U.S. patent application number 14/462974 was filed with the patent office on 2014-12-04 for aqueous dispersion of an ionomer-polyolefin blend.
The applicant listed for this patent is E I DU PONT DE NEMOURS AND COMPANY. Invention is credited to RICHARD ALLEN HAYES.
Application Number | 20140357779 14/462974 |
Document ID | / |
Family ID | 47049363 |
Filed Date | 2014-12-04 |
United States Patent
Application |
20140357779 |
Kind Code |
A1 |
HAYES; RICHARD ALLEN |
December 4, 2014 |
AQUEOUS DISPERSION OF AN IONOMER-POLYOLEFIN BLEND
Abstract
Disclosed is a method to form an aqueous dispersion comprising a
blend composition comprising or consisting essentially of about 75
to about 99.9 weight % of an ionomer composition and about 0.1 to
about 25 weight % of an ethylene acrylate ester copolymer
composition, a grafted polyolefin composition or a combination
thereof, the method comprising mixing the solid blend composition
with water heated to a temperature from about 80 to about
100.degree. C.
Inventors: |
HAYES; RICHARD ALLEN;
(Beaumont, TX) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
E I DU PONT DE NEMOURS AND COMPANY |
Wilmington |
DE |
US |
|
|
Family ID: |
47049363 |
Appl. No.: |
14/462974 |
Filed: |
August 19, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13290415 |
Nov 7, 2011 |
8841379 |
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14462974 |
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Current U.S.
Class: |
524/504 ;
524/522; 525/221; 525/78 |
Current CPC
Class: |
C08L 23/0876 20130101;
C08L 2205/03 20130101; C08L 2201/54 20130101; C08L 23/0876
20130101; C08L 23/0869 20130101; C08L 23/08 20130101; C08L 2205/025
20130101 |
Class at
Publication: |
524/504 ;
524/522; 525/78; 525/221 |
International
Class: |
C08L 23/08 20060101
C08L023/08 |
Claims
1. An aqueous dispersion comprising water and about 0.001 to about
50 weight % of a mixture of polymers comprising (a) about 75 to
about 99.9 weight %, based on the combination of (a) and (b), of an
ionomer composition comprising a parent acid copolymer that
comprises copolymerized units of ethylene and about 18 to about 30
weight % of copolymerized units of acrylic acid or methacrylic
acid, based on the total weight of the parent acid copolymer, the
acid copolymer having a melt flow rate (MFR) from about 200 to
about 1000 g/10 min., measured according to ASTM D1238 at
190.degree. C. with a 2160 g load, wherein about 50% to about 70%
of the carboxylic acid groups of the copolymer, based on the total
carboxylic acid content of the parent acid copolymer as calculated
for the non-neutralized parent acid copolymer, are neutralized to
carboxylic acid salts comprising potassium cations, sodium cations
or combinations thereof; and (b) about 0.1 to about 25 weight %,
based on the combination of (a) and (b), of (i) at least one
ethylene ester copolymer comprising copolymerized units of ethylene
and about 10 to about 45 weight % of copolymerized units of an
alpha, beta-ethylenically unsaturated carboxylic acid ester, based
on the total weight of the ethylene ester copolymer; (ii) a grafted
polyolefin composition comprising a parent polyolefin grafted with
about 0.1 to about 5 weight % of an alpha,beta-ethylenically
unsaturated carboxylic acid or anhydride, based on the total weight
of the grafted polyolefin; or (iii) a combination of the ethylene
ester copolymer and the grafted polyolefin.
2. The aqueous dispersion of claim 1 wherein the mixture of
polymers consists essentially of the ionomer and at least one
ethylene ester copolymer.
3. The aqueous dispersion of claim 2 wherein the at least one
ethylene ester copolymer is an ethylene methyl acrylate
dipolymer.
4. The aqueous dispersion of claim 1 wherein the mixture of
polymers consists essentially of the ionomer and the grafted
polyolefin.
5. The aqueous dispersion of claim 4 wherein the grafted polyolefin
is a metallocene polyolefin grafted with maleic anhydride.
6. The aqueous dispersion of claim 1 wherein the mixture of
polymers consists essentially of the ionomer, the ethylene ester
copolymer and the grafted polyolefin.
7. The aqueous dispersion of claim 6 wherein the ethylene ester
copolymer is an ethylene methyl acrylate dipolymer and the grafted
polyolefin is a metallocene polyolefin grafted with maleic
anhydride.
8. The aqueous dispersion of claim 1 comprising an ionomer wherein
the cations of the carboxylate salts consist essentially of sodium
cations.
9. The aqueous dispersion of claim 1 comprising an ionomer wherein
the cations of the carboxylate salts consist essentially of
potassium cations.
10-16. (canceled)
17. A blend composition comprising (a) about 75 to about 99.9
weight %, based on the combination of (a) and (b), of an ionomer
composition comprising a parent acid copolymer that comprises
copolymerized units of ethylene and about 18 to about 30 weight %
of copolymerized units of acrylic acid or methacrylic acid, based
on the total weight of the parent acid copolymer, the acid
copolymer having a melt flow rate (MFR) from about 200 to about
1000 g/10 min., measured according to ASTM D1238 at 190.degree. C.
with a 2160 g load, wherein about 50% to about 70% of the
carboxylic acid groups of the copolymer, based on the total
carboxylic acid content of the parent acid copolymer as calculated
for the non-neutralized parent acid copolymer, are neutralized to
carboxylic acid salts comprising potassium cations, sodium cations
or combinations thereof; and (b) about 0.1 to about 25 weight %,
based on the combination of (a) and (b), of (i) at least one
ethylene ester copolymer comprising copolymerized units of ethylene
and about 10 to about 45 weight % of copolymerized units of an
alpha, beta-ethylenically unsaturated carboxylic acid ester, based
on the total weight of the ethylene ester copolymer; (ii) a grafted
polyolefin composition comprising a parent polyolefin grafted with
about 0.1 to about 5 weight % of an alpha,beta-ethylenically
unsaturated carboxylic acid or anhydride, based on the total weight
of the grafted polyolefin; or (iii) a combination of the ethylene
ester copolymer and the grafted polyolefin.
18. The blend composition of claim 17 wherein the mixture of
polymers consists essentially of the ionomer and at least one
ethylene ester copolymer.
19. The blend composition of claim 18 wherein the at least one
ethylene ester copolymer is an ethylene methyl acrylate
dipolymer.
20. The blend composition of claim 17 wherein the mixture of
polymers consists essentially of the ionomer and the grafted
polyolefin.
21. The blend composition of claim 20 wherein the grafted
polyolefin is a metallocene polyolefin grafted with maleic
anhydride.
22. The blend composition of claim 17 wherein the mixture of
polymers consists essentially of the ionomer, the ethylene ester
copolymer and the grafted polyolefin.
23. The blend composition of claim 22 wherein the ethylene ester
copolymer is an ethylene methyl acrylate dipolymer and the grafted
polyolefin is a metallocene polyolefin grafted with maleic
anhydride.
24. The blend composition of claim 17 comprising an ionomer wherein
the cations of the carboxylate salts consist essentially of sodium
cations.
25. The blend composition of claim 17 comprising an ionomer wherein
the cations of the carboxylate salts consist essentially of
potassium cations.
26-29. (canceled)
Description
FIELD OF THE INVENTION
[0001] The present invention is directed to a method to form
aqueous dispersions comprising ionomer-polyolefin blends.
BACKGROUND OF THE INVENTION
[0002] Ionomers of ethylene copolymers with
alpha,beta-ethylenically unsaturated carboxylic acids are known in
the art, wherein at least a portion of the carboxylic acid groups
of the copolymer are neutralized to form carboxylate salts
comprising alkali metal, alkaline earth metal or transition metal
cations. See for example U.S. Pat. Nos. 3,264,272; 3,338,739;
3,355,319; 5,155,157; 5,244,969; 5,304,608; 5,688,869; 6,245,858;
6,518,365; and U.S. Patent Application Publication
2009/0297747.
[0003] Aqueous dispersions of ionomers are also known in the art.
See for example U.S. Pat. Nos. 3,904,569; 4,136,069; 4,269,937;
4,508,804; 5,409,765; and Japanese Patent Applications JP01009338
and JP05075769. They have been produced by dissolving the acid
copolymer precursors in a solvent, neutralization of the acid
functionalities with generally ammonia, amines or alkali metal
ions, and dilution of the solution into water followed by partial
or complete removal of the solvent. See for example U.S. Pat. Nos.
2,313,144; 3,389,109; 3,562,196; 5,430,111; 5,591,806; Japanese
Patent Applications JP50084687 and JP2009091426.
[0004] Aqueous ionomer dispersions have also been produced by
heating acid copolymer precursors or ionomers in hot aqueous
ammonia and other neutralizing agents. See for example U.S. Pat.
Nos. 3,553,178; 3,644,258; 3,674,896; 3,823,108; 3,872,039;
3,899,389; 3,970,626; 3,983,268; 4,400,440; 4,540,736; 5,160,484;
5,206,279; 5,330,788; 5,387,635; 5,550,177; 6,852,792; U.S. Patent
Application Publication 2007/0117916; Japanese Patent Application
JP06000872; and PCT Patent Application Publication
WO2000/044801.
[0005] Aqueous ionomer dispersions have also been produced by
dispersing the acid copolymer precursor in aqueous solutions of
neutralizing agents at temperatures under high shear process
conditions above the boiling point of water, necessitating the use
of pressure vessels such as autoclaves and extruders. See for
example U.S. Pat. Nos. 5,082,697; 5,374,687; 5,993,604; 6,482,886;
7,279,513; 7,470,736; U.S. Patent Application Publications
2006/0124554; 2007/0243331; PCT Patent Application WO2011/087478;
and Japanese Patent Applications JP10006640; and JP50135141.
[0006] Aqueous ionomer dispersions have also been produced by
dispersing the ionomer in aqueous solutions under high shear
process conditions at temperatures above the boiling point of
water, necessitating the use of pressure vessels such as autoclaves
and extruders. See for example U.S. Pat. Nos. 4,173,669; 4,329,305;
4,410,655; 6,458,897; Japanese Applications JP11158332;
JP2005075878; JP 200575879; and PCT Patent Application Publication
WO1999/10276.
[0007] Aqueous ionomer dispersions have also been produced by
dispersing highly neutralized, low melt index (MI) ionomers in hot
water. See for example U.S. Pat. Nos. 3,321,819; 3,472,825; and
4,181,566.
[0008] Blends incorporating a polyolefin with an ionomer are known.
See for example U.S. Pat. Nos. 5,179,168; 5,445,893; 5,542,677;
5,591,803; 6,100,336; U.S. Patent Application Publication U.S.
20080132628; PCT Patent Application Publication WO2009072600; and
Japanese Patent Applications JP09-040924; JP09-175592; JP10-060186;
JP10-316872; JP11-147288; JP11-291406; JP2868862; JP3356376;
JP3878268; JP3926486; JP3985881; JP4197901; JP2002-012722;
JP2002-234975; JP2003-026868; JP2003-291283; JP2004-217759;
JP2006-026986; JP2007-138004; JP2007-301797; JP2007-302764;
JP2008-138116; JP2008-273998; JP2009-035699; JP2009-084324;
JP2009-101677; JP2009-138139; JP2868862; JP09040924; JP09175592;
and JP3599912.
[0009] Aqueous dispersions incorporating a major portion of a
polyolefin with a minor portion of an ionomer, generally
functioning as a dispersant for the polyolefin, are known. See for
example U.S. Pat. Nos. 3,296,172; 3,356,629; 3,896,065; 4,174,335;
4,336,210; 4,440,908; 4,775,713; 4,970,258; 4,978,707; 7,439,276;
7,528,080; 7,588,662; U.S. Patent Application Publications
2005/0271888; 2007/0137808; 2007/0137809; 2007/0137810;
2007/0137811; 2007/0137813; 2007/0144697; 2007/0284069;
2007/0292705; 2007/0295464; 2007/0295465; 2008/0000598;
2008/0000602; 2008/0009586; 2008/0041543; 2008/0073045;
2008/0073046; 2008/0076844; 2008/0135195; 2008/0230195;
2008/0216977; 2008/0295985; 2009/0202829; 2009/0253321; PCT Patent
Application Publications WO2007/008633; WO2008/052122;
WO2009/035877; WO2009/055275; WO2009/064993 and Japanese Patent
Applications JP2958102; JP 2001-1355185.
[0010] Aqueous dispersions incorporating a major portion of a
polyolefin with a minor portion of an ionomer have also been
produced by dispersing the polyolefin and the ionomer in aqueous
solutions under high shear process conditions at temperatures above
the boiling point of water, necessitating the use of pressure
vessels such as autoclaves and extruders. See for example U.S.
Patent Application Publications 2005/0100754; 2007/0141323;
2008/0118728; 2008/0176968; 2008/0182040; 2008/0292833;
2009/0194450; 2010/0048784; 2010/0137501; and PCT Patent
Application Publications WO2005/021638; WO2008/005501;
WO2009/045731; WO2011/058121; WO2011/068525.
[0011] Aqueous dispersions incorporating a major portion of ionomer
and a minor portion of polar polyolefin were produced, for example,
by mixing preformed dispersions of each component. See for example
British Patent GB1243303; European Patent Application EP1163276;
and Japanese Application JP2000328046.
[0012] Aqueous dispersions incorporating a major portion of ionomer
and a minor portion of polar polyolefin were produced, for example,
by preparing a solid blend of an acid copolymer with the polar
polyolefin, and treating the blend with a heated aqueous ammonia
solution (PCT Patent Application Publication WO2011/058119).
SUMMARY OF THE INVENTION
[0013] The invention relates to a blend composition comprising or
consisting essentially of [0014] (a) about 75 to about 99.9 weight
% of an ionomer composition comprising or consisting essentially of
a parent acid copolymer that comprises copolymerized units of
ethylene and about 18 to about 30 weight % of copolymerized units
of acrylic acid or methacrylic acid, based on the total weight of
the parent acid copolymer, the acid copolymer having a melt flow
rate (MFR) from about 200 to about 1000 g/10 min., measured
according to ASTM D1238 at 190.degree. C. with a 2160 g load,
wherein about 50% to about 70% of the carboxylic acid groups of the
copolymer, based on the total carboxylic acid content of the parent
acid copolymer as calculated for the non-neutralized parent acid
copolymer, are neutralized to carboxylic acid salts comprising
potassium cations, sodium cations or combinations thereof; and
[0015] (b) about 0.1 to about 25 weight %, based on the combination
of (a) and (b), of (i) at least one ethylene ester copolymer
comprising copolymerized units of ethylene and about 10 to about 45
weight % of copolymerized units of an alpha, beta-ethylenically
unsaturated carboxylic acid ester, based on the total weight of the
ethylene ester copolymer; (ii) a grafted polyolefin composition
comprising a parent polyolefin grafted with about 0.1 to about 5
weight % of an alpha,beta-ethylenically unsaturated carboxylic acid
or anhydride, based on the total weight of the grafted polyolefin;
or (iii) a combination of the ethylene ester copolymer and the
grafted polyolefin.
[0016] The invention provides a method for making an aqueous
dispersion comprising a mixture of an ionomer and an ethylene ester
copolymer, a grafted polyolefin composition or a combination
thereof, the method comprising or consisting essentially of [0017]
(1) providing a solid blend composition comprising or consisting
essentially of the composition described above; [0018] (2) mixing
the solid blend composition with water heated to a temperature from
about 80 to about 100.degree. C. (under low shear conditions) to
provide a heated aqueous blend dispersion; and [0019] (3)
optionally cooling the heated aqueous blend dispersion to a
temperature of about 20 to 30.degree. C., wherein the blend remains
dispersed in the liquid phase.
[0020] One embodiment is wherein (2) comprises (i) adding an
article formed from the preformed solid blend composition to water
at a temperature of about 20 to 30.degree. C. to form a mixture of
solid blend and water; and subsequently (ii) heating the mixture to
a temperature from about 80 to about 100.degree. C.
[0021] Another embodiment is wherein (2) comprises adding an
article formed from the preformed solid blend composition to water
preheated to a temperature from about 80 to about 100.degree.
C.
[0022] The invention also provides an aqueous dispersion of a blend
composition as described above. The aqueous dispersion may be
produced using the methods described above.
DETAILED DESCRIPTION OF THE INVENTION
[0023] Unless otherwise defined, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this invention belongs. In case
of conflict, the specification, including definitions, will
control.
[0024] Although methods and materials similar or equivalent to
those described herein can be used in the practice or testing of
the invention, suitable methods and materials are described
herein.
[0025] Unless stated otherwise, all percentages, parts, ratios,
etc., are by weight.
[0026] When an amount, concentration, or other value or parameter
is given as either a range, preferred range or a list of lower
preferable values and upper preferable values, this is to be
understood as specifically disclosing all ranges formed from any
pair of any lower range limit or preferred value and any upper
range limit or preferred value, regardless of whether ranges are
separately disclosed. Where a range of numerical values is recited
herein, unless otherwise stated, the range is intended to include
the endpoints thereof, and all integers and fractions within the
range. It is not intended that the scope of the invention be
limited to the specific values recited when defining a range.
[0027] When the term "about" is used in describing a value or an
end-point of a range, the disclosure should be understood to
include the specific value or end-point referred to.
[0028] As used herein, the terms "comprises," "comprising,"
"includes," "including," "containing," "characterized by," "has,"
"having" or any other variation thereof, are intended to cover a
non-exclusive inclusion. For example, a process, method, article,
or apparatus that comprises a list of elements is not necessarily
limited to only those elements but may include other elements not
expressly listed or inherent to such process, method, article, or
apparatus. Further, unless expressly stated to the contrary, "or"
refers to an inclusive or and not to an exclusive or.
[0029] The transitional phrase "consisting essentially of" limits
the scope of a claim to the specified materials or steps and those
that do not materially affect the basic and novel characteristic(s)
of the claimed invention. Where applicants have defined an
invention or a portion thereof with an open-ended term such as
"comprising," unless otherwise stated the description should be
interpreted to also describe such an invention using the term
"consisting essentially of".
[0030] Use of "a" or "an" are employed to describe elements and
components of the invention. This is merely for convenience and to
give a general sense of the invention. This description should be
read to include one or at least one and the singular also includes
the plural unless it is obvious that it is meant otherwise.
[0031] In describing certain polymers it should be understood that
sometimes applicants are referring to the polymers by the monomers
used to produce them or the amounts of the monomers used to produce
the polymers. While such a description may not include the specific
nomenclature used to describe the final polymer or may not contain
product-by-process terminology, any such reference to monomers and
amounts should be interpreted to mean that the polymer comprises
copolymerized units of those monomers or that amount of the
monomers, and the corresponding polymers and compositions
thereof.
[0032] The term "copolymer" is used to refer to polymers formed by
copolymerization of two or more monomers. Such copolymers include
dipolymers consisting essentially of two copolymerized
comonomers.
[0033] As used herein, "disperse," "dispersing" and related terms
refer to a process in which solid articles such as pellets of
polymer are mixed with water and over a brief period of time
disappear into the liquid phase. The terms "aqueous dispersion" and
"dispersion" describe a transparent, free-flowing liquid with no
solids visible to the human eye. No characterization is made
regarding the interaction of the polymer molecules with the water
molecules in such aqueous dispersions. "Self-dispersible" means
that the material disperses readily in hot (80 to 100.degree. C.)
water without need for additional dispersants or reagents.
[0034] Methods to produce aqueous dispersions comprising certain
ionomer- polyolefin blends are disclosed herein. Surprisingly, we
have found that certain ionomer-polyolefin blends with certain
compositional characteristics readily form aqueous dispersions when
mixed with hot water under low shear conditions. In contrast,
previous methods required significantly more rigorous conditions to
form dispersions.
[0035] The dispersion method provides a process simplification
which requires less energy and is inherently safer than disclosed
in the prior art dispersion methods, such as high pressure, high
shear, autoclave processes or extrusion processes.
[0036] Ionomer Composition
[0037] The ionomer used herein is derived from certain parent acid
copolymers comprising copolymerized units of ethylene and about 18
to about 30 weight % of copolymerized units of an alpha,
beta-ethylenically unsaturated carboxylic acid such as acrylic acid
or methacrylic acid. Preferably, the parent acid copolymer used
herein comprises about 19 to about 25 weight %, or more preferably
about 19 to about 23 weight %, of the alpha, beta-ethylenically
unsaturated carboxylic acid, based on the total weight of the
copolymer.
[0038] Preferably, the alpha, beta-ethylenically unsaturated
carboxylic acid is methacrylic acid. Of note are acid copolymers
consisting essentially of copolymerized units of ethylene and
copolymerized units of the alpha, beta-ethylenically unsaturated
carboxylic acid and 0 weight % of additional comonomers; that is,
dipolymers of ethylene and the alpha, beta-ethylenically
unsaturated carboxylic acid. Preferred acid copolymers are ethylene
methacrylic acid dipolymers.
[0039] The parent acid copolymers used herein may be polymerized as
disclosed in U.S. Pat. Nos. 3,404,134; 5,028,674; 6,500,888; and
6,518,365.
[0040] The parent acid copolymers used herein preferably have a
melt flow rate (MFR) of about 200 to about 1000 grams/10 min as
measured by ASTM D1238 at 190.degree. C. using a 2160 g load. A
similar ISO test is ISO 1133. Alternatively, the parent acid
copolymers have MFR from a lower limit of 200, 250 or 300 to an
upper limit of 400, 500, 600 or 1000. The preferred melt flow rate
of the parent acid copolymer provides ionomers with optimum
physical properties in the final shaped article while still
allowing for rapid self-dispersion in hot water. Ionomers derived
from parent acid copolymers with melt flow rates below about 200
grams/10 minutes have minimal hot water self-dispersibility, while
ionomers derived from parent acid copolymer melt flow rates of
greater than about 1000 grams/10 minutes may reduce the physical
properties in the intended enduse.
[0041] In some embodiments, blends of two or more ethylene acid
copolymers may be used, provided that the aggregate components and
properties of the blend fall within the limits described above for
the ethylene acid copolymers. For example, two ethylene methacrylic
acid dipolymers may be used such that the total weight % of
methacrylic acid is about 18 to about 30 weight % of the total
polymeric material and the melt flow rate of the blend is about 200
to about 1000 grams/10 min.
[0042] The ionomers disclosed herein are produced from the parent
acid copolymers, wherein from about 50 to about 70%, or preferably
from about 55 to about 60%, such as about 60%, of the total
carboxylic acid groups of the parent acid copolymers, as calculated
for the non-neutralized parent acid copolymers, are neutralized to
form carboxylic acid salts with potassium ions, sodium ions or
combinations thereof. The parent acid copolymers may be neutralized
using methods disclosed in, for example, U.S. Pat. No. 3,404,134.
Ionomers wherein the cations of the carboxylate salts consist
essentially of sodium cations are notable.
[0043] Importantly, the ionomer compositions combine the properties
of being self-dispersible in hot water along with being
thermoplastic, allowing for melt fabrication into many articles of
commerce. Preferably, the ionomers used herein have a melt flow
rate (MFR) of at least 1 gram/10 min, such as about 1 to about 20
grams/10 min as measured by ASTM D1238 at 190.degree. C. using a
2160 g load. More preferably, the ionomer composition has a MFR of
about 1 to about 10 grams/10 min, and most preferably has a MFR of
about 1 to about 5 grams/10 min. The combination of the above
described parent acid copolymer melt flow rates and the
neutralization levels provides ionomers which combine the
properties of being easily self-dispersible in hot water and easily
melt fabricated into articles of commerce.
[0044] In some embodiments, blends of two or more ionomers may be
used, provided that the aggregate components and properties of the
blend fall within the limits described above for the ionomers.
[0045] The ionomer composition may also contain other additives
known in the art. The additives may include, but are not limited
to, processing aids, flow enhancing additives, lubricants,
pigments, dyes, flame retardants, impact modifiers, nucleating
agents, anti-blocking agents such as silica, thermal stabilizers,
UV absorbers, UV stabilizers, surfactants, chelating agents, and
coupling agents.
[0046] Ethylene Ester Copolymer Composition
[0047] The ethylene ester copolymer used herein comprises or
consists essentially of copolymerized units of ethylene and about
10 to about 45 weight % of copolymerized units of an alpha,
beta-ethylenically unsaturated carboxylic acid ester, based on the
total weight of the ethylene ester copolymer. Preferably, the
ethylene ester copolymer comprises about 15 to about 40 weight %,
or more preferably about 20 to about 35 weight %, of the alpha,
beta-ethylenically unsaturated carboxylic acid ester, based on the
total weight of the copolymer. Of note is the dipolymer consisting
essentially of copolymerized units of ethylene and copolymerized
units of an alpha, beta-ethylenically unsaturated carboxylic acid
ester.
[0048] The alpha, beta-ethylenically unsaturated carboxylic acid
ester comonomer includes, but is not limited to, methyl acrylate,
methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl
acrylate, propyl methacrylate, isopropyl acrylate, isopropyl
methacrylate, butyl acrylate, butyl methacrylate, isobutyl
acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl
methacrylate, octyl acrylate, octyl methacrylate, undecyl acrylate,
undecyl methacrylate, octadecyl acrylate, octadecyl methacrylate,
dodecyl acrylate, dodecyl methacrylate, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, isobornyl acrylate, isobornyl
methacrylate, lauryl acrylate, lauryl methacrylate, 2-hydroxyethyl
acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl
methacrylate, poly(ethylene glycol)acrylate, poly(ethylene
glycol)methacrylate, poly(ethylene glycol) methyl ether acrylate,
poly(ethylene glycol) methyl ether methacrylate, poly(ethylene
glycol) behenyl ether acrylate, poly(ethylene glycol) behenyl ether
methacrylate, poly(ethylene glycol) 4-nonylphenyl ether acrylate,
poly(ethylene glycol) 4-nonylphenyl ether methacrylate,
poly(ethylene glycol) phenyl ether acrylate, poly(ethylene glycol)
phenyl ether methacrylate, dimethyl maleate, diethyl maleate,
dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl
fumarate, dimenthyl fumarate, and the like and combinations
thereof. Preferable alpha, beta-ethylenically unsaturated
carboxylic acid ester comonomers include, but are not limited to,
methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate
and combinations thereof. More preferably, the alpha,
beta-ethylenically unsaturated carboxylic acid ester comonomer is
methyl acrylate.
[0049] Grafted Polyolefin Composition
[0050] The grafted polyolefin composition comprises a parent
polyolefin grafted with about 0.1 to about 5 weight % of an alpha,
beta-ethylenically unsaturated carboxylic acid or anhydride, based
on the total weight of the grafted polyolefin.
[0051] The parent polyolefin may comprise ethylene-based polymers,
such as polyethylene and ethylene-alpha olefin copolymers,
propylene-based polymers, such as polypropylene and propylene-alpha
olefin copolymers, and propylene-ethylene copolymers. For example,
the parent polyolefin may be polypropylene, polyethylene, and
copolymers thereof, and blends thereof, as well as
ethylene-propylene-diene terpolymers. The parent polyolefin
includes homogeneous polymers described in U.S. Pat. No. 3,645,992;
high density polyethylene (HDPE) as described in U.S. Pat. No.
4,076,698; heterogeneously branched linear low density polyethylene
(LLDPE); heterogeneously branched ultra low linear density
polyethylene (ULDPE); homogeneously branched, linear
ethylene/alpha-olefin copolymers; homogeneously branched,
substantially linear ethylene/alpha-olefin polymers, which can be
prepared, for example, by a process disclosed in U.S. Pat. Nos.
5,272,236 and 5,278,272, the disclosures of which are incorporated
herein by reference; and high pressure, free radical polymerized
ethylene polymers and copolymers such as low density polyethylene
(LDPE). Parent polyolefin compositions described in U.S. Pat. Nos.
6,566,446, 6,538,070, 6,448,341, 6,316,549, 6,111,023, 5,869,575,
5,844,045, or 5,677,383 are also suitable in some embodiments.
Blends of polymers can be used as well. In some embodiments, the
blends include two different Ziegler-Natta polymers. In other
embodiments, the blends can include blends of a Ziegler-Natta and a
metallocene polymer. In still other embodiments, the polymer used
herein is a blend of two different metallocene polymers. In other
embodiments single site catalysts may be used.
[0052] Examples of ethylene-alpha olefin copolymers comprise an
alpha-olefin interpolymer of ethylene with at least one comonomer
selected from the group consisting of a C.sub.4-C.sub.20 linear,
branched or cyclic diene, and a compound represented by the formula
H.sub.2C.dbd.CHR wherein R is a C.sub.1-C.sub.20 linear, branched
or cyclic alkyl group or a C.sub.6-C.sub.20 aryl group. Examples of
comonomers include propylene, 1-butene, 3-methyl-1-butene,
4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene,
1-octene, 1-decene, and 1-dodecene. In some embodiments, the
interpolymer of ethylene has a density of less than about 0.92
g/cc.
[0053] Examples of propylene-alpha olefin copolymers comprise an
alpha-olefin interpolymer of propylene with at least one comonomer
selected from the group consisting of ethylene, a C.sub.4-C.sub.20
linear, branched or cyclic diene, and a compound represented by the
formula H.sub.2C.dbd.CHR wherein R is a R is a C.sub.1-C.sub.20
linear, branched or cyclic alkyl group or a C.sub.6-C.sub.20 aryl
group. Examples of comonomers include ethylene, 1-butene,
3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-heptene, 1-hexene, 1-octene, 1-decene, and 1-dodecene.
[0054] Further examples of parent polyolefins which may be used
include homopolymers and copolymers (including elastomers) of an
olefin such as ethylene, propylene, 1-butene, 3-methyl-1-butene,
4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene,
1-octene, 1-decene, and 1-dodecene as typically represented by
polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene,
poly-3-methyl-1-pentene, poly-4-methyl-1-pentene,
ethylene-propylene copolymer, ethylene-1-butene copolymer, and
propylene-1-butene copolymer; copolymers (including elastomers) of
an alpha-olefin with a conjugated or non-conjugated diene as
typically represented by ethylene-butadiene copolymer and
ethylene-ethylidene norbornene copolymer; and polyolefins
(including elastomers) such as copolymers of two or more
alpha-olefins with a conjugated or non-conjugated diene as
typically represented by ethylene-propylene-butadiene copolymer,
ethylene-propylene-dicyclopentadiene copolymer,
ethylene-propylene-1,5-hexadiene copolymer, and
ethylene-propylene-ethylidene norbornene copolymer.
[0055] Preferably the grafted polyolefin is made from a parent
polyolefin made from ethylene and an alpha-olefin having 3 to 20
carbons having a density of about 0.92 g/cc (ASTM D792) or less,
grafted with about 0.1 to about 5 weight % of an alpha,
beta-ethylenically unsaturated carboxylic acid or anhydride. The
grafted polyolefin is made by grafting the alpha,
beta-ethylenically unsaturated carboxylic acid or anhydride onto
the parent polyolefin.
[0056] Preferably the grafted polyolefin is made from a parent
polyolefin that has a density of about 0.92 g/cc (ASTM D-792) or
less, or about 0.90 g/cc or less, about 0.88 g/cc or less, or about
0.88 to about 0.84 g/cc.
[0057] Preferably the parent polyolefin is a polyolefin copolymer
comprising ethylene and alpha-olefin comonomers. The parent
polyolefin copolymer comprises at least two monomers, but may
incorporate more than two comonomers, such as terpolymers,
tetrapolymers and the like. Preferably, the parent polyolefin
copolymer comprises from a lower limit of about 5 weight % m about
15 weight %, about 20 weight % or about 25 weight % to an upper
limit of about 35 weight %, about 40 weight %, about 45 weight % or
about 50 weight % (all based on the total weight of the parent
polyolefin copolymer).
[0058] The alpha-olefin comonomer contains from 3 to 20 carbons and
may be a linear, branched or cyclic alpha-olefin. Preferable
alpha-olefins are selected from the group consisting of propene,
1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene,
1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 3-cyclohexyl-1-propene, vinyl
cyclohexane and the like and mixtures thereof. The alpha-olefin
comonomer preferably contains 3 to 10 carbons. The density of the
alpha-olefin copolymer will generally depend on the type and level
of alpha-olefin incorporated.
[0059] The parent polyolefin copolymer may optionally incorporate a
minor amount of other olefinic comonomers; for example cyclic
olefins such as norbornene; styrene; dienes such as
dicyclopentadiene, ethylidene norbornene and vinyl norbornene; and
the like and mixtures thereof. When included, the optional
comonomer may be incorporated at a level of about 15 weight % or
less, based on the total weight of the parent polyolefin
copolymer.
[0060] The parent polyolefin may be produced by any known method
and may be catalyzed with any known polymerization catalyst such
as, for example, radical-, Ziegler-Natta- or metallocene-catalyzed
polymerizations (e.g., U.S. Pat. Nos. 3,645,992, 5,026,798,
5,055,438, 5,057,475, 5,064,802, 5,096,867, 5,132,380, 5,231,106,
5,272,236, 5,278,272, 5,374,696, 5,420,220, 5,453,410, 5,470,993,
5,703,187, 5,986,028, 6,013,819, 6,159,608, and EP514828).
[0061] Blends of two or more parent polyolefin copolymers may be
used if desired.
[0062] The grafted polyolefin comprises an alpha,
beta-ethylenically unsaturated carboxylic acid or anhydride grafted
to the parent polyolefin. In a grafted polymer, none of the atoms
originally contained in the alpha, beta-ethylenically unsaturated
carboxylic acid or anhydride moiety are included in the polymer
backbone. The alpha, beta-ethylenically unsaturated carboxylic acid
or anhydride preferably is selected from the group consisting of
maleic anhydride, maleic acid, fumaric acid, acrylic acid,
methacrylic acid, itaconic anhydride, itaconic acid, citraconic
acid, citraconic anhydride, crotonic acid, crotonic anhydride,
methyl crotonic acid, cinnamic acid,
endo-bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid,
endo-bicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride,
cis-4-cyclohexene-1,2-dicarboxylic acid,
cis-4-cyclohexene-1,2-dicarboxylic anhydride and the like and
mixtures thereof. Metal salts, anhydrides, esters, amides or imides
of the above acids may also be used. More preferably, the alpha,
beta-ethylenically unsaturated carboxylic acid or anhydride is
maleic anhydride.
[0063] The alpha, beta-ethylenically unsaturated carboxylic acid or
anhydride may be grafted onto the parent polyolefin by any known
method. For example, the alpha, beta-ethylenically unsaturated
carboxylic acid or anhydride may be grafted onto the parent
polyolefin by the methods disclosed in U.S. Pat. Nos. 3,236,917,
3,932,368, 4,612,155, 4,888,394, 4,950,541, 5,194,509, 5,346,963,
5,523,358, 5,705,565, 5,744,250, 5,955,547, 6,545,091, 7,408,007,
U.S.2008/0078445, U.S.2008/0115825, and EP0266994.
[0064] The level of the alpha, beta-ethylenically unsaturated
carboxylic acid or anhydride grafted onto the parent polyolefin is
preferably from about 0.1 to 5 weight %, based on the total weight
of the grafted polyolefin. The level of the alpha,
beta-ethylenically unsaturated carboxylic acid or anhydride may be
from about 0.3 to 4 weight % or from about 0.5 to 2 weight %, based
on the total weight of the grafted polyolefin.
[0065] Blend Composition
[0066] The blend composition comprises or consists essentially of
about 75 to about 99.9 weight % of an ionomer composition and about
0.1 to about 25 weight % of an ethylene ester copolymer
composition, a grafted polyolefin composition or a combination
thereof. The blend composition comprises or consists essentially of
preferably about 80 to about 99 weight %, more preferably about 90
to about 99 weight % and most preferably about 95 to about 99
weight % of an ionomer composition and preferably about 20 to about
1 weight %, more preferably about 10 to about 1 weight % and most
preferably about 5 to about 1 weight % of an ethylene acrylate
ester copolymer composition, a grafted polyolefin composition or a
combination thereof.
[0067] Of note is the blend composition consisting essentially of
the ionomer and at least one ethylene ester copolymer, such as a
blend comprising about 3 to about 15 weight % of an ethylene ester
copolymer or about 3 to about 15 weight % of a combination of two
different ethylene ester copolymers. Also of note is the blend
composition consisting essentially of the ionomer and the grafted
polyolefin. Also of note is the blend composition consisting
essentially of the ionomer, the ethylene ester copolymer and the
grafted polyolefin, such as a blend comprising about 3 to about 5
weight % of the ethylene ester copolymer and about 3 to about 6
weight % of the grafted polyolefin.
[0068] The process to produce the blends can be performed by any
high shear, intensive melt mixing process known in the art.
Preferably, such a process would involve intensive mixing of the
molten ionomer composition with the ethylene acrylate ester
copolymer composition, the grafted polyolefin composition or a
combination thereof. For example, the intensive mixing may be
provided through static mixers, rubber mills, Brabender mixers,
Buss kneaders, single screw extruders or twin screw extruders.
Extruders are the most convenient to use because of their high
throughput, possible modular construction and ease of assembly,
choice of many mixing screws, and ease of control and maintenance
of process temperatures.
[0069] The ionomer composition, the ethylene ester copolymer
composition and/or the grafted polyolefin composition can be dried
prior to any mixing step. The blend composition resins can be mixed
as a dry blend, typically referred to as a "pellet blend", prior to
feeding to the melt mixing process. Alternatively, the blend
composition resins can be co-fed through two or more different
feeders. In an extrusion process, the blend composition resins
would typically be fed into the back, feed section of the extruder.
However, the blend composition resins independently can be
advantageously fed into two different locations of the extruder.
For example, the ionomer composition can be added in the back, feed
section of the extruder while the ethylene ester copolymer
composition, the grafted polyolefin composition or a combination
thereof is fed in the front of the extruder near the die plate. The
extruder temperature profile is set up to allow the blend
components to melt under the processing conditions. The screw
design will also provide stress and, in turn, heat, to the resins
as it mixes the molten blend composition resins. Generally, the
blend components' melt processing temperature will be within the
range of about 50.degree. C. to about 300.degree. C. However, the
exact processing conditions will depend on the chemical
compositions of the blend component resins used. Alternatively, the
ethylene ester copolymer composition, the grafted polyolefin
composition or combination thereof can be blended as a part of the
parent acid copolymer neutralization process to form the ionomer
composition, as described above. For example, a composition
comprising a neutralizing compound such as sodium carbonate and an
ethylene ester copolymer can be mixed with the acid copolymer
precursor to the ionomer in the extruder.
[0070] After the blend composition has been melt blended, it is
removed from the mixer and allowed to cool to a solid. For example,
the melt blend is extruded through a die, cut into pellets and
quenched in a cooling bath.
[0071] The ethylene ester copolymer composition, the grafted
polyolefin composition or combination thereof is not dispersible in
hot water through the dispersion method described below in the
absence of the ionomer blend component. Pellets or other articles
comprising the ethylene ester copolymer composition, the grafted
polyolefin composition or combination thereof are also not
dispersible in hot water even in the presence of pellets or other
articles comprising the dispersible ionomer composition. Without
being held to theory, it is believed that the ethylene ester
copolymer composition, the grafted polyolefin composition or a
combination thereof must provide a small enough particle size
through the melt compounding process to allow for
self-dispersibility of the total blend. The level of the ethylene
ester copolymer composition, the grafted polyolefin composition or
combination thereof is advantageously low, as described above, to
maintain it as the dispersed phase within the total blend
composition. Importantly, the ethylene ester copolymer composition,
the grafted polyolefin composition or combination thereof provides
the compatibility with the ionomer blend component necessary to
provide the needed small particle size.
[0072] Dispersion Method
[0073] The dispersion method described herein surprisingly allows
for the production of aqueous blend composition dispersions under
very mild process conditions, such as low shear (e.g. simply
stirring a mixture of hot water and solid blend composition) and
low temperature (less than the boiling point of water) at
atmospheric pressure, requiring less energy than prior art
dispersion processes. This dispersion method further provides an
inherently safer dispersion process through the use of preformed
blend compositions by allowing for the avoidance of strong bases,
such as aqueous sodium hydroxide (caustic), aqueous potassium
hydroxide or ammonia, during the dispersion process.
[0074] The dispersion method comprises contacting an article
comprising the blend composition with water at a temperature from
about 80 to about 100.degree. C. In some embodiments, the
temperature is in the range from about 85 to about 90.degree. C.
Surprisingly, the blends described herein can be dispersed in water
at 80 to 100.degree. C., lower than that expected based on the
prior art and requiring signifcantly less energy. However, one can
appreciate that if the blends disperse in that temperature range
they can also be dispersed at temperatures above 100.degree. C.
[0075] The blend composition article may take any physical form
desired, such as powder, pellets, melt cut pellets, coatings,
films, sheets, molded articles and the like. The blend dispersion
may be produced in any suitable vessel, such as a tank, vat, pail
and the like. Stirring is useful to provide effective contact of
the bulk blend article(s) with water as dispersion proceeds.
Preferably the dispersion is produced in about 1 hour or less, such
as in about 30 minutes or in about 20 minutes or less. Due to the
surprisingly rapid dispersibility of the articles comprising the
blend compositions, it is further contemplated that the process may
proceed within a pipeline in which the components of the dispersion
are charged at one end of the pipeline and form the dispersion as
they proceed down the length of the pipeline. For example, the
article may be mixed with water and passed through a heated zone,
with or without added mixing, such as through static mixers.
Alternatively, the article may be mixed with hot water and passed
through a pipeline, with or without added mixing, such as through
static mixers.
[0076] In one embodiment, the article comprising the blend
composition is mixed with water under low shear conditions at room
temperature (about 20 to 25.degree. C.) and the temperature is
raised to about 80 to about 100.degree. C. In another embodiment,
the article comprising the ionomer composition is mixed with water
under low shear conditions at room temperature and the temperature
is raised to about 85 to about 90.degree. C.
[0077] In another embodiment, the article comprising the blend
composition is mixed with water preheated to a temperature of about
80 to about 100.degree. C. under low shear conditions. In another
embodiment, the article comprising the blend composition is mixed
with water preheated to a temperature of about 85 to about
90.degree. C. under low shear conditions.
[0078] The aqueous blend dispersion preferably comprises from a
lower limit of about 0.001 or about 1% to an upper limit of about
10, about 20, about 30 or about 50 weight %, of the blend
composition based on the total weight of the blend composition and
the water.
EXAMPLES
[0079] Table 1 summarizes the ethylene methacrylic acid dipolymers
with copolymerized units of methacrylic acid at the indicated
weight % of the total acid copolymer used to prepare the ionomers
in Table 2. lonomers were prepared from the acid copolymers using
standard conditions. Melt flow rate (MFR) was measured according to
ASTM D1238 at 190.degree. C. using a 2160 g load. A similar ISO
test is ISO 1133.
TABLE-US-00001 TABLE 1 Methacrylic acid (weight %) MFR (g/10 min)
ACR-1 19 400 ACR-2 15 200 ACR-3 19 180 ACR-4 19 60 ACR-5 21.7 30
ACR-6 19 250 ACR-7 23 270
Ionomers
[0080] Table 2 summarizes the ionomers derived from the ethylene
methacrylic acid dipolymers, with the indicated percentage of the
carboxylic acid groups neutralized with sodium hydroxide to form
sodium salts or potassium carbonate to form potassium salts. The
water dispersibility was determined according to the following
General Procedure.
[0081] The General Procedure illustrates addition of the
non-neutralized acid copolymer or ionomer to heated water. The
procedure produced a mixture of water and 10 weight % solid loading
(as weighed prior to addition to the water). Into a 1 quart (946.4
ml) metal can placed into a heating mantle element was added 500 ml
of distilled water. An overhead paddle stirrer (3-paddle propeller
type stirrer) was positioned into the center of the metal can and
turned on to provide slow mixing. A thermocouple was positioned
below the water surface between the paddle stirrer and the metal
can surface. The paddle stirrer was typically set at a speed of
about 170 rpm at the beginning of the process and generally raised
to about 300 to 470 rpm as the viscosity built during dispersion
formation. The distilled water was then heated with an Omega
temperature controller to a temperature of 90 C. The
non-neutralized acid copolymer resin ACR-1 or ionomer (55.5 grams,
in the form of melt cut pellets) indicated in Table 2 was then
added in one portion and the resulting mixture was stirred for a
total of 20 minutes. The resulting mixture was then allowed to cool
to room temperature.
[0082] Materials that did not form dispersions are denoted as "No"
in Table 2, below. For those materials that formed a dispersion
(denoted as "Yes" in Table 2), the dispersion was generally formed
in less than 10 minutes and was stable even after being cooled to
room temperature. As used herein, "stable" means that the
dispersion, a clear liquid with no visible solids, did not exhibit
any visual change after the initial cooling or on storage at room
temperature. The Example dispersions remained as transparent
liquids with no settling after storing at room temperature for
periods of several weeks or longer.
TABLE-US-00002 TABLE 2 Water Base Neutralization MFR Dispersibility
Sample Copolymer Ion Level (%) (g/10 min.) at 90.degree. C. C1
ACR-1 -- 0 -- No ION-1 ACR-2 Na 51 4 No ION-2 ACR-2 Na 70 0.9 No
ION-3 ACR-1 Na 40 12.7 No ION-4 ACR-3 Na 45 3.7 No ION-5 ACR-4 Na
50 0.8 No ION-6 ACR-5 Na 40 0.7 No ION-7 ACR-1 Na 50 5.3 Yes ION-8
ACR-6 Na 60 1.4 Yes ION-9 ACR-1 Na 70 1 Yes ION-10 ACR-7 Na 55 1.4
Yes ION-11 ACR-2 K 65 2.3 No ION-12 ACR-4 K 50 0.9 No ION-13 ACR-6
K 50 3.9 Yes ION-14 ACR-1 K 50 5.4 Yes
[0083] The data in Table 2 show that ionomers prepared from an acid
copolymer with 15 weight % of methacrylic acid did not form aqueous
dispersions using this procedure, even with high neutralization
levels (Ionomers ION-1, ION-2 and ION-11). Ionomers with
neutralization levels less than 50% did not form dispersions, even
with acid comonomers above 19 weight % of the acid copolymer
(Ionomers ION-3, ION-4 and ION-6). Ionomers ION-5, ION-7, ION-12
and ION-14 involved acid copolymers with the same weight % of
methacrylic acid and neutralized to the same level, but with
different melt flows. ION-5 and ION-12, each derived from a parent
acid copolymer with MFR of 60 and having MFR less than 1, did not
provide dispersions. However, ION-7 and ION-14, each derived from a
parent acid copolymer with MFR of 400 and having MFR greater than
1, provided dispersions.
Examples 1-4 and Comparative Example C2
[0084] The melt extrusion compounded blends described below in
Table 3 were produced and tested for dispersibility in heated water
as described above in the General Procedure, providing the results
summarized below in Table 3. EMA-1 was a poly(ethylene-co-methyl
acrylate) incorporating 24 weight % methyl acrylate comonomer with
a MFR of 20. LDPE was a low density polyethylene. EMA-2 was a
poly(ethylene-co-methyl acrylate) incorporating 35 weight % methyl
acrylate comonomer with a MFR of 3. GPO was a metallocene
polyolefin grafted with 0.9 weight % maleic anhydride.
TABLE-US-00003 TABLE 3 Water Blend Composition MFR Dispersibility
Example Component (weight %) (g/10 min) at 90.degree. C. 1 ION-14
95.3 6.7 Yes EMA-1 4.7 2 ION-14 90.4 8.3 Yes EMA-1 9.6 C2 ION-14
90.4 8.1 No EMA-1 4.4 LDPE 5.2 3 ION-14 90.4 8.3 Yes EMA-1 4.4
EMA-2 5.2 4 ION-14 90.4 6.3 Yes EMA-1 4.4 GPO 5.2
Example 5
[0085] Into a 1 quart (946.4 ml) metal can placed into a heating
mantle element was added 300 ml distilled water. An overhead paddle
stirrer was positioned into the center of the metal can and turned
on to provide slow mixing (assumed to be about 170 rpm). A
thermocouple was positioned below the water surface between the
paddle stirrer and the metal can surface. The distilled water was
then heated to 90.degree. C. with an Omega temperature controller
to the temperature. The blend from Example 1 (129 grams, in the
form of melt cut pellets) was then added in one portion and the
resulting mixture stirred for a total of 20 minutes to form the
viscous dispersion. The resulting dispersion was then allowed to
cool to room temperature. The dispersion was stable even after
being cooled to room temperature.
Example 6
[0086] Into a 1 quart (946.4 ml) metal can placed into a heating
mantle element was added 300 ml distilled water. An overhead paddle
stirrer was positioned into the center of the metal can and turned
on to provide slow mixing (assumed to be about 170 rpm). A
thermocouple was positioned below the water surface between the
paddle stirrer and the metal can surface. The distilled water was
then heated to 90.degree. C. with an Omega temperature controller
to the temperature. The blend from Example 2 (129 grams, in the
form of melt cut pellets) was then added in one portion and the
resulting mixture stirred for a total of 7 minutes to form the
viscous dispersion. The resulting dispersion was then allowed to
cool to room temperature. The dispersion was stable even after
being cooled to room temperature.
[0087] Examples 7-12 and Comparative Example C3 illustrate addition
of the blend to cold water followed by heating according to the
following general procedure.
[0088] Into a 1 quart (946.4 ml) metal can placed into a heating
mantle element was added 500 ml distilled water. An overhead paddle
stirrer was positioned into the center of the metal can and turned
on to provide slow mixing. A thermocouple was then positioned below
the water surface between the paddle stirrer and the metal can
surface. The blend, in the form of melt cut pellets, was then added
in one portion. The resulting stirred mixture was then heated to
90.degree. C. with an Omega temperature controller set to that
temperature. After dispersion was complete, the mixture was allowed
to cool to room temperature. The dispersion was stable even after
being cooled to room temperature.
Comparative Example C3
[0089] Pellets of ION-14 (52.9 grams) and pellets of EMA-1 (2.6
grams) described above were each added in one portion. After 10
minutes at 90.degree. C., ION-14 was totally converted to an
aqueous dispersion while the pellets of EMA-1 remained entirely
undispersed.
Example 7
[0090] The blend from Example 1 described above (55.5 grams) was
added in one portion. The mixture had been totally converted to an
aqueous dispersion as the temperature approached 90.degree. C.
Example 8
[0091] The blend from Example 2 described above (55.5 grams) was
added in one portion. The mixture had been totally converted to an
aqueous dispersion after achieving the temperature of 90.degree.
C.
Example 9
[0092] The blend from Example 3 described above (55.5 grams) was
added in one portion. The mixture had been totally converted to an
aqueous dispersion as the temperature approached 90.degree. C.
Example 10
[0093] The blend from Example 4 described above (55.5 grams) was
added in one portion. The mixture had been totally converted to an
aqueous dispersion as the temperature approached 90.degree. C.
Example 11
[0094] The blend from Example 1 described above (26.3 grams) was
added in one portion. The mixture had been totally converted to an
aqueous dispersion as the temperature approached 87.degree. C.
Example 12
[0095] The blend from Example 1 described above (125 grams) was
added in one portion. The mixture had been totally converted to an
aqueous dispersion as the temperature approached 90.degree. C.
* * * * *