Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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WATER-BASED SULFONATED POLYMI~R COMPOSITIONS
Field Of The Invention
r This invention relates to water-based poly~ners, specifically to a method
S for the ~lepa.dLion of water-based sulfonated polymer compositions having enh~nt~ed
mechanical and adhesion ~vpellies.
Rq~l~round Of The Invention
There are several patents which disclose the ~le~ lion of water-based
sulfonated polymer compositions:
U.S. Pat. No. 5,334,690 (Hoechst Aktiengesellschaft) discloses water-
based sulfonated polyule~ e-urea polymers which can be combined with and are in
general compatible with other aqueous polymer dispersions.
U.S. Pat. No. 4,888,383 (E.I. DuPont De Nemours and C~ ~ly)
discloses a process wher,~in water-based polyurethane-urea modified acrylic polymers are
p~cpared by reacting amine and/or hydrazide functional polyacrylic polymers withisocyanate t~rmin~te~l polyurethane prepolymers.
U.S. Pat. No. 4,491,646 (Ashland) discloses adhesives wherein hydroxyl
functional polyvinyl polymers are blended with water dispersible polyfunctional
iso-;y~,ale~.
Other related patents include U.S. Pat. No. 5,371,133 (National Starch),
U.S. Pat. No. 5,200,463 (Huels), U.S. Pat. No. 5,204,404 (DuPont), U.S. Pat. No.5,173,526 (Air Products & Chemicals, Inc.) and U.S. Pat. No. 5,071,904 (PPG).
S~mr-:lry Of The Invention
The present invention discloses water-based sulfonated polymer
compositions comprising:
A) at least one water-based sulfonated polyurethane-urea polymer compri~in~:
1) at least one polyisocyanate; and
2) at least one sulfonated polyester polyol wherein the sulfonate
groups are present in the form of alkali metal salts;
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B) at least one aqueous polyvinyl dispersion compri~ing;
1) at least one ethylenically nncz~ r~te~1 monomer;
2) and optionally, at least one free radically reactive protective
colloid c~ mpri~in~ active hydrogen atoms, and optionally,
C) at least one sulfonated polyurethane-vinyl polymer composition which is
the reaction product of,
I) at least one isocyanate-t~",li~ d polyurethane prepolymer
CO~
a) at least one polyisocyanate; and
b) at least one sulfonated polyester polyol wherein the
snlfon~te groups are present in the form of alkali metal
salts, with
2) an aqueous polyvinyl dispersion comprixin~;
a3 at least one ethylenically l-.-x~ tPd monomer, and
1 5 optionally,
b) at least one free radically reactive protective colloid
compri~in~ active hydrogen atoms.
Su~prisingly, the sulfonated polymer compositions have enhanced
me~h~nical and adhesion ~lu~ Lies and show stability at pH values greater than about
20 2Ø It is sllrmi~ecl that some of these unique properties can be attributed to the
development of interpenetrating polymer n~ Lv~ lks and the sulfonate character located in
the polyol segm~nt of the polyu,eLlla~e polymer.
The illV~ iVe compositions are useful as adhesives, binders, coatings and
primers on any substrate including paper, wood, metals, concrete, glass, cloth and
25 synthetic polymers, and are useful in applications including fiber grass sizing,
woodworking, automotive, film l~minslting and in the m~nllfs~cture of shoes.
In another aspect, the present invention discloses a method for the
preparation of sulfonated polymer compositions wherein isocyanate t~nnin~ted
polyurethane prepolymers are dispersed in a~ueous polyvinyl dispersions which may
30 contain primary amines, secondary ~min~s, p~ laly hydroxyl groups, secondary
hydroxyl groups and form~mi-le groups. The method comprising:
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A) forming a water dispersible isocyanate-t~rmin~tef1 polyurethane
prepolymer by rç~qcting;
1) at least one polyisocyanate; and
2) at least one sulfonated polyester polyol wherein the sulfo groups
are present in the form of aLkali metal salts;
B) forming an aqueous polyvinyl dispersion by free radically polymeri_ing;
1) at least one ethylenically unsaturated monomer; and optionally,
2) at least one free radically reactive protective colloid cc-mpri.~in~
active hydrogen atoms; and then
10 C) dispersing the product of A) into B).
In another aspect, the present invention discloses a water based sulfonated
polymer composition and a method of making the same by seed emulsion
polymeri7~tion. The composition comprises the reaction product of:
a) at least one sulfonated polyurethane dispersion;
b) at least one aqueous ethylenically unsaturated monomer pre-
emulsion comprising at least one ethylenically unsaturated
monomer; and
c) an initi~tor.
The method of p~p~ing the same comprises the steps of:
a) forming an aqueous pre-emulsion comprising at least one ethylenically
unsaturated monomer pre-emulsion comprising at least one ethylenically ullsaLuldl~d
monomer and op$ionally at least one snrf~-t~nt and
b) reacting said aqueous pre-emulsion with at least one sulfonated
polyurethane dispersion optionally in the presence of an initi~tor solution and optionally
in the presence of a reducer solution.
In another aspect, the present invention discloses a polyurethane/polyvinyl
hybrid latex and a method of making the same by seed emulsion polymerization. The
hybrid latex comprises the seed emulsion polymerization reaction of:
a) at least one sulfonated polyulc;Lll~ e dispersion, the polyurethane
serving as a seed;
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b) at least one aqueous ethylenically un~,aLul2lt~d monomer pre-
emulsion comprising at least one ethylenically ~lnczttnr~tec~
monomer; and
at least one free radical; . .;
Brief Description of the D. ~ o~
Figure 1 is a graph showing the seed polyu~ e particle size
distribution (dotted line) as a fimction of the final hybrid latex particle distribution (solid
line), for the latex (water based sulfonated polymer composition) prepared in Example 6.
Figure 2 is a graph showing the seed polyurethane particle size
distribution (dotted line) as a function of the f~al hybrid latex particle distribution (solid
line), for the latex (water based sulfonated polymer composition) prepared in Example 7.
15 Detailed Descrip~ion Of The l~vention
The sulfonated polymer compositions have enhanced mechz~nic z~l and
adhesion properties colllpaled to their corresponding water-based sulfonated
polyurethane-urea polymers, aqueous polyvinyl dispersions and their simple blends. For
the purposes of the present application, polyvinyl dispersions include dispersions of
20 addition polym~ri~zltion products of ethylencially unsaturated monomers including, but
not limited to (meth)acrylate monomers. Also, polyurethane refers in the presentapplication to a polymer co..~ ;t-g more than one urethane group and is int~n-1e~ to
include polyurethanes contztining urea groups as well (polyurethane-ureas). It is
sllrmi~ed that some ofthese unique plo~c~lies can be atEributed to the formation of
25 interpenetrating polymer networks. The term "interpenetrating polymer n~;L~c ,1~'' is
defined as a cros~linked and/or semi cro~linke~l system comprising at least two
similzlr or different polymers. IPNs are further described in the "Handbook of
Adhesives", Irving Skeist, 3rd edition, chapter 1, page 18, Van Nostrzmd, NY, 1990.
For the the purposes of the present application, "hybrid" denotes a
30 polymer comprised of two or more ~ imilzlr polymers. The ~ Similz1r polymers may or
may not be covalent linked.
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s
In the present invention, when isocyanate-termin~t~cl polyurethane
prepolymers are dispersed in aqueous polyvinyl dispersions, which may contain active
hydrogen atoms such as primary amines, secondary ~min~c, primary hydroxyl groupsand secondary hydroxyl groups, the isocyanate Lt~ ecl polyurethane prepolymer
5 dispersions interact with the aqueous polyvinyl dispersions to form IPNs and cro~link~(l
networks. The frequency of such int~r~ctions can be influenced by the quantity of
isocyanate and active hydrogen atoms present in the respective polymer dispersions. It is
possible to increase the crosslink density using a structured aqueous polyvinyl dispersion
wherein active hydrogen atoms are distributed on the surface of the particle. A
10 structured particle can be generated when ethylenically uns~ Lled monomers,
co~ls-i " i I ~p; active hydrogen atoms, are added at the end of the free radical emulsion
polymerization process. It is believed that such a particle morphology improves the
collision frequency of the isocyanate/active hydrogen atom reaction to increase the
composition's crosslink density.
The dispersed particles can contain a complex mixture of polymers
consisting of sulfonated polyurethane-urea polymers, polyvinyl polymers and sulfonated
polyurethane-vinyl polymers. The complex particle llliX~Ul~S can be formed when
subst~nti~lly ~ imil~r or substantially dirr~ lll polymers diffuse and interact or
crosslink with adjacent particles. Such diffusion processes may generate particles having
20 polyrners within the particle that are different when compare with polymers on the
surface of the particle. Examples include particles having substantially polyvinyl based
polymers on the surface of predominantly polyurethane-urea based particles or
substantially polyurethane-urea based polymers on the surface of predo. . . i ~ y
polyvinyl based particles. Such surface layers may be continuous or non-continuous and
25 can vary in thickness. If a particle's surface layer has a substantial thickness, as well as
being continuous, then the particle approaches a core-shell type structure.
The isocyanate-t~rrnin~te-l polyurethane prepolymers of the present
invention may be formed using monoisocyanates and polyisocyanates. The isocyanates
may be linear aliphatic, cyclic aliphatic, aromatic and ll~ixLu~t;s thereof. Exarnples of
30 commercially available polyisocyanates include V~st~n~t6i) IPDI which is isophorone
diisocyanate from HULS America Inc. (PiscaL~w~y, NJ), TMXDT(~) which is
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tetramethylxylene diisocyanate from Cyanarnid (Wayne, NJ), Luxate~ HM which is
he~methylene diisocyanate from Olin Corporation (Starnford, CN), diphenylmethanediisocyanate from Upjohn Polyrner Chemicals (~ 7~o~ MI), Desmodur(g) W which
is dicyclohexylmethane-4,4'-diisocyanate from Bayer Corporation (Pittsburgh, PA) and
S toluene diisocyanate CIDI). The preferred diisocyanates are hP~methylene diisocyanate,
isophorone diisocyanate and their lllixlw. s.
If des*ed, small guantities of polyisocyanates which have an isocyanate
content greater than 2.1 may be used. Additionally, modified polyisocyanates which are
prepared from hexamethylene diisocyanate, isophorone diisocyanate and toluene
10 diisocyanate may also be used. Said polyisocyanates can have functionalities including
urethanes, uretdiones, isocyanurates, biurets and mixlulcs thereof.
The sulfonated polyester polyol component used in the preparation of the
isocyanate-t(~rminzlt~?-1 polyurethane prepolymer can have hydroxyl numbers, as
det~rmint~-l by ASTM tiesi~n~tion E-222-67 (Method B), in a range from about 20 to
about 140, and preferably from about 40 to about 110. The polyols may be forrned ~,vith
components such as diacids, diols, sulfonate diols and sulfonate diacids. Such polyols
and their pl~dLion are further described in U.S. Pat. No. 5,334,690, incorporated
herein by reference. The ~l~rt;;ll~ d sulfonated polyester polyols are based on 5-
sulfoisophthalic acid monosodium salt, adipic acid and 1,6-hexanediol and/or diethylene
20 glycol. It is believed that the sulfonate character, which is present in the polyol segment,
enhances the polymer's dispersibility and stability at reduced pH.
Optionally, non-sulfonated polymeric diols may be used in combination
with the sulfonated polyester polyols. Such polyols may have lly~o~yl numbers in a
range from about 20 to about 140, and preferably from about 40 to about 110. The non-
25 sulfonated polymeric polyols may include polyester polyols, polyether polyols,polycarbonate polyols, polyu~ e polyols, polyacetal polyols, polyacrylate polyols,
polycaprolactone polyols, polye~ .ide polyols, polythioether polyols, and mixtures
thereof.
Alkylene diols may also be used in the pr~udlion of the isocyanate -
3Q tf rtninzlte(1 prepolymers. The alkylene diols may have hydroxyl numbers in a range fromabout 130 to about 1250, and preferably from about 950 to about 1250. The ~IcÇellcd
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alkylene diols include 1,4-butanediol, 1,6-hexanediol and 2-methyl-1,3-propanediol and
may be present in the isocyanate t~rmin~e~l polyurethane prepolymer in a range from
about 0.1% by weight to about 10.0% by weight, and preferably from about 0.5% byweight to about 5.0% by weight, based on 100 parts of total prepolymer solids.
Higher functional polyols may be used in the pl~ation of the
polyul~Lll~le-urea polymers. Suitable examples include glycerol, trimethylolpropane,
1,2,4-butane triol, I ,2,6-hexane triol and mixtures thereof. The pL~r~ d higherfunctional polyol is trimethylolpropane. Said polyols may be present in a range from
about 0.1% by weight to about 1.0% by weight, and preferably from about 0.3% by
10 weight to about 0.7% by weight, based on 100 parts oftotal isocyanate-t~rmin~ht
polyurethane prepolymer solids.
Optionally, dihydroxy carboxylic acids may be used when pl~ g the
isocyanate-t~rrnin~te~l poly~LIeLll~le prepolymer. A preferred dihydroxy carboxylic acid
is dimethylolpropionic acid. The dihydroxy carboxylic acid component may be present
15 in a range from about 0.05% by weight to about 1.0% by weight, and preferably from
about 0.2% by weight to about 0.5% by weight, based on 100 parts total polyult;lll~le
prepolymer solids.
~eutralization of the dihydroxy carboxylic acid groups can be
accomplished with compounds such as alkali metal hydroxides, organic tertiary ~mines,
20 ammonia and mixtures thereof. Preferred neutralizing agents are sodium hydroxide and
triethylamine. Conversion of the acid groups to ionic groups (salts) can be accomplished
before, or at the same time, that, the isocyanate terrnin:~te-l polyurethane prepolymer has
been dispersed in the polyvinyl dispersion mixture.
The isocyanate-t~rmin~t~fl polyurethane prepolymer is prepared by
25 reacting a stoichiometric excess of polyisocyanate with said polyol components. The
reactants are in such proportions that the resulting percent isocyanate may be in a range
from about 1.0% by weight to about 10.0% by weight, and preferably from about 2.0%
by weight to about 5.0% by weight, based on 100 parts total of isocyanate terrnin~t~cl
polyurethane prepolymer solids. The prepolymers may be processed at tempcldlules in
30 a range from about 30~C to about 110~C, and preferably from about 65~C to about 85~C.
Additionally, small quantities of catalysts may be used to accelerate the
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hydroxy/isocyanate reaction. The catalysts can be present in a range from about 0.05%
by weight to about 2.0% by weight, and preferably from about 0.13% by weight to about
0.15% by weight, based on 100 parts total isocyanate-tPrminzttc~l polyurethane
prepolymer solids. An exarnple includes MetacureTN' T-12 w~tich is an organic tin
S compound from Air Products and Chemicals, Inc. (Allentown, PA).
The ethylenically lln~t~lr~ted monomers can include monow~s~ dLed
monomer~, polyunsaturated monomers and ~ wes thereof. Examples include methyl
acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propylacrylate, iso-propyl
acrylate, methyl methacrylate, butyl methacrylate, vinyl acetate, vinyl propionate, vinyl
10 ethers, ethylenically unsaturated filmPr~Ps, ethylenically wl~aLul~led maleates, styrene,
acrylonitrile, acryl~tmi~les, but~tnediol diacrylate, hP.sc~n~liol diacrylate, ethylene glycol
dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
Et_ylenically unsaturated monomers co~ it~g anionic and/or ionic
groups can be used. Examples of such monomers include acrylic acid, methacrylic acid,
15 fumaric acid, crotonic acid, itaconic acid, mesaconic acid, maleic acid, citraconic acid
and/or their corresponding ionic groups. Said monomers may be in a range from about
0.1% by weight to about 25.0% by weight, and preferably from about 0.1% by weight to
about 10.0% by weight, based on 100 parts total composition solids.
Ethylenically unsaturated monomers co~ g active hydrogen atoms
20 may also be used. The term "active hydrogen atoms" refers to hydrogens which display
activity according to the Z~cwiLilloff test as described by Kohlerin, J. Am. ~*em. Soc.,
49, 3181 (1927). Examples include hydroxyethyl acrylate, allyl alcohol, allyl amine, N-
methylol acrylamide, mono-acrylic acid esters of glycols, itaconic acid and methyl-3-
arninocrotonate .
Amine and hydroxyl functional protective colloids may be used to ~ e
the aqueous polyvinyl dispersion of the present invention Suitable examples include the
water dispersible polyvinyl alcohol-copoly(vinyl amine) polymers described in EP0599245 assigned to Air Products and Chemicals, Inc. (Allentown, PA). Such protective
colloids may have an amine content in a range from about 0.5 meq. amine/gram to about
30 3.5 meq. amine/gram, and preferably from about 1.0 meq. amine/gram to about 3.0 meq.
arnine/gram. The number average molecular weight may be in a range from about
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10,000 grams/mol. to about 350,000 grams/mol., and preferably from about 30,000
grams/mol. to about 250,000 grams/mol. Said colloids can be present in a range from
about 0.1% by weight to about 20.0% by weight, and preferably from about 0.5% byweight to about 5.0% by weight, based on 100 parts total polyacrylic solids. It is
5 assumed grafting reactions occur during the emulsion polymer;7~tion process. The graft
copolym~ri7~tion process is further described in "Polyvinyl Alcohol Developments",
edited by C.A. Finch, John Wiley & Sons, New York, 1992, pp. 449-453.
Specialty monomers may also be incorporated into the aqueous polyvinyl
dispersions and include the amino organo-silane coupling agente described in U.S. Pat.
No. 4,745,02g (PPG) and U.S. Pat. No. 5,236,982, (Owens-Corning), the
imidazolidinone functional wet adhesion monomers described in U.S. Pat. No.
5,496,907, (H.B. Fuller Co., St. Paul, MN) and the Vinzlmern EF monomer which is N-
ethenylform~mi~1e from Air Products Chemicals, Inc. (Allentown, PA).
When Vinamer EF ~onomers are incorporated into the agueous polyvinyl
15 dispersions, the bound ro~ a~ide group may be hydrolyzed to a primary amine using
catalysts such as bases or acids including sodium hydroxide, hydrochloric acid and
sulfuric acid. The resulting arnine functional polyvinyl can then be used as a reactive
component in the process of the present invention.
The aqueous polyvinyls can be formed using m~t~ri~le and free radical
20 polymerization processes known in the art. For example, the free radical initiators, used
in the addition polymerization process, may be water soluble, oil soluble or ~ Lules
thereof. Exatnples include hydrogen peroxide, sodium persulfate, potassium persulfate,
ammonium persulfate, 2,2-azobis (2,4-dimethylpents~n~nitrile), 2,2-azobis (2-
methylpropanenitrile) and mixtures such as t-butylhydroperoxide, Fe-EDTA and
25 isoascorbic acid. Said initiators may be present in amounts from about 0.05% by weight
to about 1.5% by weight, and preferably from about 0.1% by weight to about 0.5% by
weight, based on 100 parts total solids. Also, oxicii7~ng catalysts may be used
independently or in combination with reducing agents such as sodium forn ~ ehyde-
sulfoxylate, ferrous salts, sodium dithionite, sodium hydrogen sulfite, sodium sulfite and
30 sodium thiosulfate. The redox catalysts may be present in amounts from about 0.05% by
weight to about 1.5% by weight, preferably from about 0.1% by weight to about 0.5% by
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weight, based on 100 parts total solids.
The ethylenically unsaturated monomers are polymerized using free
radical polymerization techniques known in the art. The free radical initi~tors can be
added all at once, slowly over time or as a partial initial charge with the r~mz~in-l~r being
added slowly over time.
Free radical polym~ri7~tion may be conducted at tempc~dlul~s in a range
from about 5~C to about 85~C, and preferably from about 25~C to about 80~C.
The water-based sulfonated polymer compositions of the present
invention are formed using a method wherein isocyanate-tf rmin~ted polyulel~
prepolymers are dispersed in an aqueous polyvinyl dispersion which may contain
primary ~mine~, secondary amines, primary hydroxyl groups~ secondary hydroxyl groups
and form~mide groups. It is also possible to disperse the isocyanate-termin~7tefi
polyurethane prepolyrner in water and then immerli~tely blend with the aqueous
polyvinyl dispersion. Optionally, the aqueous poly~inyl dispersion may be added to a
neat or water dispersed isocyanate-termin~t~d polyurethane prepolymer. The ~ imilz~r
polymers are suitably combined at temperature in a range from about 25~C to about
95~C, preferably from about 45~C to about 75~C.
If amine functional aqueous polyvinyl dispersions are used, the polymer
components may be blended using an equivalence ratio of amine active hydrogen toisocyanate in a range from about 1:10 to about 10:5, and preferably from about 1:5 to
about 5:1.
If desired, water soluble compounds co.,~ primary and/or secondary
amines may be reacted with the polymer mixture of the invention. Suitable examples
include monoethanolamine, ethylen~ mine, diethylene triamine and ammonia.
The water-based sulfonated polymer compositions may have viscosities in
a range from about 10 mPa.s to about 1,000 mPa.s, and preferably from about 10 mPa.s
to about 500 mPa.s. The particle size distribution may be monomodal or multimodal and
generally will have a mean diameter in a range from about 0.01 microns to about 2.0
mlcrons.
The water-based sulfonated polymer compositions may have a solids
content in the range from about 20% by weight to about 70% by weight, and preferably
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11
from about 3 5% by weight to about 55% by weight of the total composition.
The dried sulfonated polymer compositions may have single or multiple
glass transition (Tg.) telllptildLul~;, in a range from about -100~C to about +200~C.
The present invention is also directed to a water based sulfonated polymer
composition which may be used, inter alia, for fiberglass sizing and a method for m~kin~
the same. The water-based sulfonated polyuleLhalle polyvinyl hybrid latex of the present
invention comprises the reaction product of at least one sulfonated polyurethanedispersion, at least one aqueous ethylenically uns~Luldl~d monomer pre-emulsion
comprising at least one ethylenically ~uls~LuldL~d monomer and at least one free radical
10 initiator, such as those disclosed above.
The present invention is also directed to a water-based sulfonated poly~ner
composition comprising particles, the particles comprising a core and a surface wherein
the core and surface comprise substantially dirr~ l~lll polymers, the core comprising at
least one polymer selected from the group con~i~tinp of sulfonated polyurethane
15 polymers and sulfonated polyurethane-urea polymers and l~ ules thereof, the surface
comprising predomin~ntly polyvinyl polymers. The composition may be formed from
the free radical seed emulsion polymeri7~tion of at least one ethylencially unsaturated
monomer in the presence of a sulfonated polyurethane or polyu,cLh~lle-urea dispersion,
the polyuleLlla~le serving as a seed.
Sulfonated polyurethane dispersions such as those been disclosed in U.S.
Pat. No. 5,608,000 (Duan et al.), U.S. Pat. No. 5,610,232 (Duan et al.) are suitable for
use in the present invention. Two sulfonated polyurethane dispersions which are
embo~1iment~ of the above inventions, NP-4062-M or NP-4073, both of which are
produced by the H.B. Fuller Company, are particularly suited for use in the present
25 invention although other sulfonated polyurethane dispersions may be used as well
including sulfonated polyurethane-urea dispersions.
The aqueous ethylenically unsaturated monomer will preferably be chosen
from among acrylate monomers, (meth)acrylate mon~ mer.c, (meth)acrylic monomers,vinyl monomers, allylic monomers, acrylamide monomers or ~ Lules thereof.
30 Examples include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-propylacrylate, iso-
propyl acrylate, butyl methacrylate, hç~nç-liol diacrylate, ethylene glycol
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WO 98/06768 PCTAUS97114386 12
dimethacrylate, trimethylol~l.,p~ule triacrylate and pentaerythritol triacrylate and
lllixLul~;s thereof. Preferably, the emulsion comprising the monomer will comprise
methyl meth~rrylate, n-butyl acrylate, hydroxy ethyl methacrylate and mixtures thereo~
However, any of the ethylenically unsdluldl~d monomers mentioned above such as
5 ethylenically lm~tllr~ted monomers cornpricing anionic and/or ionic groups, orethylenically unsaturated monomers cont~ining active hydrogen atoms may be used as
well. A suitable s-lrf~- t~nt such as Pluronic L64 (m~mlf~ctured by BASF) or a
combination of surfactants may be used in ple~ g the pre-emulsion
In one embodiment the ratio of sulfonated poly~Lllalle solids to
polyvinyl solids is from about 9:1 to about 1:9. Preferably, the ratio is from about 4:1 to
about 1:4 and most preferably, the ratio is from about 4,1 to about 2:1.
The present invention is also directed to a water-based sulfonated
polyurethane polyvinyl hybrid latex comprising polyurethane polyvinyl particles wherein
the average particle size is at least 200 nm.
The water-based sulfonated polymer compositions formed via the seed
emulsion polymeri7~tion are characterized by high lap shear strengths of at least about
350 psi.
The present invention is also directed to a method for plt;~ g the
above-mentioned polyurethane polyvinyl latex hybrid. The method comprises the steps
20 of forming an aqueous pre-emulsion compri~ing at least one ethylenically lmc~tllrs~te~l
monomer, the pre-emulsion compri~ing at least one acrylate and optionally a sllrf~rt~nt
and reacting the aqueous pre-emulsion with at least one sulfonated polyurethane
dispersion in the presence of at least one free radically ini~i~tr,r.
The aqueous polyvinyl pre-emulsion may be formed by dispersing
25 ethylenically ull:idluldled monomers in water, with a surfactant and ~git~ting the mixture.
The pol~ u~ haue polyvinyl latex dispersion is then formed by adding an
initiator solution such as t-butyl hydrogen peroxide, a reducer solution such ashydrosulfite and the pre-emulsion to a polyurethane dispersion. ~ltrrn~tively, the
initi~tr,r may already be present in the pre-emulsion or in the polyurethane dispersion.
30 The rnixture is allowed to react over a period of time at a t~ dlllre between 50~C and
100~C, preferably at 65~C.
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- 13
The characteristics of the water-based sulfonated polymer compositions
may be modified by the addition of compounds including surfactants, defoaming agents,
coalescing aids, fungicides, bactericides, polyfunctional cro~linking agents, plasticizers,
thickenin~ agents, fillers, pi~ment~, reactive pi~ment~, dispersing agents for the
S pigments, colors, perfume-like m~teri~l~, W stabilizers, seqllest~?ring agents, waxes,
oils, fire lel~dail~ agents and organic solvents. Such materials may be introduced at any
stage of the production process.
The present invention is further illustrated by the following examples.
EXAMPLI~S
In the examples, the following test methods were used.
Tensile Strength and ElongatiQn
The polymer dispersions were cast to generated dried films having a thickness ina range from about 20 mils. to about 40 mils. Type V dogbones were cut with a Dewes
15 Gumbs Die and conditioned at least 24 hours in an environment having 50% relative
hllmitlity at 23~C. The samples were run using ASTMD-638 at a crosshead speed of 5.0
cm./min.
Shear Strength:
The polymer dispersions were coated on steel, acrylonitrile-butadienestyrene
(ABS) and glass then dried 24 hours. Like substrates were mated using hand ~les~ e
then heat activated at 70~C for 30 minlltes- The samples, which has a bond area of 0.5 x
1.0 inches, were run using ASTM-D-1002 at a crosshead speed of 1.27 cm/min.
Peel Sll . ~h
Peel strength was measured as follows. A precut sheet (10.5 x 12.75 inch)
of 10 mil thick clear, pressed, polished PVC was cleaned with isopropyl alcohol and
placed on a glass or alnminllm plate co~ g a small amount of isopropyl alcohol.
Excess isopropyl alcohol was removed to produce a good seal. The exposed PVC
surface was wiped with isopropyl alcohol. An adhesive film, dispensed from a film
applicator set to S mils, was cast over the PVC sheet, according to the method of ASTM
30 specification D323-87. The adhesive was allowed to dry at ambient temperature. A
second sheet of PVC, cleaned similarly to the first sheet, was placed over the first coated
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14
PVC sheet. The PVC adhesive sandwich was cut into 1 inch strips and allowed to dry
over 2 hours.
The strips were placed into a heat sealer with the uncoated PVC in contact
with the upper platen, the upper platen having been preheated to 1 90~F and with a
5 ~ c; setting of 50 psi. Following a 30 second dwell time, the temperature at the bond
line was 1 60~F. A . " i l ,i,, .. ~ of 6 bonds per strip were heat sealed with a total bond area
of 1 inch by 7 inches with 1.5 inches of no bond on both ends.
The bonds were allowed to age at ambient temperature for 1 to 2 hours
and 1 week prior to testing. Testing was performed on a Thwing Albert Intellect 500
with a cross head speed of 12 inches per minute, a 1 inch prepeel and 3 inches of
recorded peel.
Lap Shear Strength:
The sample was coated on glass and allowed to dry ov~rni~ht The bond
area was 0.5xl.0 in2. The lap shear satnple was m~int~ined at 160~F for 30 mimltes Lap
shear strength was then measured using ASTM D-1002 with a crosshead speed of 0.5in/mimlte. The measurement was made under an ~llvh~ cnt of 50% relative humidityat a temperature of 23 ~C.
F~s-ml le 1:
This example describes the pl~pdld~ion of a water-based sulfonated
polyurethane-vinyl polymer composition. The composition and its pl op~,~ lies are
compared to its corresponding polymer components.
Compound lA
Compound lA is an aqueous polyvinyl dispersion prepared with a
reactive emulsifying agent which is polyvinyl alcohol/polyvinylamine copolymer
(PVOE~-PVAM) from Air Products & Chemicals, Inc. (Allentown, PA3.
(I) Reactor char~e Grams
PVOH/PVAM (6% vinyl amine, medium M.W.) 1.50
De-ionized water Acetic acid 350.00
Acetic acid 0.30
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(2) Pre-emulsion
Methyl Methacrylate 155.00
N-butyl acrylate 145.00
Methacrylic acid 3.90
Thiolacetic acid 0.10
(3) DelaYed Sllrf~t~nt feed
T-Det 0-407 from Harcros 7.50
De-ionized water 30.00
(4) Initiator feed
T-butyl hydroperoxide 1.28
De-ionized water 20.00
(5) Reducer feed
Sodium formaldehyde sulfoxide 0.92
De-ionized water 20.00
To a reactor equipped with an agitator, thermometer, con~len~r and
nitrogen purge was added reactor charge (1). The mi~ul~ was heated to 65~C and
it:~te~l for 30 mimltes While m~ g the reaction tel~ d~ule at 65~C, the pre-emulsion (2) and surfactant feed (3) was added over a 3 hour period. The initiator feed
(4) and reducer feed (5) were added over a 3.5 hour period. Once all the materials were
added, the dispersion was heated an additional 30 minllt~s. The polymer had a solids
25 content of 33.2% and a p~ of 2.65.
Compound lB
Compound 1 B is a water-based sulfonated polyurethane-urea polymer.
A reactor was charged with 4.5 grams (0.099 hydroxyl equivalence) 2-
methyl-1,3-propanediol and 95.4 grams (0.093 hydroxyl equivalents) molten Rucoflex~).
XS-5570-55 which is a sulfonated polyol from Ruco Polymer Corporation based on 5-
sulfoisophthalic acid monosodium salt (4% by weight), adipic acid and diethyleneglycol. The ll~ ul~ was charged with 39.96 grams isophorone diisocyanate, eye drop of
dibutyl tin dilaurate and heated to 80~C for 2 hours to produce an isocyanate-termin~te~l
polyurethane prepolymer.
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16
The reslllting isocyanate-t~rmin~tecl polyurethane prepolyrner was
dispersed in 247.0 grams de-ionized water at 70~C, using mild agitation, and heated an
additional 2 hours at 65~C.
Compound lC
Compound lC is a water-based sulfonated polyurethane-vinyl polymer.
139.86 grams of a isocyanate-t~orrninsit---l polyurethane prepolymer, (prepared in
the manner of compound lB), which had a temperature of 80~C, was dispersed in 139.86
grarns de-ionized water and ~gihted for 5 i"i"~ The dispersed prepolymer was
charged with 341.5 grams of an amine and hydroxyl functional polyvinyl dispersion
10 (Compound lA). The mi~ t; was agitated and heated to 65~C for 2 hours. The water-
based sulfonated polyurethane-vinyl polymer had a solids content of 40.2% and a pH of
6.4.
The compounds were tested for tensile strength, elongation and shear
strength on glass, steel and acrylonitrile-butadiene-styrene copolymers (ABS). The
15 results are provided in Table I below:
Table 1. Tensile Strenth, clc gS~tiq and shear strength
Compound Tensile ~i~n~ptif~n ShearSti-ength (Kgs./cu.cm.)
Strength (~/0)
(Kgs./cu.cm)
Steel/Steel Glass/Glass ABS/ABS
Compo-ln~l lA 117.40 1,020 20.38 18.98 40.07
Compound lB 60.45 3,810 18.98 21.79 26.71
Compound lC 75.92 1,680 33.04 40.07 39.36
Compound IA 44.29 1,130 21.79 26.71 37.26
and lB (50/50
Blend~
The data shows the sulfonated polyurethane-vinyl polymer (Compound
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17
lC) has enhanced mechanical ~lupel~ies compared to the blend of Compound lA and
lB. The data also shows Compound lC has enh~n-e~l adhesion properties compared to
Compound lA, Compound lB and their 50/50 blend, thus showing the utility ofthe
invention.
s
F~s-ml~le 2:
This exarnple describes the ~l~d~ion of a water-based sulfonated
polyurethane-vinyl polymer using vinyl acetate. The inventive polymer properties are
compared to its corresponding polymer components.
Compound 2A
Compound 2A is an aqueous polyvinyl acetate dispersion using a reactive
emulsifying agent, which is polyvinyl alcohol-polyvinylamine copolymer (PVOH-
PVAM), from Air Products & Chemicals, Inc. (Allentown, PA).
The polymer was pl~_~alcd as described in Example 1 (Compound lA)
with the exception that the pre-emulsion contained 265.0 grams vinyl acetate, 35.0 grams
n-butyl acrylate, 3.9 grams methacrylic acid and ~).10 grams thiolacetic acid. The
reslllting polymer dispersion had a solid content of 33.6% and a p~I of 2.5.
Compound 2B
Compound 2B is a sulfonated polyurethane prepolymer.
The polymer was prepared exactly as described in Example 1 (Compound
lB).
Compound 2C
Compound 2C is a water-based sulfonated polyurethane-vinyl acetate
polymer.
139.86 grams of an isocyanate-termin~tefl polyurethane prepolymer prepared in
the manner of compound lB but before dispersion, which had a temperature of 80~C,
was dispersed in 247 grarns de-ionized water (70~C) and ~git~t~l for approximately 10
minlltes. The dispersed prepolymer was charged with 341.5 grams of the amine and
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18
hydroxyl functional polyvinyl dispersion described as Compound 2A. The mixture was
mildly ~3~it~e-1 and heated to 65~C for 2 hours. The resulting water-based sulfonated
polyul~Lllalle-vinyl acetate polymer composition had a solids content of 35.5% and a pH
of 6.5.
The compounds were tested for tensile strength, elongation and shear
strength on glass, steel and acrylonitrile-b~lt~1iene-styrene copolymers (ABS). The
results are provided in Table 2:
Table 2. Tensile Strenth, elongation and shear strength
- Compound Tensile Elongation ShearStrength (Kgs./eu.cm.)
Strength (~/0)
~Kgs./cu.cm)
Steel/Steel Glass/Glass ABS/ABS
Compound2A 131.46 330 9.14 3.51 16.17
Compound 2B 60.45 3810 21.79 21.79 26.71
Compound 2C 120.91 1,190 26.71 32.33 34.45
Compo~md 71.00 920 18.28 33.74 47.10
2Aand 2B
(50/50 Blend)
The data shows the sulfonated polyurethane-vinyl acetate polymer
(Compound 2C) has enhanced m~ch~nical pl~lpCL ~ies compared to the blend of
Compounds 2A and 2B. The data also shows Compound 2C has enh~nc~ecl adhesion
properties compared to Compound 2A and Compound 2B thus showing the utility of the
1 5 invention.
Example 3:
This example describes the plcpalc~Lion of a water-based sulfonated
polyurethane-vinyl polymer wherein the amine functional polyvinyl dispersion is formed
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19
using Vinamer EF monomer which is N-ethenylformamide from Air Products &
Chemicals, Inc. (Allentown, PA).
-
Compound 3A
S Compound 3A is an arnine functional polyvinyl dispersion using N-
ethenylform~mi~le
(1)
Reactor Char~e Grams
De-ionized water 295.0
Potassium persulfate 0.42
De-ionized water 20.0
(2)
Pre-emulsion Grams
De-ionized water 80.0
T-Det 0-407 (Hacros) 8.86
Fo~ t~r 111 0.325
Potassium persulfate 0.55
Methyl methacrylate 155.0
N-butyl acrylate 155.0
Methacrylic acid O.S
10 (3)
Initiator feed Grams
De-ionized water 20.0
Potassium persulfate 0.42
(4)
Monomer feed Grams
- Vinamer EF 3.1
The pre-emulsion (2) was ~l~al~,d using the following procedure. The
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water, s~lrf~f~ntJ defoamer and initi~tor were combined and ~it~tçfl for 15 minl~t~s.
The monomers were added to this mixture over a 30 minute period, using agitation, to
form a milky white pre-emulsion.
To a reactor equipped with an agitator, thermometer, condenser and
S nitrogen purge was added the reactor charge (1). The m~t.?ri~l~ were heated to
approxin~Rtely 80~C and charged with 2% of the total pre-emulsion (2) then stirred an
additional 15 minlltt~ While Ill~ A;II;II~ a reaction lelllpc~dlul~ of 80~C, the pre-
emulsion (2) was added over a 3 hour period. The monomer feed (4) was added
approxim~ly 1.5 hours after the pre-emulsions initial feed. Once all the m~tf.ri~l~ were
10 added, the reaction mixture was heated an additional 30 minutes. To the dispersion was
charged 3.1 grams Igepal C0-710, which is a surfactant from Rhone-Poulenc, and the
reaction mixture was heated an additional hour to allow the complete free radical
polymerization of said mon~mer~ The incorporated Vinamer EF monomer was then
hydrolyzed to a primary amine. This was accomp!i~hed by adding 17.5 grams of a 5%
15 sodium hy~o~side solution and heating an additional 2 hours at 80~C.
Compound 3B
Compound 3B is a water-based sulfonated polyurethane-vinyl polymer.
To a reaction flask was charged 95.4 grams (0.093 hydroxyl equivalents)
20 Rucoflex(~ XS-5570-55 and 4.5 grams 2-methyl-1,3-propanediol. The m~teri~ls were
heated to 50~C and then charged with 39.96 grams isophorone diisocyanate and 1 drop of
dibutyl tin dilaurate. The mixture was heated an additional 2 llours at 80~C. The
rçs~llting isocyanate-tt;, .";ll~ 7 polyurethane prepolymer was dispersed in a solution
cont~ining 315 grams of an arnine functional polyvinyl polymer (Compound 3A) and25 244 grams de-ionized water. The dispersion was stirred for 2 hours at 60~C.
The compounds mechanical and adhesion ~ 3p~ ~ies are provided in Table
3:
Table 3. Tensile Strenth, elongation and shear strength
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21
Compound T~nsile F.lnn~linn Shear Strength (Kgs./cu.cm.)
Strength (%)
(Kgs./cu.cm)
Steel/Steel Glass/Glass ABS/ABS
Compound 3A 55.46 1,987 10.89 14.34 23.90
Compound 3B 48.36 2,118 19.47 17.78 27.27
Example 4:
Exarnple 4 describes the p~ dlion of water-based polymer
compositions wherein isocyanate-terrnin~tcd sulfonated polyulc;llldlle prepolymers are
S dispersed in hydroxy functional water-based polyacrylic dispersions.
Compound 4A
Compound 4A is a hydroxyl functional polyacrylic dispersion wherein the
hydroxyl groups are within the latex particle.
(1)
Reactor Char~e Grams
De-ionized water 275.0
Methacrylic acid 1.0
(2)
Pre-emulsion Grams
De-ionized water 80.0
T-Det 0-407 (Hacros) 8.86
Methyl methacrylate 155.0
N-butyl acrylate 155.0
Hydroxyl ethyl acrylate 10.85
N-dodecyl mc~.;~l~l 0.31
(3)
Initiator fee Grams
De-ionized water 20.0
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22
T-butyl hydroperoxide 1.37
(4)
Reducer feed rams
De-ionized water 20.0
Sodium forrnaldehyde sulfoxide 0.97
To a reactor equipped with an agitator, thermometer, condenser and
nitrogen purge was added the reactor charge (1). The water was heated to approximately
5 65~C and then charged with 3% of the total pre-emulsion. While m~ a reaction
temperature of 65~C, the pre-emulsion (2), was added over a 3 hour period while the
initiator feed (3) and reducer feed (4) were added over a 4 hour period. The reaction
mixture was charged with 10.85 grams hydroxyl ethyl acrylate after addition of
approximately 75% of the pre-emulsion. Once all the m~t.o.ri~s were added, the reaction
10 lni~ulG was heated an additional hour. The dispersion had a solids content of 45.2%, a
pH of 2.65 and a number average particle size diameter of 443 nanometers.
Compound 4B
Compound 4B is a hydroxyl functional polyacrylic dispersion wll~ lGi,l a
portion of the hydroxyl groups are distributed on the surface of the particle.
(1)
Reactor Char~e Grams
De-ionized water 275.0
Methacrylic acid 1.0
(2)
Pre-emulsion Grams
De-ionized water 80.0
T-Det 0-407 (Hacros) 8.86
Methyl methacrylate 155.0
N-butyl acrylate 155.0
N-dodecyl mGrc~l~l 0.31
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23
(3)
Initiator fee Grams
De-ionized water 20.0
T-butyl hy-llopwoxide 1.37
(4)
Reducer feed Grams
De-ionized water 20.0
Sodium form~ hyde sulfoxide 0.97
To a reactor equipped with an agitator, thermometer, con(len~r, and
nitrogen purge was added the reactor charge (1). The water was heated to approximately
65~C and then charged with 3% ofthe total pre-emulsion (2). While mz~ g a
reaction temperature of 65~C, the pre-emulsion (2) was added over a 3 hour period while
the initiator feed (3) and reducer feed (4) were added over a 4 hour period. The reaction
mixture was charged with 10.85 grams of hydroxyl ethyl acrylate after addition of
approximately 75% of the pre-emulsion. Once all the m~t~ri~l~ were added, the reaction
ll~i~l~u~ was heated an additional hour. The dispersion had a solids content of 45.2%, a
pH of 2.65 and a number average particle size diameter of 443 nanometers.
Compound 4C
Compound 4C is a sulfonated polyurethane prepolymer.
A reactor was charged with 4.5 grams (0.099 hydroxyl equivalents) 2--
methyl-1,3-propanediol and 95.4 grams (0.093 hydroxyl equivalence) molten Rucoflex(~
XS-5570-SS which is a sulfonated polyol from RUCO Polymer Corporation based on 5-
sulfoisophthalic acid monosodium salt (4% by weight), adipic acid and diethyleneglycol. The mixture was charged with 39.96 grams isophorone diisocyanate, 1 drop of
dibutyl tin dilaurate and heated to 80~C for 2 hours.
Compound 4D
Compound 4D is a water-based sulfonated polyurethane-urea polymer.
139.86 grams of the prepolymer (80~C) described as Compound 4C was
charged with 629.3 grams de-ionized water (65~C) and stirred for 2 hours keeping the
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Lt~ dLult; below 65~C.
Compound 4E
Compound 4E is of a water-based sulfonated polyurethane-acrylic
polymer composition.
139.86 grams ofthe prepolymer (80~C) described as Compound 4C was
dispersed in 309.4 grams of a hydroxyl functional polyacrylic dispersion (65~C)
described as Compound 4A. The dispersion mixture was stirred for 5 ll~il~uLt~S and then
charged with 250.0 grams of de-ionized water ~65~C). The m~tf~ were heated an
additional 2 hours at 65~C to generate a polymer composition having a solids content of
10 40.2% and a pH of 6.5.
Compound 4F
Compound 4F was ~ d as simil~riy described as Compound 4E with
the exception that 312.2 grams of the hydroxyl functional polyacrylic dispersiondescribed as Compound 4B was used. The polymer composition had a solids content of
15 40% and a pH of 6.5.
The compounds mech~niç:~l properties are diagramed below in Table 4:
Table 4. Tensile Strenth and elongation
CompoundTensile StrengthElongation(S)
(Kgs./cu.cm.)
Compound 4A 71.8 1,484
Compound 4B 94.3 1,648
Compound 4C 60.7 3,807
Compound 4D 120.8 2,205
Compound 4E 117.0 2,437
Compound 4A and 4C61.0 2,620
(50/50 Blend)
Compound 4B and 4C68.3 2,537
(50/50 Blend)
The data shows the inventive polymer compositions ~Compounds 4E and
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4F) have enhanced tensile strength compared to Compound 4A, Compound 4B,
Compound 4D, the S0/S0 blend of Compound 4A and 4D and the S0/S0 blend of
Compound 4B and 4D.
Example 5:
S This example describes the ~ lion of a water-based sulfonated
polyurethane-urea/polyvinyl polymer and its ~ lies culllp~ed to its corresponding
polymer components.
Compound SA
Compound S~ describes the ~ lion of a polyvinyl dispersion which
is free of active hydrogen atoms.
(1)
Reactor Charge Grams
De-ionized water 290.0
(2)
Pre-emulsion Grams
De-ionized water 90.0
T-Det 0-407 (Hacros) lS.0
Methyl methacrylate 170.0
N-butyl acrylate 180.0
Methacrylic acid 7.0
N-dodecyl m~ L~l 7.0
(3)
Initiator fee Grams
De-ionized water 30.0
T-butyl hydr~,pe~o2~ide 2.15
lS (4)
Reducer feed ~ams
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De-ionized water 30.0
Sodium formaldehyde sulfoxide 2.10
To a reactor equipped with an agitator, thermometer, con~1en~Pr and
nitrogen purge was added (1) the reactor charge. The water was heated to approxirnately
65~C and then charged with 3% by weight of the total pre-em~ ion (2). While
~; m~ g a reaction Le~ dL Ire of 65~C, the pre-emulsion (2), initi~tor feed (3),
reducer feed (4) were added over a 3 hour period. Once all the mz~teri?ll~ were added, the
dispersion was heated an additional hour.
Compound SB
Compound SB is a water-based sulfonated polyurethane-urea polymer.
To a reaction vessel was charged 95.4 grams (0.093 hydroxyl equivalents)
Rucoflex(l~) XS-5570-SS and 4.5 grams 2-methyl-1,3-propanediol. The mixture was
heated to 50~C then charged with 39.96 grams isophorone diisocyanate and 1 drop of
dibutyl tin dilaurate. The lllixLult; was heated to 80~C for approximately 2 hours using
mild agitation. The isocyanate-t~ . . " i. ~ cl polyu~lal e prepolymer was then dispersed
in 339.4 grams de-ionized water and charged with a solution cu~ llg 2.88 grams
ethylene ~ mine, 1.09 grams diethylene triamine and 20 grams de-ionized water.
ComPound 5C
Compound SC is a water-based sulfonated polyurethane-urea/polyvinyl
dispersion.
To a reaction vessel was charged 95.4 grams (0.093 hydroxyl equivalents)
Rucoflex~ XS-5570-SS and 4.5 grams 2-methyl-1,3-propanediol. The mixture was
heated to 50~C then charged with 39.96 grams isophorone diisocyanate and 1 drop of
dibutyl tin t~ lnqte The mixture was heated to 80~C for approximately 2 hours using
mild agitation to give an isocyanate-terrnin~e~i polyurethane prepolymer. The
isocyanate te~min~te~l polyurethane prepolymer was then dispersed in a mixture
CO~ g 339.4 grams de-ionized water and 969.3 grams of the polyacrylic dispersion,
compound SA, which mixture had been adjusted to a pH of 9.3, using 10% sodium
hydroxide/water mixture, before the dispersion process. The resulting isocyanate-
termin~d polyurethane prepolymer/polyvinyl dispersion was charged with a solution
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27
co~ 2.88 grarns ethylene ~i~min~, 1.09 grams diethylene tri~mine and 20 grams
de-ionized water. The resulting water-based sulfonated polyur,ll,~le-urea/polyvinyl
polymer had a solids content of 35% and a pH of 9Ø
The compounds described above were tested for shear strength on glass,
5 steel and acrylonitrile-butadiene-styrene copolymers (ABS). The results are provided in
Table 5 below:
Table 5. Shear ~
Shea~ Strength Shea~ Strength (Kgs./cu.cm.)
(Kgs./cu.cm.)
GlassMlass SteeVSteel ABS/ABS
Compound SA 41.6 55.95 19.19
Compound 5B 20.87 11.17 25.94
Compound 5C 75.71 59.82 31.21
Compound SA and 23.48 23.97 23.12
5B (50/50 Blend)
The data shows the inv~ ive; polymer (Compound 5C) has increased
10 shear strength compared to Compound SA, Compound SB and the 50/50 blend of
Compound 5A and 5B showing the utility of the invention.
Examples 6 and 7 relate to the formation of water based sulfonated
polymer compositions in which a polyurethane dispersion is used as a seed to polymerize
(meth)acrylic monomers. The reslllting water based sulfonated polymer composition
15 may be used for fiberglass sizing. As used herein, acrylic denotes acrylate, methacrylic
acid, and acrylamide.
Example 6. Synthcsis of pol~ ~r~lhane dispersion aclylic hybrid latex
Example 6 describes the prepalation of a water based sulfonated polymer
20 composition by seed emulsion polymerization and its p,~ . Lies compared to the blend of
its coll~s~onding polymer components.
Compound 6A
Compound 6A is a polyacrylate pre-em~ n
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(l) Reactor char~e Grams
Deionized water 90.8
Pluronic L64 (a sl~ t~nt, BASF) 9.08
(2) MonomerMixture
Methyl methacrylate (ICI) 159.6
N-butyl acrylate (Hoechst Ce1~n~osc) 163.5
Hydroxyl ethyl methacrylate (Rohrn & Haas) 6.49
Reactor charge (1) was added to a kettle with an agitator and mixed for 10
minllt~s at a temperature of 25~C. Monomer mixture (2) was then added over a period of
30 mimltes under agitation to the kettle. The mixture was mixed for an additional 10
minutes at a temperature of 25~C. The r~slllting pre-emulsion was transferred to a feed
15 tank.
Compound 6B
Compound 6B is a polyurethane dispersion for use in the preparation of
the inventive compositions.
(1) Reactor char~e Grams
Deionized water, 181.7
Thiolactic acid (Evans) 0.065
Hydrosulfite AWC (Henkel) 0.065
Hamp-O 14.5 % Iron (H~llp~ G) 0.039
Reactor charge ~1) was added to a j~ eted clean reaction kettle equipped
with agitator, thermometer, condenser and nitrogen purge and mixed well. 332.3 Grams
of NP-4062-M (a polyul~Ll~e dispersion, H.B. Fuller Company) was added to the
e. The reactor, under nitrogen purge, was ~g1tZ~tefl and the ten-~G~ re raised to
65~C.
Compound 6C
Compound 6C is a water based sulfonated polymer composition prepared
by seed emulsion polymerization.
Over a period of 4.5 hours, the polyacrylate pre-emulsion ~Compound
6A), an initiator solution co~ i . .g 1.95 grams of t-butyl hydrogen peroxide (Akzo) and
19.5 grams of deionized water, a reducer solution COl ~1~; l l i l ~g 0.91 grams of hydrosulfite
AWC (Henkel) and l9.5 grams of deionized water, were fed to a jacketed clean reaction
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29
kettle equipped with agitator, therrnometer, contl~n~er and nitrogen purge CO~ the
polyurethane dispersion llliXIWC (Compound 6B). Following completion of the feeds,
the 111i2~Ul~; was held at constant temperature for another hour to allow the full
Col~ ion of monomers. The reactor was then cooled to ambient temperature and theresulting latex filtered through 200 mesh filter. A stable latex with 45% solids, pH 7.35
and viscosity of 316 cps was obtained.
Additional compounds were prel)~ed similarly to compound 6C varying
the amount of compound 6B res-llting in a water based sulfonated polymer composition
with dir~Lclll pol~ lane /polyacrylate (PU/PA) ratios. Compound 6C, and similarly
10 prepared compounds with different polyurethane/polyacrylic ratios, and blends of
compounds 6A and 6B, (absent the initisltor and reducer solutions) were tested for tensile
strength and elongation, peel strength (using a clear and a white PVC sheet as ~ub~lldlcs)
and lap shear strength. The results are provided in Tables 6-9. Note that the
polyurethane to polyacrylate ratio is based on solids content of the polyurethane and the
15 polyacrylate. Thus a PU/PA ratio of 75/25 inrlic~f.os that there are 3 parts polyurethane
solids for every part of polyacrylate solids. Also note that the "hybrid" referred to in
Table 9 is ~ ucd as in Compound 6C with a PU/PA ratio of 25/75. The blend in Table
9 has a PU/PA ratio of 25/75.
Table 6. Tensile Strenth and elo t~
Tensile Streng~ (PSI) Tensile Elongation (%)
PU/PA Ratio Blend Hybrid Blend Hybrid
100/0 6505 - 3383
75/25 3285 3386 3383 3636
50/50 1793 1860 301 1 3166
25/75 1190 1317 2356 2386
0/100 908 - 1780
CA 02259364 1998-12-29
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Table 7. Peel Strength, Clear PVC Film
Green strength (PSI) 7 Day Strength (PSI)
PU/PA Ratio Blend Hybrid Blend Hybrid
100/0 5.6 - 3.2
75/25 5.4 6.1 5.1 6.8
50/50 4.3 5.9 1.7 6.g
25/75 2.0 6.3 0.6 5.4
0/100 2 5 - 0.8
Table 8. Peel Strength, White PVC Film: ~Hybrid prepared with Example 6)
Green streng~ 7 Day Strength (PSI)
(PSI~
PU/PA Ratio Blend Hybrid Blend Hybrid
100/0 2.6 - 2.0
75/25 4.6 4.4 4.2 3.7
50/50 5.4 5.3 4.6 5.1
25/75 4.6 5.4 1.1 4.4
0/100 4.3 - 2.2
Table 9. Lap Shear Sl, ~..~,11,: (glass to glass)
Material Lap Shear Strength (PSI)
~IP-4062 54
Hybrid 393
Blend 210
Acrylic 60
E2cample 7. Synthesis of Wate~Chain-Extended Water Based Sulfonated
Polymer Composition
With the sample process of Example 6, another water based sulfonated
10 polymer composition was p~ aLed in ~e manner of Example 6C except that the
CA 02259364 1998-12-29
W 098/06768 PCTtUS97tl4386 31
polyul~,lh~le dispersion NP-4062 used to prepare compound 6B was replaced by NP-4073 (a sulfonated polyurethane dispersion, H.B. Fuller Co.llpa~ly).
Capillary Hydrodynamic Fractionation was used to monitor the latex
particle growth in Exarnples 6 and 7. Figures 1 and 2 present the seed polyurethane
S particle si~e distribution (dotted line) as a function of the final hybrid latex particle
distribution (solid line), for the latex (water based sulfonated polymer composition)
prepared in Examples 6 and 7. Both figures demonstrate that no new population ofacrylic particles was generated, implying that a polyurethane-core-polyacrylic-shell
hybrid structure was formed. The unique hybrid morphology of the water based
10 sulfonated polymer composition latex in this disclosure leads to superior physical
properties compared to the corresponding blend or comrnon alloy.
