CA1115875A - Polyurethane thickeners - Google Patents

Abstract

Abstract of the Disclosure Latex and other aqueous systems are thickened by incorporation or a low molecular weight polyurethane characterized by at least three hydrophobic groups inter-connected by hydropnilic polyether groups. The thickeners are nonionic, hydrolytically stable and are resistant to biodegradation.

Description

J~115~7~

~ACKGROUND OF THE NVENTION
Thi~ appllcation relate~ to a new cla3~ of non-ionic polyurethanes u~eful for thickening a wide range of aqueou~ system~, and more part~cularly relate~ to rela-tlvely low molecular weight thickeners, characterized by hydrolytic ~tability, versatility and ef~iciency, and to a wlde variety of aqueou~ sy~tem~ contalning the thickeners.
The thickeners o~ thi~ invention provide a combi-nation o~ properties not ~ound in any one clas~ of known thickener~. For example, they are noniolc and ln many case~ are highly efflclent visco~lty lmprovers although having a relatlvely low molecular welght. They are stable to water and alcohol and are not sensitlve to biodegrada-tion. They are ver~atlle in that not only do they thlcken virtually unlimited type~ of aqueou~ ~y~tems, but they al~o lmpart many auxlllary propertle~ as descrlbed herelna~ter.
Thu~, as addltlves to textile blnder compo~ltlons, they actually sorten rather than harden the fabrlc. In latex paint~, e~peclally, they not only thlcken but ln many cases also provlde ~uperlor flow and levellng, and glve excellent vi~coslty control under both low and ~gh ~hear condltlon~.

SUMMARY
The thlckener~ of the lnventlon are urethane polymer~ havlng at lea~t three low molecular welght hydro-phobic group~ at least two of whlch are termlnal (external) hydrophobic groups. Many of the polymer~ also contaln one or more lnternal hydrophoblc group~, The hydrophoblc

- 2 -groups together contain a total of at least 20 carbon atom~
and are llnked through hydrophillc (water soluble) group~
containlng polyether ~egments of at least about 1500, prererably at lea~t about 3000, molecular weight each so .
that the polymers readlly ~olublllze ln water, elther by sel~-solubillzatlon or through lnteractlon with a known solubllizing agent ~uch as a water miscible alcohol or ~ur-~actant The molecular welght o~ the polyurethane~ 1~ o~
the order o~ about 10,000 to 200,000.
The polymers are prepared ln non-aqueous medla and are the reactlon products of at least reactant~ (a) and (c) o~ the followlng reactants: (a) at least one water soluble polyether polyol, (b) at lea~t one water in~oluble organic polyisocyanate, (c) at least one mono-~unctlonal hydrophoblc organlc compound selected from mono-functlonal active hydrogen compounds and organic monolso-cyanates, and (d) at lea3t one polyhydrlc alcohol or poly-hydric alcohol ether. The product~ formed lnclude the ~ollowlng:
(1) Reaction product~ of a reactant (a) contaln-ing at least three hydroxyl groups, and the foregoing organlc monolsocyanates;
(2) Reactlon products Or reactant (a), reactant (b) containlng two l~ocyanate groups, and the foregolng actlve hydrogen containlng compound~ Such compound~ wherein the ratlo Or equivalents of (a) to tb) 18 0.5:1 to 1:1 are belleved to be new per ~e; all are bel~eved to be userul ln certaln ~y~tems;

li~S~75

(3) Reactlon products o~ reactant (a), reactant (b) contalning at least three l~o-cyanate groups, and the actlve hydrogen con-talnin~ compounds;

(4) Reactlon product~ Or reactant (a), reactant (b) and the organlc monolsocyanate~; and

(5) Reaction product~ o~ reactants (a), (b), (d) and the organlc monoi~ocyanate~.
The reactants are normally employed in sub~tan-tlally stolchlometrlc proportlons, that 1~, the ratlo o~
total equlvalents of actlve hydrogen containlng reactants (whether mono or polyfunctional) to i~ocyanate reactants 18 at lea~t l:l. A slight stolchiometrlc exces~ (e.g., about 5-10%) o~ mono~unctlonal actlve hydrogen containing compound may be used to ellmlnate any unreacted lsocyanate functlonallty, thus avoidlng toxiclty Prom thi~ sour¢e.
Greater exces~es, partlcularly o~ capplng hydroxyl compound, may be used to lncrease thlckenlng ef~iclecy. A sllght ex¢ess Or a monolsocyanate i9 30metlmes deslrable ln cases where such isocyanate 19 a capplng hydrophobe, to ensure capplng o~ all avallable actlve hydrogen functlonallty.
By "mono~unctlonal actlve hydrogen compound" i~
meant an organlc compound havlng only one group whlch ls reactive with l~ocyanate, such group there~ore contalnlng an actlve hydrogen atom, any other runctlonal groups, i~
pre~ent, being ~ub~tantlally unreactive to l~ocyanate. Such compounds lnclude monohydroxy compounds ~uch a~ alcohols, alcohol ethers and monoamines, as well a3 polyfunctional compounds provldin~ the compound is only mono~unctional to isocyanates. For example, the prlmary amines, although dlfunctlonal ln many reactions, are only monofunctional towards isocyanates, the hydrogen atom in the resultlng urea group beln~ relatively unreactlve to isocyanate as compared with the hydrogen atom Or the amino group or o~
unhindered alcohols.
Reactant (c) is a "capping" compound, meaning it reacts with ("caps") the terminal runctional groups Or the reaction product Or reactants (a) and (b~.
The polyether polyol reactant (a) is an adduct Or an alkylene oxide and a polyhydric alcohol or polyhydric alcohol ether, a hydroxyl-terminated prepolymer of such adduct and an organic polyisocyanate, or a mixture Or ~uch adducts with such prepolymers.
Reactant (d) may be employed to termlnate i80-cyanate runctlonallty or to llnk lsocyanate-termlnated reactlon intermediates. Reactant (d) may be a polyhydric alcohol or polyhydrlc alcohol ether of the same type as used to form the adducts Or reactant (a). The polyhydrlc alcohols or alcohol ethers may be aliphatlc, cycloallphatlc or aromatic and may be used slngly or ln mlxtures of elther type or mixtures of the two types.
The organic polyisocyanates include simple dl-and triisocyanates, lsocyanate-termlnated adducts o~ such polyhydric alcohols and organlc di- or triisocyanates, as well as isocyanate-termlnated prepolymers Or polyalkylene ether glycols and organlc dl- or trllsocyanates.

lllX875 The hydrophoblc groups of the polyurethanes occur ln the re~idues of reactants (b) and (c~ and may also occur ln the resldue of reactant (d) 1~ present. The terminal (external) hydrophobes are the resldues Or the monofunc-tional active hydrogen compounds, organlc monolsocyanates, or comblnatlons Or the residues of such compounds.
By appropriate selection Or reactants and reac-tion conditlons, lncludlng proportlons and molecular weights Or reactants, a varlety Or polymeric products may be obtained. The products exhlblt good thlckening properties due to the presence and dlstributlon thereln Or hydro-phillc (polyether) groups (residues of the polyol reactant) and hydrophoblc groups (resldues of hydroxy compounds, amines and/or isocyanates). From a structural standpoint the products may be classified into three groups as des-cribed herelnbelow Some Or the polymers have readily identiriable structures, such as the essentlally llnear ~tructures Or formulas I-IV and the generally star-shaped structures Or formulas V-VII. The remaining polymers are complex mixtures.
The polymers may be substituted for known thlcke-ners ln any aqueous system in which thickeners are normally utilized and therefore the rield~ o~ use Or the thickeners Or the invention include a host o~ industrial, household, medical, personal care and agricultural compositions. As indicated above, thickenlng ln such compositlons is o~ten also accompanied by other improvements, such as leveling, flow, stabilization, suspension, hlgh and low 3hear l~lS875 vlscoslty contr~l, and blnding propertie~. While all Or the polymers Or Groups A, B and C are use~ul as thickeners ror latex paints and many other aqueous systems, preferred thickeners for pigment printing pastes and acid dye baths are those Or Groups B and C.
In this specification the term "hydrophobe"
includes not only the hydrocarbon residues o~ hydroxyl, amino or isocyanate reactats but also the combination of such residues with next adJacent urethane ad other groups remaining in the structure after reaction. The term "hydrophobe" or like term there~ore is used herein to mean all those portions or segments o~ the polymeric reaction products which cotribute to water insolubility. All por-tions or segments other than the residues of the polyether polyol reactants there~ore are hydrophobic.

~11587~

DescriPtion of the Pol~mers The polymeric thickeners useful accordin3 to the invention are pol~rethanes which may be cla~sified as follows:
GrouP A - Linear Products A~ ~ ~Eq~~~B-E ~ Br-Et-A
where each of p, q, r and t independently i9 either zero or 1;
at least one of q and r is ?, and t is zero when r i9 zaro;
provided that, when q is 1, then a) each of p, r and t i9 zero (as in formula I, below);or b) p i8 zero and each of r and t is 1 (as in formula II, below); or c) t is zero and each of r and p is 1 (as in formula III, below); and when q is zero, then r i9 1 and each of p and t i8 zero (as in formula IV, below).
2G Polymer3 coming within the foregoing formlla are:
ExamPles L ~A-E--~B-E}--nA 1 - 10 IL A-E--~B-E ~ B-E-A 24-28 IIL A-B-E--~B-E ~ B-A 29-34 25IV. A--~B-~ B-A 11-23 The equivalent ratio of tetal active hydrogen to tot~l iso-cy~nate in the Group A compounds is about 1:1 to 2~

Group B - Star-ShaDe~ Products [H-E-ocH2]sL[Qv ( Du E At )w z]m where L is X, Y or -O-, Q is -CH2C--, D is-cH2 m is 2-4, s is zero to 2, the sum of m and s i~ ths valence of L (2-4), w i5 1-3, a~d each of t, u and z independently is zero or l;
and where X is a hydrocarbon radical containing at least 1 carbon atom, preferably 1-4 carbon atoms; and Y is a triv~lent radical selected from -oco~H(c~2)6N[coNH(cH2)6NH
CH3C[CH20-OCNHC7H6NHCO ~ .~nd CH3CH2C[CH20-OCNHC7H6!~HCO ~ ;
provided that, 1~ a) when L is X, then t, u and w are each 1, v and z are each zero, the sum of m and 9 iq 4, and m is at least 2 (as in form~la V below);
b~ when L is Y, then t, u, v and s are each zero, . m is 3, w is 2-3, and z is zero or 1 (as in formula VI below); and c) when L is -~-, then t, u and v are each 1, W i9 1-3, m is 2 and each of s and z is zero (as in formula VII below);
2~ Polymers coming within the foregoing formula are:
Exam~les V. (H-E-OCH2)sx[cH2o-h-A]~ 35 _ 47 VI. Y[E-R]3 48 - 50 _ g _ 'C

-1~15875 VII.0[cH2c~cH20-E-A~3]2 51 - 63 In esch of the polymers of G~ou~s A and B:
A and R are hydrophobic organic radicals containing at least one carbon atom;
B is a divalent hydrophobic group of the structure where G i8 the residue of an organic di- or triisocyanate, the residue having no remA~ning unreacted isocyanate groups;
E is a divalsnt, hydrophilic, nonionic polyether group; and B ~i9 at least 1, such as about 1-20, preferab y 1_10 In ~tructures V and VII the equivalent ratio of total activs hydrogen to total isocyanate i8 from about 1.2:1 to a stoichiom~tric excess of isocyanate; and in structure VI from about 1:1 to a stoi-chiometric excess of active hydrogen.
It will b~ apparent to the polymer chemist that values of n given in this specification are average rather than absolute values since in reaction products of the type of this invention, the reaction product will often be a ~xture of csveral products having different values for n.
The star-shaped polymer configurations of formulas V-VII re~ult from a polyhydric reactant such a~ trimethylolpropane or pentaeryth-ritol (residue X in formula V) or a triisocyanate (residue Y in for-mula VI), or result from a polyhydroxy ether ~uch as dipentaerythritol 11~5~7s (Q and D of formllla VII). L, Q and D form a central hydrophobic nucleus from which radiate hydrophilic polyether segment~ E, partially or fully capped (terminated) with hydrophobic groups A qnd R. The pointq or arms may have the same or different chain length and may contain hydrophobic segments alternating with hydrophilic pGrtions.
5 B When Q is greater than zero, partial capping results. In formulas V
and VII, A is the residue of an organic monoiso~cyanate.
Group C - Complex Poi~mers The polymers of Group C are complex mixtures of line r, branched and sub-branched products which form networks of hydrophobes and hydrophobic segments interspersed with hydrophilic segmants. The products result from the multitud~ of different interactions which may take place between the polyfunctional reactants used to form the~.
The e~sential reactants are a polyfunctional compound containing at least three hydroxyl or isocyanate groupq, a difunctional compound reactive with the polyfunctional compound, and a monofunctional reactant such as a monohydroxy or mono~mino compound. The reactants mqy each be present ~ingly or in mixtuL~es of two or more. The di-functional compound is a diisocyanate (for reaction with the triol or higher polyol) or a diol (for reaction with the triisocyanate) and can also be pre~ent singly or in mixtures of two or more. The mono-hydroxy or monoamino compound, or mixture thereof, i8 added to tha reaction mixture to cap isocyanate of the triisocyanate not reacted with the diol in order to prevent gelation. A monoisocyanate may be added to the reaction mixture if some of the polyol (diol, triol or higher polyol) remainq unreacted or if it i~ desired to cap all hydro~yl groups.
It should be understood that in preparing the product_ of Group C

11~587S

as well as t~ose of Groups A and B, cappin~ ~f all hydroxyl is not required. Oap?ing or hydrolyzing of all isocyarate, although not absolutely necessary, is preferred to avoid toxicity in the polymeric product Generally, no mo-e than about 25~ of the hydro~yl should remain uncapped since the hy~roxyl increases the wate~ solubili'.y ar.d reduces thic'~a m ng efficiency. Of course, if the product contains a relatively nigh proportion of hydrophobic rssidues, a gre~ter amount of u capped hydroxyl can be tolerated.
ID summary, the Group C produsts are polymeric compositions pre-pared by reacting: (a) a polyfunctional reacta~t selected from an organic polyol having at least thres hydro~yl groups, an organic polyisoc7anate having at least three isocyanate groups, and mixturss th~reof; (b) a difunctional re~ctant selQcted from a~ org.~ic diol, an organic diisocyanate, and mixtures therebf, the diol being present in the r~a~tion mixture when the polylsocyanate is present and the diisocyanate being present when the polyol 19 Pr95ent; (C) a mono-functional hydroxyl or ami~o compound in an amount sufficient to cap any unreacted isocyanate remaining from the reac'ion of reactant3 a) and b) ~rd to prevant gelation of the reaction lixture; and op-tion~lly d) a hydrophobic organic ~onoisocyanate to cap hydroxyl groups remaining from the reaction of reactants a) and b); wherein at least one of the polyol ar,d diol contains at least one water soluble poly-ether segment of at least 1500 molecular weight, wherein ~he total carbon conte~t of all hydrophobic grou~s is at lsast 20 and the avarags mol~cular weight of the polyurethane product is about 10,000-200,000 Examples 64-117 below illustrate these products.

~ .
P ~

The present invention, then, provides a latex composition containing an emulsion polymer and from about 0.1 to about 10% by weight based on emulsion polymer solids of a thickener selected from polymers of Groups A, B and C
as follows:
Group A:
polymers selected from AE (BE)n A
and A (BE)n BA, wherein n is at least one;
Group B:
polymers selected from those of the formulas V-VII as follows:
V (H-E-OCH2)sX[CH2O-E-A]m VI Y[E-R]3 VII O[CH2C(CH2-O E A)3]2 and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure O O

-CNH-G-NHC-O-where G isthe residue of an organic di-or triisocyanate, said residue having no remaining unreacted isocyanate groups; and E is a divalent, hydrop'nilic, nonionic polyether group;

-12a-~, 1~15~75 Group C:
a composition prepared by reacting a) a polyfunctional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof; b) a difunctional reactant selected from an organic diol, an organic diiso-cyanate, and mixtures thereof, said diol being present in the reaction mixture when said polyisocyanate is present and said diisocyanatebeing present when said polyol is present;
c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants a) and b) and to prevent gelation of the reaction mixture; and optionally d) an organic mono-isocyanate to cap hydroxyl groups remaining from the reaction of reactants a) and b); wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000-200,000.
As a general rule, the foregoing conditions are true for all of the polymers of Groups A, B and C. That is, the polymers will provide good thickening if the polyether se~ments have molecular weights o.f at -12b-lllS87~

least 1500 (preferably 3000-20,000), the polymer~ contain, on the average, at least th ae hydrophobic groups and at least two water soluble polyether segments linking the hydroph~bss, the sum of the carbon atoms in the hydrophobic groups being at l~ast 20, preferably at least 30, and the total molecular ~eight is about 10,000-200,000, preferably 12,000-150,000. The optimum polyether content will depend, of course, on the bulk And distribution of the hydrophobic groups in the poly~?r. Whereas a total polyether molecular weight of 4000-5000 may be suitable when the polymer con~ains small external and in-ternal hydrophobes, the polyether content may have to be substanti~lly increased when heavier and/or more extensively b.anched hydrophobic groups are to be built into the polymer, such as long chain fatty polyols or amines. About 200 carbon atoms in the hydrophobic portion is the practical upper limit ~lthough it will be understood that it ~5 is a relative matter since the proportion of polyether may be inereased to offset incraased hydrophobicity. Howeve~, as total molecular weight inerease~ the viscosity increa~ss and ease of handling dec.ease~, and therefore the eeonomic usefulness of the products is substantially dlmlnlshed.
The r~lati~ely low molecular weights of the polymers ir. conjunc-tion with their nonionic character promote their efficiency as thick-eners, since their thicke~ing capabilities ~re mueh greater for equiva-lent molecu~r weigh~ in a given ~queou~ system, as compared with known thickeners, and the polymers are believed to thicken by an associati~3 mechanism such as micellar or other form of association, rathsr than by molecular weight or chain extension alone. For example, 1.0% by weight of the polym~rs in an aqueous dispersion will provide thickening equiva-lent to that afforded by other nonio~ic thickeners at much hig~er ~lS875 concentrations. Of course, the ability to obtain good thickening at relatively low molecular weight and solids levels also promotes other properties, such as softening effects on fabrics when the polymers are used in fabric finishing compositions. In addition, the use of organic isocyanate residues as internal or external hydrophobes also makes the polymers relatively stable to hydrolytic degradation, thereby greatly expanding their usefulness, as in systems requiring extended shelf life.
In certain applications, such as latex paints, polymers of the invention can provide excellent flow and leveling as well as thick-ening. In other applications, such as paper coating compositions where high shear thickening is important, polymers of the invention can easily be ~elected which are superior in this respect, while also retaining good thickening capabilities and low shear viscosity.
Preparation of the Polymeric Products The first class of reactants (a) used to form the polyure-thanes of the invention-are water soluble polyether polyols. Typically, these are adducts of an aliphatic, cycloaliphatic or aromatic poly-hydroxy compound such as a polyhydric alcohol or polyhydric alcohol ether and an alkylene oxide such afi ethylene oxide or propylene oxide, or they may be hydroxyl-terminated prepolymers of such adducts and an organic polyisocyanate. The adducts or prepolymers may be mixtures of two or more of such adducts or prepolymers, and mixtures of such adducts with prepolymers may also be used. The polyhydric alcohols lnclude not only the simple glycols s,uch as ethylene glycol and propy~
lene glycol but also hydroxy compounds containing three or more hydroxyl groups, such as polyalkylolalkanes (e.g., trimethylol propane, pentaerythritol) and polyhydroxyalkanes (e.g., 11~5875 glycerol, eryth~itol, sorbitol, mannitol, and the like). The poly-hydric alcohol ethsrs usually are a~uct~ of polyhydric alco-1ols and alkylene oxides but in some cases are present as byproducts with other polyhydrox~ compounds. For example, pentaerythritol as ordinar-ily prepared contains about 15% of the ether, dipentaerythritol.
Typical of cycloaliphatic polynydric compounds are cyclopentandiol-1,2,1,4-cyclohexandiol, hexahydroxycyclohexa~e, and the like. The polyhydroxy compounds also include aromatic compounds such as di-and trihydroxy benzene and the lika.
The foregoing and numerous other h~droxyl compounds, adducts and prepolymers are well known and thoroughly descri~3d in the tech-nical literature, includlng standard textbooks such as Whitmore, Or~anic Chemistry, 2d Ed., Dover Publications, Inc., New York, 1961, two ~olumes, pages 302-330, 547-559 and 671-674.
A convanient source of th3 hydrophilic polyether polyol adducts is a polyalkylene glycol (also known as a polyoxyalkylene diol) such as polyethylsne glycol, polypropylene glycol or polybutylene glycol, of about 4,000-20,000 molecular weight. Howe~er, adducts o an al-kylene oxide and a monofunctional reactant such as a fatty alcohol, a phenol or an amine, o~ adducts of an alkylene oxid- and a difunctional reactant such as an alkanolamine (e.g., ethanolPm1ne) are also useful.
Such adducts are also known as diol ethers ~nd alkanolamine sthers.
Suitable compounds pro~iding polyether segments also in~lude Am~no-terminated polyoxYethylenes of the formula NH2(CH2C.q20)XH where x range9 from about 10 to 200. Such compounds are sold under the trade~ark "Jeffaminen, a typical compound being "Jeffamine 2000n of about 2000 molecular weight.
The sscond class of reactants (b), the water insoluble organic l~lSB7~

polyisocyanates, or isocyanates used to form the hydroxyl-terminated prepolymers included among reactants (a), may be aliphatic, cycloaliphatic or aromatic, such as the following, and may be used singly or in admixture of two or more thereof S including mixtures of isomers:
1,4-tetramethylene diisocyanate 1,6-hexamethylene diisocyanate ("HDI") 2,2,4-trimethyl-1,6-diisocyanatohexane l,10-decamethylene diisocyanate 1,4-cyclohexylene diisocyanate 4,4-methylenebis(isocyanatocyclohexane) l-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclo-hexane _- and _-phenylene diisocyanate 2,6- and 2,4-tolylene diisocyanate ("TDI") xylene diisocyanate 4-chloro-1,3-phenylene diisocyanate 4,4'-biphenylene diisocyanate 4,4'-methylene diphenylisocyanate ("MDI") 1,5-naphthylene diisocyanate 1,5-tetrahydronaphthylene diisocyanate polymethylene polyphenylisocyanates sold under the brand name "PAPI," such as "PAPI 135"
(equivalent weight of 133.5 and average isocyanate func-tionality of 2.7) and "PAPI 901" (equivalent weight of 133 and average isocyanate functionality of 2.3) aromatic triisocyanate adduct of trimethylol propane and tolylene diisocyanate sold under *Trademark ~15~375 the brand name "Mondur CB-75'~
aliphatic triisocyanate product of the hydrolytic trimerization of 1,6-hexamethylene diiso-cyanate, sold under the brand name "Desmodur N" **
C36dimer acid diisocyanate sold under the brand ***
name "DDI", based on dimer acids as discussed in J. Am. oii Chem. Soc. 51, 522 (1974) The monoisocyanates ~epresentative of one form o~ reactant (c) include straight chain, b-anched chain and cyclic iso-yanates s~lch as butyl isocy~nate, octyl isocyanate, dodecyl isocyanata, octadecyl isocyan~te, cyclohexyl isoc~Janate an the lik~. These isocyanates al90 may be used singly or in m xtures of two or more thereof and are a convenient method of introducing terminal h7drophobes into the polymer.
The mono or polyisocyanates also include any polyfunctional iso-cyanate derived from reaction of any of the foregoing isocyan.~tes and an active hydrogen ompotmd having a functionality of at least two, such that at lea3t one isocyanate g.oup remains unreacted. Such isocyanates are equiv2~nt to chain-a3~ending an isocyanate term nated isocyanate/diol reaction product with a reactant containing at least two active hydrogen atoms in a manner well known in polyurethane synthe3is.
A variety of other useful mono- or polyisocyanates are set f~Lth in text~ on urethane chemistry, including "Advance3 In Ursthane Science and Technology", ~. S. Frisch snd S. L. Reeg~n, editors, Tech~omic Publishing Co., Inc., Volume 1 (1971) and Volume 2 (1973), and references sited therein. The isocyanatzs may contain any number o~ carbon stoms effective to provide the required degree of nydrophobic *Trademark - 17 -**Trademark 1C~ ***Trademark D

character. Generally, about 4 to 30 carbon atoms are sufficient, the selection depending on ehe proportion of the other hydrophobic groups and hydrophilic polyether in the product.
Representative of monofunctional active hydrogen compounds of the third class of reactants (c) wherein the functional group is hydroxyl are the fatty (Cl-C24) alcohols such as methanol, ethanol, octanol, dodecanol, tetradecanol, hexadecanol, and cyclohexanol;
phenolics such as phenol, cresol, octylphenol, nonyl and dodecyl phenol; alcohol ethers such as the monomethyl, monoethyl and monobutyl ethers of ethylene glycol, and the analo~ous ethers of diethylene glycol; alkyl and alXaryl polyether alcohols such as stsaight or branchet (Cl-C22 ) alkanol/ethylene oxide ant alkyl phenol/ethylene oxite atducts (e.g., lauryl alcohol, t-octylphenol or nonylphenol-ethylene oxlte atducts containing 1-250 ethylene oxide groups); ant other alkyl, aryl ant alkaryl hytroxy compounts incluting mixturqs ther f~ su h as C10 C20 normal alcohol mixtures known as "Alfol"
alcohols .
Amino compounds, which may be used in place of all or a por-t~on of the monohydroxy compounds as monofunctlonal active hydrogen compounds, are prlmary or secondary aliphatlc, cycloaliph2tlc or aromatic amines such as the straight or branched chain alkyl amines, or mixtures thereof, containing about 1-20 carbon atoms in the alkyl group. Suitable amines include n- and t-octyl amine, n-dodecyl amines, C12-C14 or C18-C20 t-alkyl amlne mixtures, and secondary amines such as N,N-tibenzyl amine. N,N-dicyclohexyl amine and N,~ diphenyl amine.
The lower alkyl (Cl-C7) amines may be used if there is sufficient hydrophobic residue in the product from other sources such as isocya-nate or hydroxyl compound to provide a total of at least ten carbon atoms in the terminal groups (taken together) of the polymeric products.
The amino compounds may con~ain more than one active hydrogen atom provided that under normal reaction conditions ~t is only monofunc-tional towards an isocyanate grqup. A primary 2m~ ne is an * Trademark - 18 -~15875 exa~ple of such a compound.
The foregoing Pnd numerous other useful monohydroxy and ~m; no compounds are well Xnown as described in stanlard organic textbooks and oth_r reference works, such a3 the Whitmore text noted above, a~
on pages 102-138 and 165_170 Tho polymers are prepared according to techniques generally known for the synthesis of ureth~nes preferably such that no isocyanate remains unreac ed. Water should be excluded ~rom the reaction since it will cons~me isocyanate functionality. Anhydrous conditions ~re accomplished by azeotro~ic distillation to remove ~ater, by heating under a nitrogen s~arge, or by prior drying of reactant3.
If desired, the reaction may be run in a solvant medium in order to reduce viscosity in those reactions leading to higher molecular weight products. High viscosity i~ the reaction medium causes poor heat transfer and difficult mixin~. Generally, a solvent is u3eful when molecular weights of 30,000 or higher are en~ountersd. Below this molecular wsight a solvent is not required. When used, the solvent should be inert to isocyanate And capabls of dissolving the polyoxy~lkylene reactant and the urethane product at reactio~ tempera-ture. Suitable inert solvents include non-active hydrogen containing compounds such a~ bsnzene, toluene~ xylene and other well-known solvents rich in aromatic hydrocarbons such as the solvents solA
under the trademarks "Solvesso 100"1or "Solvesso 150"2 as wel~ as e~ters such as ethyl acetata, butyl acetate and "Cello~olve"3acetate, and dialkyl ethers of ethylene glycol, ~iethylene glycol, and the like. Many other well-known solvents can also be used.
Reaction temperature is not critical. A convenient rea~tion temperature is about 40C. to 120C., preferably about 603C. to 110~C.
Reaction temperature should be selected to obtain reasonably fast l.and 2. "Solvesso 100" and "Solvesso 150" are high purity aromatic petroleum solvents having narrow boiling ranges. "Solvesso 100" has a flash point cf about 100 F., and "Solvesso 150" has a flash point of about 150F.
_ 3. Trademark,"Cellosolve" acetate is ethylene glycol monoethyl ether acetate 5~ 7~

reaction rate while avoiding undesirable side .eactions, such as isocyanate~urethane con~ensation.
The order of reactant charging is not critical in most cases~
However, in some instances, a9 where the reactants are higher molecu-lar weight or polyfunctional, order of addition obviously should be controlled to avoid gelation. For example, to avoid high molecular weight while obtalning a good proportion of hydrophobic character, it may be desirable to first charge the hydrophobe-contributing reactant~
such as mono-hydro-~y compound, amine or monoisocyanate, followed by the polyoxyalkylene glycol. If higher molecular weight is desired, the hydrophoba-contributing reactant may be charged after the polyoxy-alkylene glycol, or a portion of the hydrophobic reactant may be charged initially and the balance addad after the remaining reactants.
~ Charging also may be continuous or semi-continuous, if desired.
; Order of addition, reactant pxoportions and other conditions of reaction thus may be varied to control the geometry, molecular weight and other characteristics of the products, in accordance with well-known principles of polyurethane synthesis.
As is evident from their formulas and the Examples following, the Group A polymers are conveniently prepared by formin~ a prepolymer of a polyoxyalkylene glycol and a diisocyanate, and then capping th3 prepolymer with a monoisocyanate or mono-diisocyanate mix, when the prepolymer has hydroxyl terminal groups, or with a monohydric or amino compound (or alkylene oxide adduct of a monohydric compound or of an amdno compound) when the prepolymer has isocyanate terminal groups.
The Group B polymers are prepared in a similar manner except for use of a polyfunctional compound such as trimethylolpropan3 or a tri-isocyanate as a reactant. For example, ganerally star-shaped polymers result when a trim3thylolpropane-ethylene oxide adduct or a triiso-- 2~ -i$15875 cyanate is reacted with ~ monoisocyanate or monohydroxy ccmpound-ethylene oxide adduet, respectively. Suitable polyisocyanates are "Desmodur N" and "Mondur CB-75", deseribed below.
The more complex polymer mixtures of Group C result from reaetion of a polyol (at least three hydroxyl groups) or triisoeyanate with a diisocyanate or polyether diol, resp3etively, followed by eapping of unreaeted isocyanate with a monol or monoamine or capping of unreacted hydroxyl with a monoisoeyanat3. Exampl3s of suitable polyols are polyalkylolalkanes suc~ as trimet~lolpropane or trimethylolbutAne, hydroxy compounds having ether linkages such a-q the erythritols, (dipentaerythritol, tripentaerythritol, and the like) and hydroxy-alkanes containing three or more hydroxy groups, such as glycerol, butane tstraol, sorbitol, mannitol, and the like. As indieated, not all of the hydroxyl groups must be capped with ~onoisocyanate hydro-phobe~.
Reaetant ratios ean play an important role in determlning the pro-perties of the polymers. For exam~le, when the line&r polymers of Group A are prepared from isoeyanate-terminated polyethylene glyeol (PEG-moleeular weight 600~-7500) prepolymers eapped with decyl or dodecyl aleohol and where the isoeyan~te is tolylene diisocyanate (TDI), an aleohol/PE&/TDI equivalent ratio of 0.2-0.3/0.~-0.7/1.0 givas polymers whieh are excellent thickeners for latex paints. When, how-ever, the ratio is about 0.1/0 9/1 0 the thickening ability is ~o~ewhat less but flow and leveling eapabilities in the paints are very good.
Further deseription of these ~nd other properties is given below, following disclosure of preparation of the polymers.
Prepolymers, adducts or other reaetants eontaining ester groups should be avoided, due to hydrolytic instability of products containing sueh groups. However, the reaetants may eontain any other groups l~S875 provided such groups are inert, i.e., they do not interfere in forma-tion of the desired products. For example, halogens such as chlorine and bromine normally would not prevent formation of useful polymers.
ODUCT~ CONSISTENCY

S The consistency of the polymeric thickener products can be controlled either by a solvent reaction medium (mentioned above) or by combining the product with a softening agant after synthesis. With-out such treatment the higher molecular weight products tend to be tough and intractible. Depending on the molecular weight o the pro-10 . duct, the solids content, and the type an~ amount of additive, the product can be made to vary in consistency from a soft wax to ~
paste. Such consistency is important for subsequent handling of the product, including the ease with which it will disperse in aqueous systems to be thickened b~ it. While on a laboratory sc~18 it is possible to control consistency of the higher molecular weight pro-ducts merely by including more solvent during synthasis, production scale norm~lly requires minimal u~e of a non-polar solvent during synthesis to maintain kettle capacity, followed by addition of a soften-ing agent to the mixture toward3 the end of or following synthesis.
Although certain polar solvents may ~lso be present during syn-thesis (those which are inert to isocyanate, such as ketones and esters), s~ch presence is not preferred because of solYent recevery cost, the difficulty of keeping polar ~olvents moisture-free, and pha~e separation. Preferably, product consistency is controlled by 2~ synthesizing ~he higher molecular weight products in the presence of a non-polar solvent and then adding the softening agent to the reaction product mixture. A useful softening agent is a polar or non-polar organic solvent, a nonienic surfactant such as a polyethoxylated alkyl phenol, or any mixtures of two Gr ..-oYe o~ such solvents and/or SU--factants. The product may bo isolated prior~o treatment with the softening agent but there is u3ua117 no advantage to t.llis due to increased process cost.
The amount of softening azsnt may v~ -~idely, for example on th~
order of about 1-50% by weight o. the rea~ product mixture, and preferably is about 2-15% by wcight. The --~r.ening agent may also include a minor amount of water, on the or-^r of about 0.5-10%, p-eferably about 1-2%, based on total ra lc i~ product mixt-~Ire weight.
The prePerred softening agants are mixturDC ^f nonpolar a omatic hydro-carbon solvent3 and polar organic solvent3, -~th or without water, such as thq reaction :nedium solvents ment. :3d above. Typical mix-tures and amo-mts effecti ~e for softenin~ ' 9 polyurethane produo',s include the following, where the IlSolvesscll ~trademar~) 100 nonpo~ar aromatic solvent may be added as part of tk~ softener or may alread;y be present i~ the reaction product mixture, ~nd the polyurethane reaction product mixture is at about 800C. d~ring ~oftener addition:
SOFTE21h~l WT ~ ON P~7TJRETHA~E ~RODUCT
" Solvesso 100,~isopropanol 50/5-10 " Solvesso 100j~ethanol 50/5 " Solv2sso lOOj~n-butanol 50/5 Solvesso 10G)~t-but~nol 50/5-10 " Solvesso 100yn-but~nol/wate~ 50/5-10/2 " Solvesso 100,~butyl Cellosolve 50/10 ".Solvesso 1007butyl"Cellosolve'j~t~r 50/10/2 *Trademark, Butyl "Cellosolve" is ethylene glycol monobutyl ether.

B

lllS~375 Lat~x P_int Compositions The invention includes latex paint compositions containing an emulsion or dispersion of a water-insoluble polymsr and a polymeric thickener of the foregoing polymer groups. The water-insoluble polymers ~ay be any of the types conventionally utilized in latex paint compositions and include natuL~al rubber latex ingredients and synthetic latices wherein th~ water-insoluble polymer is an emulsion polymer of mono- or poly-ethylenically unsaturated olefinic, vinyl or acrylic monom~r types, including homopolymers and copolymers of such monomsrs. Specifically, the water-insoluble emulsion polymer may include poly (vinyl acetate) and copolymers of vinyl acetate ~preferably at least 50% by weight) with ona or more of vinyl chloride, vinylidene chloride, styrene, vinyltolusne, acrylonitril~, methacrylo-nitrile, acryl~m;de, methacrylamide, malsic acid and esters thereof, or one or more of the acrylic and methacrylic acid esters mentioned in U. S. Patent Nos. 2,795,564 and 3,356,627, which polymers are well-known as the film-forming component of aqueous b~se paints; ho -polymer~ of C2-C40 alpha olefins such as ethylene, isobutylene, octene, nonene, and styrene, and the like; copoly~ers of one or more of these hydrocarbons with one or more esters, nitrile3 or d des of acrylic acid or of m3thacrylic acid or with vinyl e3ters, such a~
vinyl acetate and vinyl ¢hloride, or with vinylidene chloride; and diene polymer3, such as copolymers of butadiene with one or more of styrene, vinyl toluene, acrylonitrile, methacrylonitrile, and ester~
of acrylic acid or msthacrylic acid. It is also quite common to in-clude a small amount, such as 0.5 to 2.5% or more, of an acid monomer in the monomer mixture used for making the copolymers mentioned above by emulsion polym~rization. Acids used include ~crylic, methacrylic, 1~15~75 itaconic, aconitic, citraconic, crotonic, maleic, fu~aric, the dimer of methacrylic acid, and so on.
The vinyl acetate copolymers are well-known and inclu~e co-polymers suc~ as vinyl acetate/butyl acrylate/2-ethylhexyl acrylate, vinyl acetate/butyl m~leate, vinyl acetate/ethylene, vinyl acetate/
vinyl chloride/butyl acrylate and vinyl acetate/vinyl chloride/ethylene.
Throughout t.kis specif~cation the term "ac~ylic polymer" means any polymPr wherein at least 50% by weight is an acrylic or methacrylic acid or ester, including mixtures of such acids an~ esters individually and together. The term "vinyl acet~te polymer" means any polymer containing at least 50% by weight of vinyl acetate.
Even small particle size (about 0.1-0.15 micron) acrylic and other latices ara thickened effectively, and flow and leveling improved, by thickeners of the invention. Such latices are notoriously resist nt to improvement with conv ntional thickeners The aq1leous polym3r dispersions may be prepared according to well known procedures, using one or more emulsifiers of an anionlc, catio~ic, or nonionic type. Mixtures of two or more emulsifiers reg~rdless of type may be used, except that it is generally undesirable to mix a cationic with an ~nionic typs in any appreciable amolmts since they tend to neutralize each other. The amount of emulsifier may range from about 0.1 to 6~ by weight or som~times evsn more, based on the weight of the total monomsr charge. When using a persulfate type of initiator, the addition of emulsifiers is often unnecessary. This omission or the use of only a small amount, e.g., less than about 0.5%, of emlllsifier, may sometim~s be de~irable from a cost standpoint, and less sensitivity of the dried coating or impregnation to moisture, and hence less liability of the coated substrate to be affected by i l~lS~7~

moisture. In general, the molecular weight of these emulQion polymers is high, e.g., from about 100,000 to 10,000,000 viscosity average, most commonly above 5~0,000.
The foregoing and oth~r emulsi~n polymer systems which may be thickensd with the polymeric thickensrs of the invention are set forth in the extensive lltsrature on the subject, such as ~. S. Patents ~ 3,035,004; 2,7~5,564; 2,875,166 and 3,037,952, for exa~ple. The polymeric thickeners are also suitable as substitutes for the pol-meric thi^:~eners in the polymeric syste~s disclosed in U. S. Patents 2,875,166 and 3,035,004 and in Canadian Patent 623,617.
One of the outstanding benefits when using the polymeric thick-eners of the invention is the capability of "fin tuning" the ~tructure of the polymers to obtain optimum values and balance of vis-cosity in aqueous dispersions containing the polymers, u~der high and lou shear conditions, a3 well as film building ability, flow and leveling, and other properties especially desirable in latex paint composition~. This is achieved by building into the polymeric thickener specific types and sizes of hydrophobic groups and by se-lecting hydrophil molecular weight 90 as to provide inter-hydrophobe 2~ d~stances effective for good thickening by an associative mechanism.
The hy~1rophobic groups whlch lend themselves most readily to such control are the terminal hydrophobic ~roups preferably containing about 4-20 carbon ato~3 based on aliphatic or aromatic ~onohydroxy or monoamino compounds (alcohols, phenols, amines) and organic monoiso-cyanates. It is especially surprising that such control can be effectsd with small, relatively low molecular weight hydrophobic capping g.oups.
The polymeric thickaners may be added to polymer latex systems at any time during the preparation theraof, including during or after ~ 26 -1115~75 poly~erization or copolym3rization and by single or multiple additions.
Normally, from about 0.1% to about 10%, preferably 1-3%, by weight of polymeric thickener on polymsr latex solids is adequate to pro-vide suitable levels of thickening and other properties. However, the amount may ~e higher or lower depending on the particular system, other additi-es present, and similar reasons understood by the formu-lator.
Since the polymeric thickeners are nonionic they ~re especially useful in latex paint and other latex compositions having an alka-line pH. They are also compatible with a great variety Or latex composition additives such as defoa~in~ agents, pigment dispersants, and surfactants of all types, and permit extended shelf life. The thickeners may be admixed with other components of the paint or other composition at any point during manufacture thereof and may even be the final ad~ition to the composition. From the st~ndpoint of capa-bility of tailoring the thickeners to obtain an optimum balance of properties in paint compositions and from the standpoint of resis-tance to degradation,the polym~7ric thickeners offer substantial advantages over natu~al or semi-synthetic thickening agents such as 2~ hydroxyethyl cellulose, casein, alginates and starches.
Other APPlica'ions Other aqu~ous systems in whic~ the polymeric thickeners are use-ful include aqueous coating compositions for the paper, leather and textile industries, oil well flooding composition3 and drilling muds, detergen+3, adhesives, waxes, polishes, cosmetics and toiletries, topical pharmQceuticals, and pesticidal or agricultural compositions for the control of insects, rodents, fungi, parasites of all kinds, and undesirable pla~t growth.

~lSB75 Moreover, the polymers are useful for the thickening Or water alone, the re3ulting solution then being useful for addition to another system to bc thickened. For example, the addition Or a suit-ablc amount Or a water soluble alcohol such as meth~nol to a water ~olution containing 25% by weight of the thickener forms a "clear concentrute" usc~ul in preparing pigment printing p~stes.
In the textile field the thickeners are useful in warp si~es, textilc finishes, bonding agents for both wovens and non-woqens, tie-coats, and for the thickening of dyeing and coloring compositions Or all types. For printing paste emulsions and dispersions it has been found that the Croup B and C polymers (Examples 35 ~
perform better than the linear polymers Or Group A, pos~ibly because the Group B and C polymers contain more hydrophobic groups and/or higher molecular weight hydrophobic groups. The textile printing ~astes may be simple aqueous dispersion or oil-in-water e ~lsions. Any water soluble or insoluble coloring material may be used, such as inorganic pigments and vat dyes. For example, thickeners Or the invention may be used as sub6titutes ror the thickeners dis~bsed in the dyestuff or coloring assistant composition~
Or U. S Patents 3,46~,62~; 3,467,485 and 3,391,985.
Although an organic isocyanate is an essential reactant in forming the polymeric thickeners Or the invention, any residual iso-cyanate is easily eliminated by dispersing the thickeners in water.
This removes any isocyanate toxicity from the thickeners and thereby make3 them suitable as additives to various types Or cosmetics such as hand creams, hand lotlons, cleansing creams, hair creams, cold w~ving lotions, shampoos, creme rlnses and the like. The thickeners Or the invention also form "ringing" gels in aqueous solution in the lilSE~7~

manner Or the polyoxyethylene-polyoxypropylene gel3 Or U.S, Patent 3,740,421 and can be used in cosmetic and pharmaceutlcal compositions similar to the gels o~ that patent.
The followlng examples wlll ~urther illustrate the invention in one or more o~ its various aspect~. All parts and percentages in the Example~ are by weight unless otherwise indicated. Molecular weights o~ polyalkylene ether reactant~ or residue~ are by hydroxyl number unless otherwi.se indicated.

Example~ 1 - 34 Group A - Linear Polymers Example 1 ~ . . _ . .
~olylene diisocyanate (TDI) - polyethylene glycol (P~G) prepolymer capped with dodecyl isocyanate A mixture o~ 60 g. o~ PRG (molecular weight 60oo) and 200 g. o~ toluene was dried by azeotropic di~tillation.
The mixture wa~ cooled to 75C, and o.o6 g. Or dibutyltin dilaurate and 1.4 g. Or TDI was added. Arter 2 hours at 75C, 1.7 ~. o~ dodecyl i~ocyanate was added. The mlxture was then malntained at 60C for 4 day~. The re~ulting ~olid polymer, i301ated after toluene evaporation from a ~lab mold, had a gel permeation chromatogram lndicating a weight average molecular weight (Mw) Or 71,100 and a number average molecular weight (Mn) Or 15,900.

lllSB7~

Examples ~ and 3 TDI-PEG prepolyms~ capped ~ith dodecgl isocyanate and octadecyl isosvanate A mixture o~ 400 g. of P2G (molecular weight 4000) and about 600 g. of toluen~ was dried by azeotropi~ distillation. The mixture was cooled to 75C. and 0.4 g. of dibutyltin dilaurate was added. To one-third of this reaction mixture was added 6.34 g. of dodecyl iso-cyanate (Example 2). To another third of the reaction mixture was added 8.9 g. of octadecyl isocyanate (Example 3). The solid polymeric products were i~ol~ted as described in Example 1.
The structures of the poly~eric products of Examples 1 - 3 ars set forth below in con~unction with Table 1. This table ~180 includes similar products prepared essentially a~ the foregoing ~ith the major variations as indicated.-R-X ~ (OCH2CH2)X-t~O-C-N-RI'-N-C~CH2CH2)X ~ 0-~-N-R' Table 1 x No. R _ R~ R" x n 1 n-C12H25 n-C12H25 ~ C7H6 136 3 2 n-C12H25 n-C12H25 C7H6 91 2 3 n-C18H37 n-C12H25. C7H6 91 2 -C18H37 n-C18~37 ~ C36 based 455 n-C18H37 n-C18H37 ~ C13H22 455

6 n-C18H37 n-C18H37 C7H6 455

7 n-C8H17 n-C8H17 C36 based 136

8 n-C18H37 n-C18H37 C36 based 136

9 n~C13H37 n-C18~37 C13H22 136 n-Cl8H37 ~ C18H37 C7H6 136 3 ~115875 l/ The dilsocyanate provldlng thls resldue throughou' all examples o~ this applicatlon was a co~nercial mixture of the 2,4- and 2,6- isomers of tolylene dllsocyanate. The value o~ x in all example3 ls based on the nominal molecular welghts of commerclal polyethylene glycol produ~ts rather than on a~say o~ each lot~

2/ ~he dlisocyanate providlng this residue throughout all -example~ of this application was "DDI", a C36 dimer acid-~ased diisocyanate ~rom General Mllls Corporation.

3/ The dli30cyanate providing this residue throughout all examples o~ this applicatlon was 4,4~-methylenebis(lsocyana-tocyclohexane), commercially available as "Hylene W"*.*

*Trademark **Trademark 7~~~

1~15875 Examples 11-23 Isocyanats terminated prepolymers of polyo~Jethylen~ glycol and diiso-cyanate~ capped with aliphati~ alcohols o~_amines The reaction~ tabulated in Table 2 below were conducted oy predry-ing a mixture of 50 g. of PEG (4003 to 20,000 molecular weight), 0.05 g. of dibutylti~ dilaurate and 50 g. of toluene by a3eotropic distilla-tion. The reaction mixture was cooled to 60C., and an aliphatic alcohol or amine was added, followed bS ~he diisocyanate listed. The reaction tem~erature was maintained at 60C. for 3-5 days before iso~
lation of the solid polymer by evaporation of the solid thickener in a ~lab mold. The structures of the products are set forth below in con-~unction with Table 2.

R-0 ~ ~-¦-R " ~ - N-~-o-(cH2cH2o ) ~ nC-~-R" ' - ~-C-0-R

H~ ~ CP-I-R " ~ 0-(C~2C~20)X ~ nC ~ ~
" Rl' TA~LE 2 Ex.
No. R R~ R" R"~ x n -13n-C8H17 - ~ C7H6 136 14n C12H25 ~ C7H6 136 15n-C18H37 - ~ C7H6 136 17n-C12H25 - ~ C7H6 l 36 2 18C12H25 ~ C7H6. 163 4 18A ~ t-do- HC13H22 163 4 - t-do- H " 163 2 decyl 22menthol - - " 136 4 23dlcyclo- - - " 136 4 pentenyl ~/ res~due o~ "Hylene W" dli~ocyanate 1~15875 Examples ?4 - 28 Diisocyanats-p~lyethylsne glycol prepolymers cappsd with eth2~ne oxide-monoh2~ compoun~ adducts _ _ _ A mixture of 600 g. of dried PEG (6000 molecular weight), o.6 g.
of dibutyltin dilaurate, and 26.1 g. of tolylene diisocyanate was allowed to react at 60C. for 24 hours. At that time, the toluene solution was split into six equal portions; to four of these was separately added 15 milliequivalents of a predried alcoh~l of struc-ture (a) octylphenol-ethylene oxide adduct of molecular weight 3000, (b) hexadecyl alcohol-ethylene oxide adduct of molecular weight 3000, (c) dodecyl alcohol-ethylene oxide ad~uct of 2600 molecular weight, ~ld (d) octadecanol-ethylene oxide adduct of 2gO0 molecular weight. The reaction temperature of 60C. W~9 maintained for four days, and the solutions were poured out to air dry. The resulting poly~ers have the structure indicated below an~ in Table 3 (Examples 24, 26, 27 and 28 respectively).

R-O--~CH2CH20 ~ C-~-R' -N-C-0-(CH2CH2-0)~ C-N-RIX-C-~ OCH2CH ~XOR
T ~ ~ 3 Ex.
No. R Rl x y n 24t-octylphenyl C7H6 62 136 25~ C12H25 C13H22105 136 2 ~ 34 -1115~7s Examples 29 - 34 Polyethylene glycol-diisocyanate prepolymers reacted with diisoc~e~ate and caeped with monohYdric alcohol A mixture of 120 g. of PEG (20,000 molecular w3ight), 480 g.
of toluene~ and 0.12 g. of dibutyltin dilaurate ~ere dried by azeo-tropic distillation. At 75C., 2.16 g. of "DDI" diisocyanate was addad. In two hours (at 75C.), 2.2 g. of 4,4'-biscyclohexylmetha~
diisocyanate was added, and the reaction mixture was stored at 60C.
for 3 days. The mixture was then split into three equ l parts. To mixture A was added 0.355 g. of n-butanol, to mixture B was added 0 625 g. of n-octanol, and to mixture C was added 0.90 g. of n-dodecan~l. After 4 days at 60C., the samples were poured out to air dry. The p~lymeric products have the followin~ structure as ~urther defined in Examples 29-31 of Table 4 together with other products prepared in substantially the same manner.

R-0--C-N-R"-~-C--~(OCH2CH2)x-O-C-R'''-l-C~-n-O-~CH2CH2-O~ x-R~ -O-R
Table ~
Ex. N_o. R R"' R" x n 29 n-C~ C36 based C13H22 455 n-C8H17 C3~ based C13H22 455 31 n-C12H25 C36 based C13H22 455 32 8 17 C36 based C7H6 455 33 n C12H25 C36 based 7H6 455 34 1~H37 C36 based C7H6 455 ~ 35 -l~lS~75 Examples ~5 - 63 Group B - Star-Shaped Pol~mers Example _ 35 Trimethylolpropane-ethylene oxide adduct capped with octa~ecyl isoc~anate In a suitable reaction vessel 70 g. of trimethylolpropane-ethylene oxide adduct with a hydroxyl number of 12,5 (eq, wt. 4500 psr OH) and about 100 g, of toluene were dried by azeotropi^ distilla-tion, Then 0.07 g. of dibutyltin dilaurata and 6.34 g. of octadecyl isocyanate was added. After 4 days at 60~., the sP~ple was dried in a slab mold. The structure of this polymeric product is set forth below in conjunction with Table 5 which also lists s-milar polymeric products prepared in essentially the sama m~nner as the Example 3 product, with the ma~or variations as indicated in the Table, C~3C32-C~C320-(C~2C320)y~C~ ~l3 Table 5 Equivalents Ex. No. _ R x NCO/OH
n-C18H37 102 1.37/1 36 " 104 0.43/1 37 n 34 1.35/1 38 " 73 0.87/1 3g n 53 1 . 05/1 4 " 53 0.7/1 41 n 102 1/1 42 ll 53 1/1 43 n-C12H25 132 1.2/1 44 n-CgH17 1L2 1.2/1 n-C12H25 73 0.9/1 46 " 73 1.1/1 47 n-C18H37 132 1.2/1 1~15~75 Examples 48 - ~ 0 Triisocya~atD coupled with ethoxylated do-~?canol and methoxy capped-p~lyethylen~ ~1YCO1 Two mixtur~s of 40 g. each of etho~ylated dodecanol of 7300 molecular weight, 11.8 g. of monomethoxy capped-polyethylene glycol of 5000 m~lecular weight, 80 g. of toluene and 0.08 g. of dibu'yltin dilaurate were dried by ~saotropic distillationc Aft~r coolin2 to B 60C., 2.54 g. of M~ndur CB-75 (Example 48) or 2.09 g. of Desmodur N
(Example 49) were addsd to the reaction mixtures. After 3 hours at 60C., the infrared spectrum indicated complst3 reaction, and the reaction ~ixture~ were p~ured into ~lab m~lds to iqolate the solid polymer~. The structures of these an~ other polymers, prepared in ess3;qtially the same manner, are g~vsn below in con~unction with Table 6.

~R(R')(R'')-0-(CH2cH2 - )x(x,)c(xll) X~~~~~~nR

EX.
No. R R~ R~' Rl~l x x~ x~' n ~ _ _ _ 48 n-C12H25 3 ~ C12~25 C30_/ 162 113 162 3 49 ~' n 20 162 113 162 3 ~ Cl2 ~ 5 C20 55 55 55 3 1/ residue of "Mo~dur CB-75" trlisocyanate -_/ re~idue o~ "De~modur N" trii~ocyanate l~lS87S

Example3 51 - 63 Example 51 Dipentaerytnritol-ethylene oxide addu t capped with octade~1 iSocYanate A dipentaerythritol-ethylene oxide adduct of 18.1 hydroxyl Dumber (3100 equivalent weight) was heated under a nitrogen sparge to remove w~ter. Utilizing dibutyltin dilaurate as catalyst, 70 g.
Or the adduct was reacted with 7.06 g. Or octadecyl isocyanate, pro-viding an NCO/OH ratio of 1.06/1 equivalents. The reaction was con-tinued at 60C. for four days. The poly~eric product was then poured into a slab mold to dry and to solidify. The structure of this pro-duct is indicated by the for~lla below in con~unction with Table 7, which also shows similar polymers prepared in essentially the same manner as describcd above, and NCO/OH proportion3 in equivalents.
~ H
0-f-CH2-C~CH20 -(CH2CH20)X-C-l-R~3]2 ~ 39 -111587~ -Table 7 Equivalents Ex No. R x N~O/OH
51 n-C18H37 70 1.06/1 S 52 ll 27 0.89/1 53 n 44 0.81/l 54 " 44 0.49/1 n-C12H25 167 0.9/1 56 n-C18~37 167 0.9/1 57 27 0.6/1 58 n 70 0.9/1 59 n 70 0.7/1 n 70 0.53/1 61 n 44 1.06/1 62 n-C12H25 167 1.25/1 63 ~-C1 8H37 167 1.25/1 1115~37S

Examples 64-1l7_ Crovp C - Co~plex Pol~ners _ As indicated above, the presence of a difunctional reactant (polyather diol or diisoc;rm ate) in a reaction mixture w th a tri-functional reactant (or higher functionality) such as a triis3-cyanate or trihydroxy compound, respectively, leads to compl3x branching in the product and a ~~ariety of polymeric products the identity of which cannot adequately be determined. Ho~ever, the polymeric reaction product mixtures contain the re~uisite proportions of hydrophobic and hydrophilic materi~ls for good thickening proper-ties and therefore are useful products.
Tabl~ 8 below summarizes many OL the possible comb nations o reactants which provide polymeric reaction products of this class, and the proportions in equivalents of reactants affective for such reac-tion~. The subsequent Examples and Tables illustrate these reactions more particularly.

r~ I X

~1 1 o ~ o ~0 X ~ ~ X I

o W W O ~ O ~ O W u~ o o ~q O ~ ~ o ~
U~ ~ XI ~ ~ X ~ I ~ X ~ U~ ~ X
~1~ o /~)~ o 0 a~ O a) o ~- o ~3) cq r ~ o o o~ 0 o o o~ $ ~ ~1 ~ x! ~ ~ ~ o ~Y o o 2 1 'Y ' ,~, o o ~Y
ol o o o o . ~
o o ,, ~l ~o ~ ~ 0 ~ ~

lllS875 Examples 64-72 Example 64 Trimethylolpropane-P~G-TDI prepolymers capped with_~lcohols tG provide polybranc1~ed pol~mers A mixture of 2 24 g. of trimethylolpropane in 150 g. of toluene and 19.56 g. of TDI were ~ixed at 78 C. After 15 minute3, this mixture was added to 300 g. of predried PEG (6000 molecular weight) in 300 g. of toluene containing 0.3 g. dibutyltin dilqurate. After 2 hour~ of 75C , thc~ mixture was allowed to cool to room temperature and maintained there for 72 hours. The solution was then warmed to 80C., and split 1nto 3 equal portions. Po~tion A wa~ treated with 2.93 g of octanol, portion B was treated with 4.27 g. of dodecanol, and portion C was treated with 6.1 g. Or octadecanol. After 24 hours at 60C., samples A, B, and C (Examplas 64-66 ) were isolated aft~r toluen~ evaporation from a slab mold.
Example _67 Polybranched polymers from a trimsthylolpropane-ethylene oxide_adduct._TDI. PEG and octadscanol A m~xture of 61 g. of a trim3thylolpropane-ethylene oxide adduct of hydroxyl number 18.2 (3100 equivalent wt.), 240 g. of P3G (6000 molecular wt.) and 5.~, g. of octadecanol was dried by a~eotropic dis-tillation of a solut,ion in 539 g. of toluene. The mixture was cooled to 60C., 11.3 g. of TDI and 0.3 g. of dibutyltin dilaurate w~re added, and the temperature was raised to 70C. Three hours later, 4.1 g f oct~decanol wa~ added and the tem~erature wa3 raised to 800C.
Aftsr 3 hours at 80C,7 tho reaction m-xture wa~ poured into a slab ~ld and the toluene removed by evaporation.

1~J.5~375 Example 68 Polybranched polymer from trimethylolpropa~e, _ TDI PEG a~d octa~ecanol The procedure of Example 67 was followed, bu5 ~.9 g. of TMP was substituted for the trimethylolprop~ne-ethylane oxide adduct of Example 67 Exam~l~ 69 Trio~-PEG adducts reacted with monoh~lric alcohol and diisocyanats. and caP~el with monohvdric alcohol A mixture of 10.5 g. of "Pluraeol" TP-1540 (tr~ol adduct of propylene oxide and trimethylolpropane), 244.5 g. of PEG-6000 (eq. wt.
3700), 0.3 g. of dibutyltia dilaurate, 5.4 g. of octadec~no' and 400 g. of toluene was dried ~y azeotropic distillation. At 60C., 11.3 g.
of tolylene diiso~anate was added. After 3 hours a, 70C., an addi-tional 4.05 g. of octadecanol was addad. After an additional 3 hours at 80C., the mi~ture was poured ou. to air dry. Table 9 lists the foragoing and other reactants used to prepare other polymers essen-tiqlly as described above. The proportion of equival3nts of the reactants i9 given in parenthes3s.
In these and the subsequent E~amples ~'TMP" is tri~eth~lolpropane, "E0" is ethylene ox- ~9 ~nd ~P0" is propylena oxide. The subscript to E0 or P~ ln~icates th3 number of E0 or P0 units in the reactants.

*Trademark.

. . ~.
, ~. ~

1115~7~ 1 Ex. Mono-OH Dilsocya-No. Triol (eq~ Diol (eq-) Alcohol(eq.) nate(Eq.) 64 TMP (1.O)PEG-6000(2.0)C8H17(1.5) C7H6(4 5) ~ '~ n 12 25( 5) 66 " " " 18 37( 5) 67 TMP E0~6(1.0) (4~) (1.75) " (6.5) 68 TMP ( 1. O ) n n ( 1, 75) 69 TMP P08(1.O) PEG-7400(3.3) " (1.75) TMP-POg(l-O)~l (6.o)~ (1.0) ~l (8.2) 71 TMP (1.0)PEG-7600(8.0)CloH21(1. ) 13 10 .
72 TMP (1,0) C12H25( ' ) " (10) lllS875 Examples_73, 74 Polybranched Polymers from Triol, Diol, Monofunctional Amine and a Diisocyanate Example 73 A mlxture of 2,68 g, o~ trlmethylolpropane (60 meq.), 360 g. of PEG-6000 (120 meq.), o.36 g. o~ dibutyltin dilaurate and 500 g. of toluene was azeotroplcally distilled to remove water. Then ?7 meq, (23.5 g.) o~ TDI was added at 50C. After 3 hours at 75C,, one-third of the solutlon was removed and treated with 5.7 g. (30 meq.) of"Primene 81-R, a C12-C14 t-alkyl primary amine. A~ter 48 hours at 60C. the polymerlc mixture wa~ isolated by evaporation of the toluene.
Example_74 The procedure o~ Example 181 was followed using 54 g. of an ethoxylated TMP o~ 1200 equivalent weight (45 meq.), 540 g, of PEG-6000 (180 meq,) and 44,3 g, o~
'~ylene W"(337.5 meq.) diisocyanate. A~ter 4 hours at 60C,, the sample was spllt lnto 9iX equal fractions, To one fraction was added 5.7 g. (50 meq,) of"Primene 81-R"amine.
Arter an additional 72 hours at 60C. the polymeric mlxture was lsolated by evaporatlon of~the toluene, Examples 75-81 Polybranched polymer~ from PE&, a trimethylolpropane-ethylene oxide adduct, octadecyl isocyanate and a dllsocya-nate -Example 75 A mixture o~ 225 g. of PEG (20,000 molecular welght) and 400 g. o~ toluene was drled ~y azeotropic dls-tillation at 70C. Then 0.225 g. of dibuiyltin dilaurate B

lliS~75 and 3.34 g. Or octadecyl isocyanate was added. Two hours later, still at 70C., 7.4 g. of "DDI" wa~ added. In one hour, 37.5 ~. Or a trimethylolpropane-ethylene oxide adduct Or hydroxyl number 17.1 and equivalent weight 3300 pre-dried in toluene solutlon, was added.

_ 46a -lllS87S

After 5 days at 60C., the mixture was dried in ~ slab mold. Table 10 describes ~he foregoing and other reactants giving other polymeric prod~lcts prepared in essentially the same manner. The proportion of equivalents Or reac+ants is gi~Jen in parentheses.

Table 10 Ex. Monoiso-No. Triol (eq.~ Diol (eq.) Diisocyanate_(eq.) cyanate (eq.) TMP'E075 (1.0) PEG-20,000(2.0) C36 (2.0) C1~ (1.0) 76 TMP E073 (1.0) P~G-6000 (2.0) C36 (2.0) C1~ (1.o)

10 , 77 TMP E073 (1.0) " (2,0) " (1.5) " (0.67) 78 TMP E117(1') " (3.0) C7H6(3.1) " (1,1) 79 rMP E~1~7(1 0) 1l (2,0) " (2,1) " (1.1) TMP E0~42(1.0) PEG-20,000(0.4) " (0.9) ~' (0.75) 81 E142(1~) 1 (0 4) " (0,9) C12 (0 75) l~lS~7S

, amPlss 8?-~?_ _ Polyethylene glycol and mon~hydric alcohols reac'ed with diis cAyanate and triisocya~ate Exampl~ 82 A mixture of 296.3 g. of PEG (molecular weight 7400 and eq. wt.
3700 by hydroxr~l mLmber), 8.1 of octadecanol, 4~0 g. of toluene and 0.4 g. of dibutyltin dilaurate was dried by ~z~otropic distillation.
At 60C., 7.83 g. of tolylene diisocyanate and 5.2 g. of "Desmod~r N"
were a~ded. After 3 hours at 70C. an~ 3 hours at 80C., the polymeric reaction product w~s poured ou'~ to air dry. Table 11 below lists the roregoing reactan's and others used to prepare polymers in essentially the s~e manner. Equivalent proportions are given in parentheses.
Table 11 Ex, Triisocyanate Diisocyanate No. Diol (eq.)Monol (eq.~ (eq.) (eq.) 82 ÆG-7~00(4.0)C1gH37(1.5)C2o(1~0) C7H6 (4~5) 83 ll (3.3)l~ (1.75) C30(1.o) n (4.5) 84 " (4.0)~ (2.0) C2o(1.1) n (5.2) n (3,3)~ (2,0) C30(1,1) n (4,9) 86 n (3,3)C14H2g(1~75) ~ (1.0) ~ (4.5) 87 n (3,3) ~c12H25(o~7)ll (1.0) n (4,5) f8H37(0.87) 88 ÆG-7600(3.3) C1~H37(2.0) ~' (1.0) n (4,4) 89 PEG-7400(2.5) " (1,5~ n (1.0) n (3.25) n (4,0)ll (2.0) n (0.84) n (5,1) 9l n (7,0)C~2H2s(2.0) ll (1.0) n (8.0) 92 ll (4.0) ~C12H25(0,7) ll (1.0) n (4,o) (Ç18H37(0.3) l;~lS~375 Examples 93 - 97 Trimethylolpropan? 3thylene oxide adduct reacted with octadecyl isocyanate and diisocyanate Exam~le 93 A ~ixture of 150 g. of a trimethylolpropane-ethylene oxide adduc' of 9.7 hydroxyl num~er (eq. wt 5~00) and 200 g. of toluene was dried by azeotropic distillation. Tben, 0.15 g. of dibutyltin dil~urate, 6.11 g. of octadecyl iqocyanate and 3.09 of "DDI" W~3 added at 60C.
After 5 days at 60~C., the polymeric product wa~ isolated after the toluene evaporated from a slab mold. Table 12 b;3low describes the foregoing an~ other rsactants used to prepc~re polymers essentially as described with respect to Example 93. Reactant proportions in equ-va-lents are given in parenthe~es.
Table 12 Ex. No. Triol (eq.) Diisocyana~e (eq.) M~noisocYanate (eq.) 93 TMR-E0132 (1.0) C36 (0-4) C1g (0.8) 94 TMP-E0132 (1.0) n (0.4) C12 (0.8) TMP E142 (1 0) n (0.4) C8 (0 8) 96 TMP E116 (1.0) ~ (0 4) t-C12 (0.8) 97 TMP.E0116 (1 0) ~' (0.4) t-C18 (-g) liiS875 Ex~ples 98-103 _ no~ E~te~ oapped polymers from triisocyanate Examplg 98 A mixture of 150 g. of polyoxyethylene glycol (60oo ~olecular weight), 150 g. toluene and dibutyltin dilaurate catalyst was dried by azeotropic distillation. At 70 C., 5.93 g. o~ dodecyl isocyanate ~as added. A~ter 2 hours at 70C. isocyanate consumption was complete, B an~ 4.49 g. of 75% Desmodu~-N triisocy~nate was added. The reaction ~ixture was held at 60C. for 1~ hollrs and then dried in a s~ab mold.
Table 13 below lists lhe foregoing and other reactants used to prepare polymers in esssntially the s~me manner. ProyorLionq in e~uivalents are given n parentheses.
Table 13 Ex _No Diol (eq.) TriisocYanate (eq ) MonoHC0 (eq.
98 Æ G-6000 ~1.0) C20 ~0.4) C1g (0.7) 99 PEG-20,000(1.0) " (0.4) ~ (0 7) 100 PEG-6000 (1.0) n (0.4) C12 (0 7) 101 PEG-20,000(1.0) ~ (0.4) C12 (0.7) 102 PEG-6000 (1.0) n (o.4) ~ C12 ( 35) ~ C18 (0-35) 103 PE~-20,000(1.0) " (0.4) ~C12 (0.35) C C18 (0 35) ~s~

Exa~plo3 104~
Alcohol caD~ed Pol~mers from triisoc~anates ExamPles ~04.- lQ5 A mixture of 70 g. of a dodecyl alcohol-ethylen~3 oxide adduct (4800 molecular w~g'at) and 90 g. Or toluene was azeotropically dis-tilled until water evolution ceased. Then, a+. 60C., 0.07 g. of di-r B butyltin dilaurate and 6.01 g. o~ Desmodur-N triisocyanate were added.
After 80 minutes at 60C., an infrared spectrum indicated complete consumption of hydroxyl. To 8~ g. of the resulting re~c~ion mixture was added 27 g. of a 50',~ PEG (6000 molecular weight) solution in toluene (A); to ~5 g. o~ the reaction mixture was added 59 g. 40% P35 (20,000 molecular w3igllt) in toluene (B). After an additional 3 hours at 60C., polymer samples A flnd B (Examples 104,10~ were poured out to air dry. Table 14 below lists the foregolng and other reactants used to pr~pare products essentially as described above. Proportions in equivalents are given in parenthsses.
Table 14 Ex. No. Diol (eq.) TriisocYan~ts (eq.) _ Monol ~eq.
104 pErJ-6ooo (1) C20 (3) C12'E105 (2) 105 PEG-20,000 (1) n (3) " (2) 106 pEr~-2o~ooo (1) n (3) C13 E11~ (2) 107 `PEG-6000 (1) n (3) C16~E0~3g (2) 108 PeG-20,000 (1) n (3) C16~E013g (2) 109 Æ G-6000 (1) n (3) C18'c150 (2) 110 Æ G-20,000 (1) n (3) " (2) 111 PEG-6000 (1) n (3) t-octylphenyl-E01~5 (2) 112 pEr~-2o~ooo (1) n (3) t-octylphenyl-EOl45 (2) 113 ÆC-6000 (1 ) n (3) C14~Eol14 (2) - 51 _ 1115~37S

Examples ll4-1l7 Polybranched polymers from triol, ~onol and diisocyanate Essentially as described in ~xamples 64-66 , po'ymeric reaction 5products were prepared from the reactant,s and in the proportions (by equivalents) listed in Table 15 below, Table 15 Diisocyanate Ex No.Triol (eq.) Monol (eq.) (eq.) 114157 ( ) C18H37-E0211(1-25) C7H6 (2-3) 115TMP-E01s7 (1.0) C12H25~E137(1-25) " (2.3) 116" (1.0) C14H29 E1~8(1~25) ' (2,3) 117~ (1.0) C16H33 E01o7(1~25) " (2,3) Example~ l18 - 127 A, Preparation of water solutions of thickeners Table 16 below sh3ws Broo~fi~ld viscosity measurements on 3~ water solutions of various polymeric thickeners identified ll~der previous Examples of th~s specification. Ths 30'utions were prepared by stan-dard mixing techniques.
B, Pre~aration of pol~mer emulsions Table 16 below also reports Brookfield and ICI viscositi33 of various polymer emulsions prepared by standard mixing techniques from the following recip~, wherein the thickeners are f~lrther identified above under polYmer Examples:
parts by we~2ht, Acrylic copolymer (46.5% solids) 80,0 Water 11,2 Water solution of thicksner, ~3% 24.8 ~iS875 C. Preparation of latex Dain' comoositions Table 16 below also indicates pr~perties of paint compositiun3 containing polymeric thickeners of the foregoing Examples, or hydroxy-ethylcellulose ( E ,). The recipe for the paint com~ositions follows.
The pigment grind, premix and th1ckener solutions are prepared separ-ately and then intermixed with he other ingredients in the or~er gi~en. Mixing techniques and equipment are conventional. The thick-ener solutions co:ltqi~ 3.2% by weight of HEC or 6% b~ -~eight of a thickener of the inrention and the final paints are formulated to contain 1% oy ~eight of thickener base~ on emulsion ?olymer solids.
Pi~ nt Grind Portion:Parts bY We-~ht Dispersant rTamol 731'34- 10.8 Defoamer ~opco ~J~W)"5- 2.0 Rutile TiO2 ('Ti Pure R-900'3 6- 296.0 Let-down Portion:
Propylene glycol 57.3 Polymer emulsio ~ A or B 557.9 Pre-mix:
Preservative ~Super Ad-It'~ 1 0 Water 8 15 ~
Cûalescent ~Texanol'~ 15 7 nic surfactant (~riton GR-~-2.~
Defoamer ~Topco ND~ 2.9 Thickener Solution: 80.4 Table 16 shows that efficient thickening o~ latex paints and sim~
polyml3r amuisions is not predictable on the basis of water thic~znia~
alone, even though HEC thic~ens water effectively. The Table ~lso shows that in many cases t:ie pûlymeric thic~en~rs of the invention thicken la-tex p~ints with the same or greater ef~lciency (viscosity impro~ement relative to amount of thickener) tha~ does HEC, and that best overall perfor3~nce in latex i~aints (thickening, flow anl leveling, film build in terms of ~igh ICI viscosity is obtained -rom polyurethanes 'nll~ing a multiplicity of hydrophobic groups - Examples 118 and 121.
4-9 inclusive. The terms bearing these superscript numerals are all Trademarks. 8. "Texanol" is a trademark for 2,2,4-trimethyl-1,3 pentane-diol monoisobutyrate. 4. "Tahol 731" is a trademark for the sodium salt ~_~) of a sulfonated naphthalene formaldehvde conden.c~t~

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Polymer E;nulsion A is Rhoplex AC-490 copolymer acrylic e~lsion (46.5~ solids); Polymer Emulsion B is"Rhoplex AC-61"copolymer acrylic emulsion (~6.5~ solids).
~ Tnickener solids on emulsion polymer solids is 2%.
~ Krebs units -- low shear viscosity.
~ High s~ear viscosity as measured on the ICI Con9 and Plate Viscosi-meter (Research Equipment Limited, London) op~rating at about 10,000 sec.~1 shear rate to simulate the s:~ear applied to a paint during brushing. Generally, as ICI viscosity increases, film thickness ("blild") also increases. Good build translates to increased hiding po~er of the paint and also contributes to improved flow and leveling.
Determined by comparing side-by-side drawdowns of control paint (containing HEC as thickener) and the experimental paint ("Exp.") con-taining a thic~ener of the invention, on a Leneta Form 1B "~enopac"
chart. The gloss measurements were made instrumentally.
~ Visual examination of brushmarks on a Leneta Form 12H Spreading Rate c~art. Ratings are on a 0-10 scale wh~re 10 is exceptionally supsrior flow and leveling and 0 represents totally unacceptable flow an~ leveling.

***~ra~eemaar~

, .

:IllS875 Examples l28 - 130 Table 17 ~)910w compares properties of iatex Faint co~positions containing a thickener of the inven'.ion or hy~roxyethylcellulo!~e (~:C).
The formulations of Ex~ples 128 and l29 are the same a3 in the paint Examples of Table 16 but the p.qint formulation of E~cample 128 is as follows (prep~qred by st~ndard mixing ln the order given) wherein the amount of thic'cener is 2% based on emulsion po~ymer solids:
Pi~ment_Grind Po. t;on:Parts by Weight Water g5.0 Dispersant ~'raTn~l 7311' g 0 Dispersant ~tetrasodium pyrophosphate) 0.3 Sur~actant ~ergitol N~X ylO. 2.0 Milde~ ide ~uper-Ad It~' 7- 1 O
EthylenH glycol 20.0 Coalescent (he:~ylene glycol) 15 0 2-Ethylhe:~yl acetate 5.0 Defoamer ~Nop^o ~)'AT~' 2 5 TiO2-rutile ~i Pure R-~01~ 1 75.0 TiO2-anatase ~'ritanox 1000yll.50 0 Mica, water-g~;)und (325 me~h) 25 0 Talc '~Nyto' 300)' 12. 125.0 Let-down Portion:
Water 36.1 Polymer emulsion 400.0 ;~efoamer ~lopco N~W) " 2.5 Thickener solution 170.9 Table 17 illustrates preferred thickeners of the in-r3ntion with respect to utility in latex paint compositions s..nce excellent balance between knickening efficiency, flow ~nd leveling iq demon~trated a3 compared with paints contai.~g hydroxyethylcellulose.

lO. Trademark for an alkylaryl polyethylene glycol nonionic surfactant.
ll. Trademark.
12. Trademark, 7. "Super-Ad-It" is the trademark for a solution of di(phenylmercury) dodecyl succinate contain1ng 10% mercury; it is used as a fungicide.

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ExamDl~ 1 31 Pi~ent Prin'in~ Paste A pigmen' ?rinting paste conventionally ^onsists of three major ingredieut;: pigment, thickener, an.1 b_nder. Be~ors these ingredi~3n,'s are mixed to form a print paste, a "cut clear" is form~d with a thick-ener and a color concentrate. Typically, the cut clear is prepared by dissolving in wate ~ ~J weight of a thickener, such a3 the poly-meric thickener of ~Yample 68~ and admixing for ab~ut 30 minutes to form a translucsnt gel of consistency over 100,000 cps. The cut clear functions as a viscosity builder in the paste.
Next, the color concent~a e is prepared, for example by ;lending over about 15 minute3 45.2% of a presscake dispersion (a pigment dispersion in water), 18~ of ths cut clear, and 36.8~p of watsr until a flowing cre~ paste of about 1900 cps viscosity results.
The print pasts is ~ormed by mixing 10% of the color concentrate and 10% of an emuls1On binder (of about 40-50% solids). A suitable binder is"Rh~ylex E-32"acrylic polymer emulsion, 46.0% solids. The resu~tant composition is a paste of 28,000 cps viscosity and is ready for p~inting use on cotton, poly3st3r, cotton-polysstsr fabric b ends and the like.
If desired '~h~ pigment printin~ pastes may bg formulated as oil-in-water emulsions by the addition of a water immiscible org mic 301-vent such as toluene, in the mannlr of Ger~an patent 2,054,885. The printing pastes may also contain dispersing aids, such as any of ths well-~nown ionic or nonionic surfactants, ~nd auxili~ry thic~eners suc~.
as a "5arbopol" carboxy vinyl polymer.

*Trademark 8 **Trademark ~ ~ ~

, . . .

1115~7~

Exam~ 2 Acid_ e Print Paste A typical acid dye print paste formulation at~lizing polym~ric products o-~ the invention is the following:
Wt %

Dye solution - Acid Plue-25, 6~ 12 5 Cut clear (6%) of 3xample 131 25.0 Formic Acid 1.g Nopco "Foam Master" DF-160L
~lti-foPm;ng agent .2 Water 60.5 Th2 ingredients are admixed fo~ about 15 minutes in a smooth, cresmy paste of pH 2.0-2.3 and a v.scosity of about 1600 cps. The pasta m~y be applied to a fabric such as carpeting by conventional techniques, such as by use of a ~immer flat bed screen.

Exa Textile Coat~n~ Formulation The polymeric thickeners of this inventiorl a~e effective for the thickening o various textile po.ymer coat~n.~s. A typical formulation u~eful as a flocking adhesive is ths following:

" 2hoplex HA-~"acry;ic polymer (46% solids) 300.0 pa-ts by weight Catalyst solutio~ NH4N03 (25% solids) 60.0 Cut ~l~ar (6%) of Example 131 30-Ths formulation has a creamy cons-.stency of about 40,500 cps and ~y be applied to a textile fab-i^ in a conventional m~nner, such as oy padding, dipping, roller coating or other coating or impreg:lating te^h-niques.
*Trademark **Trademark ~ 59 ~
R

l~lS~37~ ~

Pigmented Paper Coating~ 'r ~.
The polymeric thickeners of the invention are ~' useful in pigmented paper coatlng~ in place o~ natural pro- ~, 5 duct~ such a~ sodlum alglnate and carboxymethyl cellulose.
A typlcal formulatlon follows. '~
In a sultable container 72.6~ by weight of clay j~
(70~ æolids), 18.3% of"Dow-620"carboxylated styrene-buta- ~-diene polymer emulsion as a pigment binder (50~ solids), ~t~
1~ of the cut clear of Example 131 and 8.1~ water are mixed.
Thls formulatlon when pi~mented may be applied to paper by a trailing blade in a known manner. It has a consistency of about 1800 cp~.

*Trademark

Claims (22)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A latex composition containing an emulsion polymer and from about 0.1 to about 10% by weight based on emulsion polymer solids of a thickener selected from polymers of Groups A, B and C as follows:
Group A:
polymers selected from AE (BE)n A
and A (BE)n BA, wherein n is at least one;
Group B:
polymers selected from those of the formulas V-VII as follows:
V (H-E-OCH2)sX[CH2O-E-A]m VI Y[E-R]3 VII O[CH2C(CH2-O-E-A)3]2 and where, in each of the polymers of Groups A and B:
A and R are hydrophobic organic radicals;
B is a divalent hydrophobic group of the structure where G is the residue of an organic di-or triisocyanate, said residue having no remaining unreacted isocyanate groups; and E is a divalent, hydrophilic, nonionic polyether group;

(claim 1 continued) Group C:
a composition prepared by reaction a) a poly-functional reactant selected from an organic polyol having at least three hydroxyl groups, an organic polyisocyanate having at least three isocyanate groups, and mixtures thereof; b) a difunctional reactant selected from an organic diol, an organic diisocyanate, and mixtures thereof, said diol being present in the reaction mixture when said poly-isocyanate is present and said diisocyanate being present when said polyol is present; c) a monofunctional hydroxyl or amino compound in an amount sufficient to cap any unreacted isocyanate remaining from the reaction of reactants a) and b) and to prevent gelation of the reaction mixture; and optionally d) an organic monoisocyanate to cap hydroxyl groups remaining from the reaction of reactants a) and b); wherein at least one of said polyol and diol contains at least one water soluble polyether segment of at least 1500 molecular weight, and wherein the sum of the carbon atoms in said isocyanate-containing reactants, said hydroxyl compound and said amino compound is at least 20 and the average molecular weight of the components of the composition is about 10,000 - 200,000.

2. A latex composition as in Claim 1, wherein in said thickener polymers:

A is R'O-, R"R'''N- or where R' is alkyl, cycloalkyl or alkaryl;
R" is hydrogen or alkyl;
R''' is alkyl; and R'''' is alkyl or alkaryl;
G is the residue of a diisocyanate selected from tolylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-methylenebis(isocyanato-cyclohexane), 4,4'-methylenebis(phenylisocyanate) and C36 dimer acid diisocyanate;
at least one E group is ?CH2CH2O?x where x is at least 25, and one of the remaining E groups may be where y is at least 8; and x is CH3CH2C?;
m is 3; and n is 1-20.

3. A latex composition as in Claim 2 wherein, in said thickener polymers, A is R''''

4. A latex composition as in Claim 2, wherein in said thickener polymers, A is R'O-.

5. A latex composition as in Claim 1 wherein, in said thickener polymers, A is R''R'''N-.

6. A latex composition as in Claim 1 wherein, in the polymers of Group C, 75-100% of all terminal hydroxyl is reacted with organic monoisocyanate.

7. A latex composition as in Claim 1 wherein the thickener is a polymer of Group A.

8. A latex composition as in Claim 1 wherein the thickener is a polymer of Group B.

9. A latex composition as in Claim 1 wherein the thickener is a polymer of the composition of Group C.

10. A method of impregnating or coating a substrate which comprises treating said substrate with the latex composition of Claim 1.

11. A method as in Claim 10 wherein said substrate is a textile.

12. A latex composition as in Claim 1 wherein the emulsion polymer is an acrylic polymer.

13. A latex composition as in Claim 1 wherein the emulsion polymer is a vinyl acetate polymer.

14. A latex composition containing an emulsion polymer and from about 0.1 to about 10% by weight based on emulsion polymer solids of a nonionic water soluble or water solubilizable polyurethane thickener composition having at least three hydrophobic groups at least two of which are terminal groups; said hydrophobic groups together containing a total of at least 20 carbon atoms, said hydrophobic groups being linked through hydrophilic polyether groups of at least 1500 molecular weight each, and the molecular weight of said polyurethane being at least 10,000; said polyurethane composition being selected from the following reaction products (1) to (5) wherein reactant (a) is at least one water soluble polyether polyol, reactant (b) is at least one water insoluble organic polyisocyanate, reactant (c) is at least one monofunctional hydrophobic organic compound selected from monofunctional active hydrogen containing compounds and organic monoisocyanates, and reactant (d) is at least one polyhydric alcohol or polyhydric alcohol ether;
(1) reaction products of reactant (a) containing at least three hydroxyl groups, and said organic monoisocyanate;
(2) reaction products of reactant (a), reactant (b) containing two isocyanate groups, and said active hydrogen-containing compound;
(3) reaction products of reactant (a), reactant (b) containing at least three isocyanate groups, and said active hydrogen-containing compound;

(4) reaction products of reactant (a), reactant (b) and said monoisocyanate; and (5) reaction products of reactant (a), reactant (b), said monoisocyanate, and reactant (d).

15. A latex composition as in Claim 14 wherein the emulsion polymer is an acrylic emulsion polymer.

16. A latex composition as in Claim 14 wherein the emulsion polymer is a vinyl acetate emulsion polymer.

17. A latex composition as in Claim 1 wherein the amount of the thickener is 1-3% by weight based on emulsion polymer solids.

18. A latex composition as in Claim 17 wherein the emulsion polymer comprises (1) a vinyl acetate polymer or (2) a copolymer of one or more acrylic acid ester monomers or one or more methacrylic acid ester monomers.

19. A latex composition as in Claim 12 wherein the acrylic polymer comprises a copolymer of one or more acrylic acid ester monomers or one or more methacrylic acid ester monomers.

20. A latex composition as in Claim 14 wherein the amount of the thickener is 1-3% by weight based on emulsion polymer solids.

21. A latex composition as in Claim 20 wherein the emulsion polymer comprises (1) a vinyl acetate polymer or (2) a copolymer of one or more acrylic acid ester monomers or one or more methacrylic acid ester monomers.

22. A latex composition as in Claim 15 wherein the acrylic emulsion polymer comprises a copolymer of one or more acrylic acid ester monomers or one or more methacrylic acid ester monomers.