101; A61Q 5/12
20130101; B41M 5/5245 20130101; C08F 26/06 20130101; A61Q 17/04
20130101; A61K 8/8182 20130101; C09D 133/14 20130101 |
Class at
Publication: |
524/804 |
International
Class: |
C08K 003/00 |
Claims
What is claimed is:
1. A rheology-modified composition including an aqueous or
alcoholic polymeric composition which forms a clear to translucent
film upon application to a substrate comprising, by weight, 5-75%
of (a) a water-soluble polymer having (b) in situ-formed,
substantially water-insoluble resinous particles of said polymer
substantially uniformly dispersed therein, and (c) 25-95% of
water.
2. A composition according to claim 1 wherein said polymer is
polyvinylpyrrolidone (PVP).
3. A composition according to claim 1 wherein said polymer is
poly(vinylcaprolactam) (PVCL).
4. A composition according to claim 1 wherein said polymer is a
copolymer of PVP or PVCL, and, optionally, one or more
comonomers.
5. A composition according to claim 4 wherein said comonomer is
dimethylaminopropyl(meth)acrylamide (DMAPMA) and
dimethylaminoethyl(meth)- acrylate (DMAEMA).
6. A composition according to claim 1 wherein said polymer is a
copolymer of PVP and PVCL, and, optionally, one or more
comonomers.
7. A composition according to claim 1 wherein said particles are
<500.mu..
8. A composition according to claim 7 wherein said particles are
<100.mu..
9. A composition according to claim 7 wherein said particles are
>1 nm and <500.mu..
10. A composition according to claim 1 wherein said substantially
water-insoluble polymer is a crosslinked or branched polymer.
11. A composition according to claim 1 wherein said polymer is
neutralized and/or functionally neutralized and/or quaternized,
and/or functionalized quaternized.
12. A composition according to claim 1 wherein the ratio of (a):(b)
is 20-95% to 5-80%.
13. A composition according to claim 12 wherein said ratio is
20-75% to 25-80%.
14. A composition according to claim 10 wherein said crosslinking
agent is a substantially water-insoluble compound.
15. A composition according to claim 14 wherein said crosslinking
agent is pentaerythritol triallyl ether (PETE), or pentaerythritol
tetraacrylate (PETA).
16. A composition according to claim 11 wherein said functional
neutralization acid is a UV active based upon derivatives of
cinnamic and/or benzoic and/or sulfonic and/or acetic and/or
terephthalic and/or maleic acids.
17. A composition according to claim 11 wherein said functional
neutralization acid is a pharmaceutically active acid.
18. A composition according to claim 11 wherein said functional
neutralization acid contains silicone.
19. A composition according to claim 15 wherein said crosslinking
agent is present in an amount of 0.02-0.5% by weight of said
composition.
20. A composition of claim 19 wherein said amount is 0.05-0.3%.
21. A composition of claim 1 having a Brookfield viscosity of 1,000
to 45,000 cps.
22. A composition of claim 21 wherein said viscosity is 2,000 to
20,000.
23. A composition of claim 1 wherein said polymer is a vinyl lactam
polymer, optionally copolymerized with a methacrylate/acrylate
and/or methacrylamide/acrylamide comonomer.
Description
CROSS-REFERENCE TO RELATED U.S. PATENT APPLICATIONS
[0001] This application is a continuation-in-part of co-pending
U.S. patent applications Ser. Nos. 09/663,010, filed Sep. 15, 2000,
and 09/784,268, filed Feb. 15, 2001.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to rheology modifiers used to adjust
the rheological properties of polymeric compositions, and, more
particularly, to non-continuous, vinyl lactam polymeric
compositions with two-phases therein, having advantageous rheology
properties in commercial applications.
[0004] 2. Description of the Prior Art
[0005] Rheology modifiers are used generally to adjust or modify
the rheological properties of aqueous compositions. Such properties
include, without limitation, viscosity, flow rate, stability to
viscosity change over time, and the ability to suspend particles in
such aqueous compositions. The particular type of modifier used
usually depends on the particular aqueous composition to be
modified and on the end-use of the modified aqueous composition.
Examples of conventional rheology modifiers include thickeners such
as cellulosic derivatives, polyvinyl alcohol, sodium polyacrylate,
and other water-soluble macromolecules, and copolymeric emulsions
in which monomers with acid groups have been introduced onto the
main chain. Such thickeners are used widely in fiber treatment and
adhesives.
[0006] The rheological properties of concentrated dispersions are
critical to many important commercial applications. Examples
include coatings, inks, films, oils, paints, food additives and
pharmaceuticals. Accordingly, the microscopic and macroscopic
dispersion structure and the resulting flow properties of such
systems are of both scientific and practical interest. The art has
established that sub-micron particles in such systems can have a
dramatic effect on the rheology of a polymeric solution or fluid.
Several physical critical parameters have been identified as
influencing its rheology, including the dispersed particle volume
fraction, particle size shape and distribution, the continuous
phase viscosity and the fluid flow field. By altering or adjusting
these microscopic parameters, certain macroscopic phenomena such as
elasticity, shear thinning, thixotropic effect and shear thickening
can be modified for a particular application or to exhibit a
desired property.
[0007] Polymeric compositions of vinyl lactam monomers generally
are one-phase, soluble, high viscosity materials. These
compositions are useful in a variety of commercial applications
such as film formers, dye transfer inhibitors, dispersants,
excipients and drug delivery. Aqueous gels of these monomers can
also be prepared by light covalent or associative crosslinking of
polymer chains resulting in one-phase materials of high viscosity
which are effective thickeners in personal care formulations,
particularly hair care products.
[0008] The prior art in this field is represented by the following
patents.
[0009] Niessner, in U.S. Pat. Nos. 5,149,750 and 5,180,804,
disclosed finely divided, water-swellable gel-like, water-swellable
copolymers by polymerization of comonomers in the presence of a
surfactant.
[0010] Liu, in U.S. Pat. No. 5,997,855, described a homogeneous
terpolymer for hair care use, however, without a crosslinking
agent.
[0011] Kopolow, in U.S. Pat. No 5,130,121, described personal care
compositions containing a stabilized cosmetically-active product
obtained by in situ polymerization of a water-soluble vinyl monomer
in the presence of discrete microdroplets of a cosmetically-active
oil in water.
[0012] Blankenburg, in U.S. Pat. Nos. 5,635,169 and 6,107,397,
described uncrosslinked aqueous copolymer dispersions of nonionic
water-soluble monomers with N-vinyl groups and hydrophobic
monomers.
[0013] Steckler, in U.S. Pat. No. 3,878,175, disclosed highly
absorbent spongy gel polymer materials by simultaneous
copolymerization and partial crosslinking of a comonomer mixture of
an alkyl acrylate and a heterocyclic N-vinyl monomer containing a
carbonyl functionality in the presence of a hydrophobic liquid
diluent in which the final polymer is insoluble.
[0014] Markus, in U.S. Pat. No. 2,810,716, described a process for
making swellable resins by copolymerizing monomers in the presence
of a water-soluble non-redox divalent-ion containing salt.
[0015] Tseng, in U.S. Pat. Nos. 5,393,854 and 5,717,045, disclosed
a one-phase, aqueous gel of crosslinked copolymers of vinyl
pyrrolidone and dimethylaminoethyl methacrylate for use in hair
care products. The crosslinking agent was 1-vinyl-3-(E)-ethylidene
pyrrolidone. The gels had a Brookfield viscosity of between 60,000
and 100,000.
[0016] These references illustrate the desire of the art to produce
a continuous network of polymer molecules, or microgel, which is a
one-phase system, and of high viscosity.
[0017] Accordingly, it is an object of this invention to provide a
new and improved rheology modifier composition to adjust the
rheological properties of commercial products.
[0018] A particular object of the present invention is to provide a
rheology modifier which is an aqueous polymeric composition of a
water-soluble polymer, and including in situ-formed, minute
resinous particles dispersed therein, that, under suitable light
magnification, shows the presence of two-discrete phases therein,
one being the water soluble polymer and the other being
water-insoluble resinous particles.
IN THE DRAWINGS
[0019] FIG. 1 is a photomicrograph of the aqueous polymeric
composition of the invention showing the presence of two discrete
phases therein.
[0020] FIG. 2 is a graphical representation of Brookfield viscosity
of the invention composition vs. .PHI. the volume fraction of
particles in the composition.
SUMMARY OF THE INVENTION
[0021] What is described herein is a rheology modifier for use in
aqueous or alcoholic compositions which includes a stable, aqueous
polymeric composition which forms a clear to translucent film upon
application to a substrate comprising, by weight, 5-75% of (a) a
water-soluble polymer having (b) in situ-formed, substantially
water-insoluble resinous particles of said polymer substantially
uniformly dispersed therein, and (c) 25-95% of water.
[0022] Preferably, the polymer is polyvinylpyrrolidone (PVP),
poly(vinylcaprolactam) (PVCL), a copolymer of PVP and/or PVCL, and,
optionally, one or more comonomers, including comonomers such as
dimethylaminopropyl(meth)acrylamide (DMAPMA) and
dimethylaminoethyl(meth)- acrylate (DMAEMA). Preferably, the
polymer is a vinyl lactam polymer, optionally copolymerized with a
methacrylate/acrylate and/or methacrylamide/acrylamide
comonomer.
[0023] In this invention, the composition includes particles having
a size of <500.mu., preferably <100.mu., and optimally
between >1 nm and <500 .mu..
[0024] Suitably, the composition includes a substantially
water-insoluble polymer which is a crosslinked or branched polymer,
neutralized and/or quaternized, and/or functionalized quaternized.
The ratio of (a):(b) is 20-95% to 5-80%, preferably 20-75% to
25-80%, and the crosslinking agent is a substantially
water-insoluble compound, preferably pentaerythritol triallyl ether
(PETE), or pentaerythritol tetraacrylate (PETA), preferably at
least partially soluble in water, and the crosslinking agent is
present in an amount of 0.02-0.5% by weight of said composition,
most preferably 0.05-0.3%.
[0025] In this invention, the composition, prior to modification,
has a Brookfield viscosity of 1,000 to 45,000 cps, preferably 2,000
to 20,000.
[0026] As a feature of the invention, there is provided herein a
process for making a stable, aqueous polymeric composition which
includes the steps of providing a reaction mixture of a
water-soluble vinyl monomer, optionally with one or more
water-soluble comonomers, a predetermined amount of a crosslinking
agent and water, heating the mixture, then periodically adding a
predetermined amount of an initiator, and polymerizing at about
30-130.degree. C., optionally further including the step of
diluting with water during or after the polymerization.
[0027] Suitably, the crosslinking agent is present in an amount of
0.02-0.5 wt. % based on monomers present, and preferably is PETE or
PETA, and the initiator is an azo initiator.
[0028] Another feature of the invention is the provision of
formulations containing the above-described composition, made by
such process, and films of the composition on a substrate.
[0029] The compositions herein may be dried if desired to provide
the polymeric composition as a solid, and, if desired, the water
soluble polymer extracted with a solvent. The dried stable
polymeric composition thereby includes, by weight, (a) 20% to 95%
of a water-soluble polymer, and (b) 5% to 80% of in situ-formed,
substantially water-insoluble resinous particles of said polymer
substantially uniformly dispersed therein.
DETAILED DESCRIPTION OF THE INVENTION
[0030] In accordance with this invention, there is provided herein
an aqueous or alcoholic polymeric composition having two phases
therein, a water-soluble polymeric phase and a discrete,
water-insoluble polymer particle phase which is generated in-situ
during the polymerization of the monomers. In the preferred forms
of the invention, the polymerization is carried out in aqueous
solution of a vinyl lactam monomer, such as vinyl pyrrolidone or
vinyl caprolactam. Optionally a comonomer may be present to form a
copolymer. Suitable comonomers include methacrylate/acrylate
monomers, such as dimethylaminoethyl(meth)acrylate (DMAEMA) and/or
methacrylamide/acrylamide monomers, such as
dimethylaminopropylacrylamide (DMAPMA).
[0031] This stable, aqueous polymeric composition forms a clear to
translucent film upon application to a substrate and comprises, by
weight, 5-75% of (a) a water-soluble polymer having (b) in
situ-formed, substantially water-insoluble resinous particles of
said polymer substantially uniformly dispersed therein, and (c)
25-95% of water.
[0032] The invention will now be illustrated in more detail by
reference to the following examples.
EXAMPLE 1
Two-Phase Polymeric Composition of VP/DMAPMA
[0033] 1. To a 2-l kettle fitted with a nitrogen inlet tube,
thermocouple, agitator, and feed lines was added 87.15 g of vinyl
pyrrolidone monomer, (VP), 697 g DI water and 0.275 g (0.25% based
upon monomer) of pentaerythritol triallyl ether (PETE) as
crosslinker.
[0034] 2. Purged with nitrogen subsurface for 30 minutes.
[0035] 3. Heated to 70.degree. C.
[0036] 4. In a separate container weighed out 22.69 g of
dimethylaminopropyl methacrylamide (DMAPMA).
[0037] 5. With kettle temperature at 70.degree. C., stop subsurface
nitrogen purge and purged above surface. Precharged 1.1 g DMAPMA
from container.
[0038] 6. Started continuous addition of the remaining DMAPMA
(21.86 g) over 210 minutes at a flow rate 0.11 ml/minute. Once the
DMAPMA flow started, initiated with first shot of Vazo.RTM. 67 in
isopropanol (IPA) (Time 0).
[0039] 7. Initiator was added in 5 separate shots at 0, 30, 60, 150
and 210 minutes. 0.2 g of Vazo.RTM. 67 in 1.0 g IPA was added for
each shot and two 0.5 g IPA washes were made.
[0040] 8. Held the reaction temperature overnight at 70.degree.
C.
[0041] 9. When residual VP level was below 400 ppm, diluted the
batch with 266.7 g of DI water.
[0042] 10. Cooled batch to 50.degree. C.
[0043] 11. Neutralized the batch with conc. HCI to pH of 6.2-6.8 at
50.degree. C. Room temperature pH was 6.8-7.2. Required
approximately 14 g of conc. HCl.
[0044] 12. Added 0.15 to 0.19% BTC 50 NF as preservative.
[0045] 13. A two-phase, aqueous polymeric composition as shown in
the Figure was obtained.
EXAMPLE 2
[0046] The process of Example 1 was repeated using 5 separate shots
of 0.3 g each of Vazo.RTM. 67 in 1.0 g of IPA. A similar polymeric
composition as in Example 1.
EXAMPLE 3
[0047] The process of Example 1 was repeated using 5 separate shots
of 0.4 g each of Vazo.RTM. 67 in 1 g of IPA, and 0.3 g of
crosslinker. A similar polymeric composition was obtained.
[0048] Results
[0049] The results of these tests, shown in Table 1 below establish
that the 2-phase polymeric composition of the invention exhibits
advantageous viscosity properties.
1TABLE 1 Results The results of these tests, shown in Table 1 below
establish that the 2-phase polymeric composition of the invention
exhibits advantageous viscosity properties. Ex. Crosslinker
Initiator Viscosity No. (%) (g/shot) (cps) 1 0.25 0.2 28,200 2 0.25
0.3 13,000 3 0.3 0.4 12,800
EXAMPLE 4
Polymeric Composition of PVP
[0050] 1. To a 2-l kettle fitted with a nitrogen inlet tube,
thermocouple, agitator, and feed lines was added 131.81 g of VP,
756 g DI water and 0.197 g PETE (0.15% based upon monomer).
[0051] 2. Purged with nitrogen subsurface for 30 minutes.
[0052] 3. Heated to 70.degree. C.
[0053] 4. Initiator was added at 0 and 30 minutes. 0.48 9 of
Vazo.RTM. 67 in 1.5 g IPA was added for each shot and two 1.0 g IPA
washes were made.
[0054] 5. Held the reaction temperature overnight at 70.degree.
C.
[0055] 6. When residual VP was below 400 ppm, diluted the batch
with 320.04 g DI water.
[0056] 7. Cooled batch to 50.degree. C.
[0057] 8. Added 0.15 to 0.19% BTC 50 NF as preservative.
[0058] 9. The product was a 2-phase, polymerization composition
with 40 to 70% resinous particles, whose soluble fraction had a
weight average molecular weight of 1,200,000 to 1,500,000.
EXAMPLE 5
Polymeric Composition of VP/DMAPMA/Quaternized with Diethyl
Sulfate
[0059] 1. To a 2-l, kettle fitted with a nitrogen inlet tube,
thermocouple, agitator, and feed lines was added 96.00 g of VP,
702.7 g DI water and 0.36 g PETE (0.30% based upon monomer).
[0060] 2. Purged with nitrogen subsurface for 30 minutes.
[0061] 3. Heated to 70.degree. C.
[0062] 4. In a separate container weighed out 24.0 g DMAPMA and
74.7 g DI water. Purged with nitrogen.
[0063] 5. When kettle temperature was at 70.degree. C., stopped
subsurface nitrogen purge and purged above surface. Precharged 4.94
g DMAPMA/water from container.
[0064] 6. Started continuous addition of the remaining DMAPMA/water
(93.76 9) over 210 minutes. Flow rate 0.48 ml/minute. Once
DMAPMA/water flow started, initiated with first shot of Vazo.RTM.
67 in IPA (Time 0).
[0065] 7. Initiator was added at 0, 30, 60, 150 and 210 minutes.
0.44 g of Vazo 67 in 1.3 g IPA was added for each shot and two 0.7
g IPA washes were made.
[0066] 8. Held the reaction temperature overnight at 70.degree.
C.
[0067] 9. When residual VP was below 400 ppm, diluted the batch
with 297.5 g DI water.
[0068] 10. Cooled batch to 50.degree. C.
[0069] 11. Neutralized the batch with 19.56 g diethyl sulfate (DES)
over 60 minutes; at flow rate of 0.28 g/ml.
[0070] 12. Stirred for 2 hours.
[0071] 13. Product.
EXAMPLE 6
VP/DMAPMA/PETE Neutralized with Benzophenone-4
[0072] 1. To a 2-l kettle fitted with a nitrogen inlet tube,
thermocouple, agitator, and feed lines was added 87.15 g of HPVP,
630 g DI water and 0.33 g PETE (0.30% based upon monomer).
[0073] 2. Purged with nitrogen subsurface for 30 minutes.
[0074] 3. Heated to 70.degree. C.
[0075] 4. Weighed out 22.69 g DMAPMA and 67 g DI water. Purged with
nitrogen.
[0076] 5. When kettle temperature was at 70.degree. C., stopped
subsurface nitrogen purge and purged above surface. Precharged 4.23
g DMAPMA/water from container.
[0077] 6. Started a continuous addition of the remaining
DMAPMA/water (85.46 g) over 210 minutes. Flow rate 0.40 ml/minute.
Once DMAPMA/water flow started, initiated with first shot of
Vazo.RTM. 67 in IPA (Time 0).
[0078] 7. Initiator was added at 0, 30, 60, 150 and 210 minutes.
0.4 g of Vazo 67 in 1.0 g IPA was added for each shot and two 0.5 g
IPA washes were made.
[0079] 8. Held the reaction temperature overnight at 70.degree.
C.
[0080] 9. When residual VP was below 400 ppm, diluted the batch
with 266.7 g DI water.
[0081] 10. Cooled batch to 50.degree. C.
[0082] 11. Neutralized the batch with benzophenone-4, 5 to 99 mole
% (2 to 38.6 g respectively). Continued neutralization with
sulfuric acid to pH of 6.8 to 7.8 at 50.degree. C.
[0083] 12. Cooled and discharged.
[0084] 13. Product.
EXAMPLE 7
VP/DMAPMA/PETA
[0085] 1. To a 2-l kettle fitted with a nitrogen inlet tube,
thermocouple, agitator, and feed lines was added 104.58 g of HPVP,
756 g DI water and 0.59 g pentaerythritol tetraacrylate (0.30%
based upon monomer).
[0086] 2. Purged with nitrogen subsurface for 30 minutes.
[0087] 3. Heated to 70.degree. C.
[0088] 4. In a separate container, weighed out 27.23 g DMAPMA and
80.4 g DI water. Purged with nitrogen.
[0089] 5. When kettle temperature was at 70.degree. C., stopped
subsurface nitrogen purge and purged above surface. Precharged 5.38
g DMAPMA/water from container.
[0090] 6. Started continuous addition of the remaining DMAPMA/water
(102.25 g) over 210 minutes. Flow rate 0.52 ml/minute. Once
DMAPMA/water flow started, initiated with first shot of Vazo.RTM.67
in IPA (Time 0).
[0091] 7. Initiator was added at 0, 30, 60, 150 and 210 minutes.
0.16 g of Vazo.RTM. 67 in 1.0 g IPA was added for each shot and two
0.5 g IPA washes were made.
[0092] 8. Held the reaction temperature overnight at 70.degree.
C.
[0093] 9. When VP was below 400 ppm, diluted the batch with 266.7 g
DI water.
[0094] 10. Cooled batch to 50.degree. C.
[0095] 11. Neutralized the batch with conc. sulfuric acid to pH of
6.6 to 7.8 at 25.degree. C.
[0096] 12. Added 0.15 to 0.19% BTC 50 NF as preservative.
[0097] 13. Product.
EXAMPLE 8
Crosslinked Vinyl Caprolactam/DMAPMA Copolymer
[0098] 1. To a 2-l kettle fitted with a nitrogen inlet tube,
thermocouple, agitator and feed lines was added 130.7 g vinyl
caprolactam, 128.7 g DI water, 171.6 g ethanol, and 0.88 g PETE
(0.6% based upon monomer).
[0099] 2. Purged with nitrogen for 30 minutes.
[0100] 3. Heated to 70.degree. C.
[0101] 4. In a syringe pump was added 32.98 g DMAPMA and 171.6 g DI
water.
[0102] 5. At 70.degree. C. added 40 ml of the DMAPMA/water mixture
to the kettle and added the first shot of initiator, 0.075 g
Vazo.RTM. 67 in 0.75 g ethanol. Washed with 0.75 g ethanol.
[0103] 6. Started addition of the remaining DMAPMAlwater mixture
(Time 0) from the syringe pump at a rate of 0.34 ml/min, added over
480 minutes.
[0104] 7. At time 60, 120, 180, 240, 300, 360, 420 and 480 minutes
added a shot of Vazo.RTM. 67, 0.075 g in 0.75 g ethanol. Washed
with 0.75 g ethanol.
[0105] 8. Held at 70.degree. C. overnight.
[0106] 9. Cooled reaction to 30.degree. C. and added 415.6 g DI
water.
[0107] 10. Mixed until uniform and then added 544.4 g DI water and
15.38 g hydrochloric acid.
[0108] 11. Mixed for 2 hours. Adjusted pH to 6.6 to 7.8 with
hydrochloric acid, if necessary.
[0109] 12. Added 0.15 to 0.19% BTC-50 NF as preservative.
[0110] 13. Product.
EXAMPLE 9
VP/DMAEMA/PETE Process
[0111] 1. To a 2-l kettle fitted with a nitrogen inlet tube,
thermocouple, agitator, and feed lines is added 87.15 g of HPVP,
630 g DI water and 0.33 g (0.30% based upon monomer)
pentaerythritol triallyl ether.
[0112] 2. Purged with nitrogen subsurface for 30 minutes.
[0113] 3. Heated to 70.degree. C.
[0114] 4. In a separate container, weighed out 22.69 g DMAEMA and
67 g DI water. Purged with nitrogen.
[0115] 5. When kettle temperature was at 70.degree. C., stopped
subsurface nitrogen purge and purged above surface. Precharged 4.23
g DMAEMA/water from container.
[0116] 6. Started continuous addition of the remaining DMAEMA/water
(85.46 g) over 210 minutes. Flow rate 0.40 ml/minute. Once
DMAEMA/water flow started initiator addition with first shot of
Vazo 67 in IPA (Time 0).
[0117] 7. Initiator was added at 0, 30, 60, 150, and 210 minutes.
0.4 g of Vazo 67 in 1.0 g IPA was added for each shot and two 0.5 g
IPA washes were made.
[0118] 8. Held the reaction temperature overnight at 70.degree.
C.
[0119] 9. When VP was below 400 ppm, diluted the batch with 266.7 g
DI water.
[0120] 10. Cooled batch to 50.degree. C.
[0121] 11. Neutralized the batch with conc. HCl to pH of 6.2 to 6.8
at 50.degree. C. Room temperature pH will be 6.8 to 7.2. Required
approximately 14 g of conc. HCl.
[0122] 12. Added 0.15 to 0.19% BTC 50 NF as preservative.
EXAMPLE 10
Drying of Example 9
[0123] The solution of Example 9 was dried on a drum dryer to a
solids of >95%. The Tg of the powder was 167.degree. C. Then it
was reconstituted in water and found to provide the same
waterproofing as the original solution.
EXAMPLE 11
Particle Isolation and Properties
[0124] 95.2 g of approximately 10% solids polyvinylpyrrolidone/PETE
was diluted in 2-liters of distilled water and stirred until
thoroughly mixed. A second solution was prepared by taking 500 ml
of the first solution and diluting in 2-liters of distilled water.
Stirred until thoroughly mixed. Poured the second solution into
four 16 oz. jars and centrifuged at .about.2250 rpm for about 90
minutes. A white precipitate was observed on the bottom of each 16
oz. jar. The precipitate was removed, via pipette, and placed into
four 8-dram vials, respectively. The four 8-dram vials were
centrifuged at .about.3000 rpm for 60 minutes. The particle size on
the precipitate was measured using a Microtrak UPA and found to be
about 4 nm.
EXAMPLE 11A
[0125] The precipitate obtained in Example 11 in three 8-dram vials
was dried, in vacuo, in a 40.degree. C. oven overnight. The result
was a thin, generally clear film upon visual observation. This
material was then exposed to either methanol, diethyl ether and
n-heptane. After 24 hours, methanol had re-dispersed the material.
Diethyl ether and n-heptane did not appear to effect the dried
material. After 14 days, all samples exhibited a similar appearance
to the original 24 hour observations. The particle size on the
methanol dispersed material was measured using a Microtrak UPA and
found to be about 4 microns.
COMPARATIVE EXAMPLE 12
[0126] An aqueous solution of 119.64 g of vinyl pyrrolidone
monomer, 0.36 g pentaerythritol trially ether (PETE), 0.6 g of Vazo
67, and 480 g water was charged to a kettle and purged with
nitrogen. The reaction mixture was then heated to 65.degree. C.
while stirring at 650 rpm. Within 25 minutes the product became so
viscous that the reaction was stopped. The product was a continuous
gel only.
COMPARATIVE EXAMPLE 13
[0127] An aqueous solution of 119.64 g of vinyl pyrrolidone
monomer, 0.36 g pentaerythritol triallyl ether (PETE), 0.23 g of
Vazo 67, and 480 g water was charged to a kettle and purged with
nitrogen. The reaction mixture was then heated to 65.degree. C.
while stirring at 650 rpm. After 2 hours at 65.degree. C., the
reaction was heated to 95.degree. C. for 1 hour. The product was a
viscous solution only.
EXAMPLE 14
DPI Film Coating Formulation
[0128]
2 Ingredient Parts by Weight VP/DMAPMA/PETE (Ex. 1) 2.00 PV-OH (88%
hydrolyzed) 8.00 Sequrez .RTM. 755 (glyoxyl) 0.75 Water 89.25
100.00
EXAMPLE 15
UV Coating Formulation
[0129]
3 Ingredient Parts by Weight VP/DMAPMA/PETE/BENZO-4 (Ex. 6) 2.00
PV-OH (88% hydrolyzed) 8.00 Sequrez .RTM. 755 (glyoxyl) 0.75 Water
89.25 100.00
EXAMPLE 16
Sunscreen Cream
[0130]
4 Ingredients Wt. % PHASE A Deionized water 15.69 Disodium EDTA
0.10 Acrylates/Steareth-20 Methacrylate Copolymer 1.00 Acrylates
Copolymer 1.00 Hexylene Glycol 1.00 Glyceryl Polymethacrylate and
Propylene 0.50 Glycol and PVM/MA Copolymer
VP/DMAPMNPETE/Benzophenone-4 50.00 Copolymer (Ex. 6) PHASE B
Glyceryl Stearate and Behenyl Alcohol and 5.00 Palmitic and Stearic
Acid and Lecithin and Lauryl and Myristyl Alcohol and Cetyl Alcohol
Oxybenzone 3.00 Octyl Salicylate 3.00 Tridecyl Neopentanoate 2.00
Octyl Palmitate 6.00 Myristyl Myristate 1.00 PHASE C Deionized
Water 5.00 NaOH, 10% Solution 1.26 PHASE D Diazolidinyl Urea and
Iodopropynyl Butylcarbamate 0.50 Methyl Paraben 0.20 Hexylene
Glycol 1.00 PHASE E Fragrance 0.25
[0131] Procedure
[0132] 1. Combine ingredients in Phase A and heat to 70-75.degree.
C.
[0133] 2. Combine ingredients in Phase B and mix and heat to
70-75.degree. C.
[0134] 3. Add Phase B to Phase A under homogenization.
[0135] 4. Add Phase C to the batch under homogenization and
homogenize for 15 minutes.
[0136] 5. Switch to propeller mixing and cool to 45.degree. C.
[0137] 6. Add Phase D at 45.degree. C. Add Phase E at 40.degree. C.
QS with water.
[0138] The UV absorbance of the cream was enhanced by the presence
of the polymeric composition of the invention therein, as compared
to similar formulations without this composition, generally an
increase of about 2-3 SPF numbers.
EXAMPLE 17
[0139] Clear Styling/Conditioning Gel
5 Ingredients Wt. % Deionized Water 74.60 Ethanol (190 Proof) 5.00
VP/DMAPMA/PETE Copolymer (Ex. 1) 20.00 Dimethicone Copolyol 0.10
Caprylyl Pyrrolidone 0.10 Panthenol 0.10
2,4-Dihydroxy-N-(3-hydroxypropyl)- 3,3-Dimethyl Butanamide
Diazolidinyl Urea and Iodopropynyl Butylcarbamate 0.10 Perfume
qs
[0140] Manufacturing Procedure
[0141] 1. In a vessel, add ethanol to water and stir until
homogeneous.
[0142] 2. Next, add VP/DMAPMA/PETE copolymer to the mixture and
stir well until homogeneous.
[0143] 3. Add dimethicone copolyol, panthenol and caprylyl
pyrrolidone to the mixture and stir well after each addition until
homogeneous.
[0144] 4. Next, add diazolidinyl urea and iodopropynyl and
butylcarbamate and stir well until homogeneous.
EXAMPLE 18
Rinse-Off Protection Hair Conditioner
[0145]
6 Ingredients Wt. % Deionized Water 81.73 Emulsifying Wax NF 4.00
Cetearyl Alcohol and Ceteareth-20 2.00 Propylene Glycol 1.00
VP/DMAPMA/PETE Neutralized with 10.00 Benzophenone-4 (Ex. 6)
Glycerin 99.7% 0.50 Lauryl Pyrrolidone 0.25 Citric Acid FCC, USP,
Anhydrous 0.02 Propylene Glycol and Diazolidinyl Urea and 0.50
Iodopropynyl butylcarbamate
[0146] Manufacturing Procedure
[0147] 1. Heat the water, propylene glycol, glycerin, and citric
acid to 80-85.degree. C. using continuous addition with a propeller
stir rod.
[0148] 2. Add the VP/DMAPMA/PETE neutralized with Benzophenone-4
and stir to homogeneous.
[0149] 3. Combine in a separate vessel lauryl pyrrolidone,
emulsifying wax NF, cetearyl alcohol and ceteareth-20, heating to
80-85.degree. C. mixing until homogeneous.
[0150] 4. Add, product step 3, to the water phase with good
agitation. Mix with continuous agitation for 10-20 minutes or
longer. Maintain temperature at 80-85.degree. C. during this
step.
[0151] 5. Begin cooling with continuous agitation until
approximately 45.degree. C. Do not force cool.
[0152] 6. Switch to a paddle mixing rod. Continue slow agitation
and cool until a temperature of 30-35.degree. C. is reached. At
30-35.degree. C. add the propylene glycol and diazolidinyl urea and
iodopropynyl butylcarbamate and continue mixing until 25.degree. C.
is reached.
EXAMPLE 19
Rheology Modifiers
[0153] A 5% aqueous polymer solution of VP/DMAPMA/PETE/sulfuric
acid (Ex. 1) was thoroughly mixed with a 5% aqueous polymer
solution of polyvinyl alcohol (PVOH). The Brookfield viscosity of
each solution, and mixtures thereof, was determined to demonstrate
the effect of rheology modification by the composition of the
invention. Under visual inspection, the solutions appeared to be
homogeneous. The results are presented in Table 2 below.
7TABLE 2 Test Solution Brookfield Viscosity (cps) Percent Scale 5%
LV, 62, 10 RPM 1470 48.9 VP/DMAPMA/ PETE/Sulfuric Acid in Water (A)
5% PVOH in LV, 00, 30 RPM 5.2 26.0 water (B) 50/50 (w/w) LV, 62, 20
RPM 464 27.6 mixture of A and B
EXAMPLE 20
[0154] A 5% aqueous polymer solution of VP/DMAPMA/PETE/sulfuric
acid (Ex. 1) was thoroughly mixed with a 5% aqueous polymer
solution of poly-2-ethyl-2-oxazoline (PEO). The Brookfield
viscosity of each solution, and mixtures thereof, was performed to
demonstrate the effect of rheology modification. Under visual
inspection, the solution appeared to be homogeneous. The results
are presented in Table 3 below.
8TABLE 3 Test Solution Brookfield Viscosity (cps) Percent Scale 5%
VP/DMAPMA/ LV, 62, 10 RPM 1470 48.9 PETE/Sulfuric Acid in Water 5%
PEO in water LV, 00, 30 RPM 4.0 21.3 50/50 (w/w) mixture LV, 62, 20
RPM 339 22.6
EXAMPLE 21
[0155] A 1% aqueous polymer solution of VP/DMAPMA/PETE/sulfuric
acid (Ex. 1) was thoroughly mixed with a 1% aqueous polymer
solution of Kelcoloid HVF Algin (HVF), an alginate. The Brookfield
viscosity of each solution and their combination was performed to
demonstrate the effect of rheology modification. Under visual
inspection, the solution exhibited turbidity. The results are
presented in Table 4 below.
9TABLE 4 Test Solution Brookfield Viscosity (cps) Percent Scale 1%
VP/DMAPMA/ LV, 00, 6 RPM 60 58.8 PETE/Sulfuric Acid in Water 1% HVF
in water LV, 62, 30 RPM 709 71.4 50/50 (w/w) mixture LV, 61, 30 RPM
20 10.4
EXAMPLE 22
[0156] A 1% aqueous polymer solution of PVP/PETE (Ex. 4) was
thoroughly mixed with a 1% aqueous polymer solution of Kelcoloid
HVF Algin (HVF). The Brookfield viscosity of each solution and
their combination was performed to demonstrate the effect of
rheology modification. Under visual inspection, the solution
appeared to be homogeneous. The results are presented in Table 5
below.
10TABLE 5 Test Solution Brookfield Viscosity (cps) Percent Scale 1%
PVP/PETE in LV, 00, 12 RPM 12.4 24.8 Water 1% HVF in water LV, 62,
30 RPM 709 71.4 50/50 (w/w) mixture LV, 61, 12 RPM 129.5 26.1
[0157] The volume fraction, .PHI., of particles in the composition
of the invention is determined by the following procedure.
[0158] (1) The two-phase aqueous polymeric composition is prepared
as in the examples above.
[0159] (2) The known amount of the composition is passed through a
resin bed to remove insoluble particles.
[0160] (3) A water soluble solution remains.
[0161] (4) The solution is subjected to light to determine its
differential Refractive Index.
[0162] (5) The amount of soluble polymer which passed through the
resin bed is determined.
[0163] (6) .PHI.=1; (#5/#2).
[0164] FIG. 2 shows a plot of Brookfield viscosity vs. .PHI., the
volume fraction of particles in the 2-phase polymeric composition
of the invention. The graph shows a dramatic increase in viscosity
of the solution with an increase in the volume fraction of the
particles therein, indicating it is an effective rheology
modifier.
[0165] The compositions of the invention may be admixed, if
desired, with one or more of the following commercially available
rheology modifiers:
[0166] Acrylic polymers, crosslinked acrylic polymers, alginates,
associative thickeners, carrageenan, microcrystalline cellulose,
carboxymethylcellulose sodium, hydroxyethylcellulose,
hydroxypropylcellulose, hydroxypropylmethylcellulose,
methylcellulose, guar and guar derivatives, locust bea gum,
organoclays, polyethylene, polyethylene oxide,
polyvinylpyrrolidone, silica, water-swellable clay, xanthan gum and
pigments (inorganic).
[0167] Product applications of the rheology modifier of the
invention include the following:
[0168] Coatings, cementitious compounds, contrast mediums, wrinkle
masking, cryoprotectants, detergents, marking Instruments,
flocculation moderators, personal care formulations such as
skin/hair care, including shampoo, conditioner, gels and creams,
pharmaceutical, such as bioadhesives, syrups and excipients),
lubricating oil additives, lubricants, adhesives and cosmetics.
[0169] While the invention has been described with particular
reference to certain embodiments thereof, it will be understood
that changes and modifications may be made which are within the
skill of the art. Accordingly, it is intended to be bound only by
the following claims, in which:
* * * * *