CA1045285A - Process for preparing particulate polyurethane polymers and the polymers derived therefrom - Google Patents

Abstract

ABSTRACT
Process for preparing particulate thermo-plastic polyurethane polymers and the polymers derived therefrom which are useful in the polyurethane elastomer art.

1.

Description

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BACKGROUND OF THE INVENTION
This lnventlon relates to a novel process for the productlon of polyurethane polymers and to the novel polyurethane polymer products derived ~rom said process. More particularly thls inventlon ls dlrected ` to a process for preparing partlculate thermoplastlc polyurethane polymers and to the pa~ticulate polymers derived rrom said process.
Thermoplastlc polyurethane polymers consti- ~ -tute a broad class o~ polymeric materials that are well known ln the art and have a wide range o~ utility.
Such polymers are essentially uncrosslinked and are I conventlonally produced through the interaction o~ a ~-¦ dilsocyanate, a dlhydric compound havlng two actlve ¦ hydrogen atoms in lts structure such as polyethers or I polyesters, and a chaln extendlng agent also havlng two actlve hydrogen atoms ln lt8 structure such as an organic dlol or diamlne. Normally sald polyurethane polymers are produced ln slab form or some other ~orm not sultable ~or use in application technlques employed wlth powdered type resins such as polyethylene. Such ~echniques include e.g. ~lame coatlng, heated substrate coatlngs, rotational coatlng, calendering, powder blendlng wlth other polymers, slntered shaped articles and coatings, and the like. Consequently such conventlonal types of thermoplastlc polyurethane products have to undergo a reductlon in particle size in order to be utillzed in such application techniques.
Whlle the polyurethane polymer may be reduced in partlcle slze by varlous expendlences such as grlndlng,

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chipplng, dicing, etc., such methods result ln coarse, non-unlform ~inal productsJ are time consuming, and have other numerous obvlous economic drawbacks. Thus there ls a definlte need in the art ror a process that wlll produce thermoplastic polyurethane polymers ln particulate ~orm.
It has now been dlscovered that partlculate thermoplastlc polyurethane polymers can lndeed be produced by the process of the lnstant lnvention whlch comprlses contactlng and reactlng an organlc dlhydrlc contalning compound, an organlc dlisocyanate, a dl-functlonal organic chaln extendlng agent and an organlc inter~acial agent ln the presence of an lnert organlc vehlcle ln which the resultlng particulate thermoplastlc polyurethane polymer ls essentially lnsoluble.
SUMMARY OF THE INVENTION
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Thererore lt ls an obJect o~ thls inventlon to provlde novel partlculate thermoplastlc polyurethane polymer~. It is a ~urther ob~ect of thls lnvention to provlde a novel dlsperslon process ~or the production of sald partlculate polymers. Other obJects and advantages of thls lnNention wlll become readily apparent ~rom the followlng descrlption and appended claims.
More speclfically, the process o~ the instant invention may be descrlbed as a process ~or producing a particulate thermoplastic polyurethane polymer which comprlses contacting and reacting (a) an organlc di-hydroxy containing polymer; (b) an organic di~unctional chain extending agent having two actlve hydrogen atoms ~ 3.

- ~ . " ' . .

9170-~

reactive with the isocyanate g:roups of the dlisocyanate compound; (c) an organic dlisocyanate compound; and (d) an organic polymerlc interfacial agent, sald lnter-faclal agent being characterlzed (1) by a solvatable ~:
constituent (i) which is solvatable in inert normally liquid saturated hydrocarbonsJ (il) which ls essent~ lly incompatible with the sort segment of the partlculate thermoplastlc polyurethane polymer product, and (iii) which has an average molecular weight o~ up to about 500,000 and (2) by a non-solvatable constituent (1) which ls non-solvatable wlth such inert normally liquldJ
saturated hydrocarbons, ~il) which is compatlble wlth the soft segment o~ the partlculate thermoplastlc poly-urethane polymer product,and (111) whlch has an average molecular welght of at least about 1000 and ls at least about 0.05 to about 10 tlmes the average molecular welght of the solvatable constltuent; (e) in the presence o~ an lnert organlc vehicle in which the ingredients (a), (b) and (~) are dlsperslble and in :
whlch the partl¢ulate thermoplastic polyurethane poly-mer product is lnsoluble; sald reactlon belng conducted under essentlally anhydrous conditlons and for a perlod of time sur~iclent to produce the particulate thermo- ~:
plastlo polyurethane polymer.

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,: . , -10~5285 DESCRIPTION OF THE PRE;FERRED EMBODIMENTS

As pointed out, the basic production of thermo-plastic polyurethane polymers involving the polymer-ization reaction of a dihydric compound, a diisocyanate and a difunctional chain extending agent is well known in the art, as witnessed for example by U.S.
Patents 2,871,218; 3,214,411; 3,432,474; 3,523,093 and

3,538,700.
The dihydric compounds employed as starting materials in accordance with the process of this invention are well known in the art and are organic -dihydroxy containing polymers, such as polyether diols, polyester diols and polymer/polyol diols which form what is commonly referred to as the soft segment of the final ~polyurethane product. Said organic dihydroxy containing polymers can have average weights ranging from about 300 to about 3,000 and hydroxyl numbers from about 375 to about 22.
Of course, it is to be understood that mixtures of such organic dihydroxy containing polymers can be employed as reactants with the diisocyanate in accordance with the process of this invention. It is also to be understood that in additîon to the above organic dihydroxy containing polymers a small amount e.g. less than 1 per cent by weight of higher poly-hydric compounds such as trihydric alcohol, e.g.
glycerine, trimethylolpropane, hexanetriol, pentaery-thritol, and the like, may also be present so long as . .

: ;

~0~5'~85 they do not unduly adversely effect the ess~ntlally uncrosslinked nature of the thermoplastic polyurethane polymer product de~ired to be obtalned. ~ ~ -~ The hydroxyl number i~ deflned as the number ; o~ mllligrams o~ potassium hydroxide needed to react with the acld generated ~rom the reaction of one gram o~ the hydroxyl contalnlng csmpound wlth phthalic , anhydrlde. The hydroxyl number can also be de~ined by the equat;lon: `
OH ~ 56.1 X 1000 X

where OH _ hydroxyl number Or the diol, ~ = functlonallty, s l.e., average number o~ hydroxyl groups per molecule of dlol, M.W. = average molecular welght o~ the dlol~
One pre~erred class o~ such dlhydroxy contalnlng materlals lncludes essentlally llnear hydroxy termlnated polyether~ such as polyoxyalkylene glycols lncludlng polytetramethylene glycols and alkylene oxide adducts of varlous di~unctional starters. Such poly-ether dlols are well known ln the art. Illustratlve examples Or such adduct~ are the alkylene oxlde adducts Or ethylene oxlde, propylene oxlde, butylene oxldes ;
and mlxtures thereo~, wlth water or dlhydrlc compounds such as ethylene glycol, dlethylene glycol, propylene glycol, dlpropylene glycol, butylene glycol, anlline, -and the llke. Pre~erred polyether dlols are the poly-tetramethylene glycol~ and the ethylene or propylene oxlde adducts o~ stralght chaln allphatlc glycols contalnlng from 2 to 10 carbon atoms. Such hydroxy termlnated polyethers pre~erably have average molecular welghts ranglng ~rom about 300 to about 4,000 and 5.

~0~5285 hydroxyl number Or about 375 to about 28. Most preferred are the polytetramethylene glycols having average molecular weights Or 1000 to 3000 and hydroxy number of 111 to 37.
The most preferred class of all such dlhydroxy contalning starting materlals are the polyester diols e.g,, essentially llnear hydroxy termlnated polyesters, and more especlally such polyesters commonly rererred to as polylactone dlols.
` 10 Illustratlve examples of such llnear hydroxy termlnated polyesters lnclude the esteriricatlon products of dlcarboxyllc acids, such as adiplc, succlnic, plmellc, suberlc, azelaic, sebaclc, phthallc, cyclohexanedlcarboxyllc acld, and the like or thelr anhydrldes wlth allphatlc glycols. Prererred aclds are those dicarboxyllc aclds Or the ~ormula HQOC-R-COOH
where ~ ls an alkylene ~adlcal contalnlng from 2 to 8 carbon atoms, especlally the polymethylene dlcarboxyllc aclds, whlle the most pre~erred acld is adlpic acld.
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Z 20 Prererred allphatlc glycols are the stralght chaln glycols contalning from 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanedlol, 1,6-hexamethylenedlol, 1,8-octamethylenedlol, and the llke, especlally the polymethylene dlols contalnlng from 4 to 8 carbon atoms, whlle the most prererred glycol ls 1,4-butanedlol. Such hydroxy termlnated ; polyesters prererably have average molecular welghts i ranglng ~rom about 500 to about 3000 and hydroxyl numbers Or about 225 to 37.
~llustratlve examples Or such polylactone dlol type esters lnclude those prepared by polymerlzlng 6.

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- D-9170-C ~
~045285 a lactone with or without a bifunctional initiator as well as those prepared by reacting a mixture of a lactone and an alkylene oxide with a bi~unctional ~ initiator. Such polylactone diols as well as the i methods for their preparation are well known in the art ` as witnessed, e.g., by U.S. Patents 3,021,309 through 3,021,317; 3,169,945; and 2.962,524. Suitable lactone ~-monomers which can be employed in the manufacture of the polylactone diols can be illustrated by the formula O
~i r- c-o 1 (R C-R)x ( (R-C-R

i wherein each R individually is a hydrogen, alkyl, halogen or alkoxy radical; x is an integer of 1 to 4; z has a ~, .
value of zero or one; the sum of x + y + z is at least 4 and no greater than 6; and the total number of R groups which are substituents other than hydrogen does not exceed 3 and preferably does not exceed 2. Illustrative R groups include methyl, ethyl, isopropyl, n-butyl, sec-butyl, t-butyl, hexyl, chloro, ~ -bromo, iodo, methoxy, ethoxy, n-butoxy, n-hexoxy, 2-ethylhexoxy, dodecoxy, and the like. It is preferred that each R individually be hydrogen, lower alkyl, e.g.
¦ methyl, ethyl, n-propyl, isobutyl and/or lower alkoxy, e.g. methoxy, ethoxy, propoxy, n-butoxy, and the like.
It is further preferred that the total number of carbon atoms in the R substituents does not exceed eight.
Illustrative cyclic ester monomers include, e.g.

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epsilon-caprolactone, delta-valerolactone, zeta-enantholactone, eta-caprylolactone, monomethyl-delta-valerolactone, monomethyl-epsilon-caprolactone, di-methyl-delta-valerolactone, and the like. Suitable bifunctional initiators include diols and diamines containing from 2 to 10 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, bis(4-aminophenyl)methane, ethylenediamine and the like, while illustrative alkylene oxides include those mentioned above. Such polylactone diol esters ; preferably have average molecular weights ranging from about 500 to 3000 and hydroxyl numbers of about 225 to 37. The most preferred polylactone diols are those prepared by reacting a lactone especially epsilon-caprolactone or methyl-epsilon-caprolactone with a lower alkylene glycol or diamine initiator.
S~ill another useful class of such dihydroxy containing materials are the polymer/polyol compositions obtained by polymerizing ethylenically unsaturated monomers in a polyol as described in Canadian Patent 735,010; British Patent 1,063,222, and U.S. Patent 3,383,351. Suitable monomers for producing such compositions include acrylonitrile, vinyl chloride, styrene, butadiene, vinylidine chloride and other such ethylenically unsaturated monomers. Suitable polyols include those diols listed and described hereinabove and in said patents. The polymer/polyol compositions can contain from about 1 to 70 weight per cent, preferably about 5 to about 50 weight per cent, and most preferably about 10 to about 10~528S
40 welght per cent monomer polymerlzed ln the polyol.
Such composltlons are conveniently prepared by polymer-izlng the monomers ln the selected polyol at a tempera-ture o~ 40C. to 150C. in the presence of a ~ree radlcal polymerizatlon catalyst such as peroxldes, persulfates, percarbonates, perborates and azo compounds.
~urther detalls o~ the composltions and methods o~
maklng same are descrlbed ln the above mentioned patents.
. The resultlng polymer/polyol composition ls believed to ` 10 be a complex mixture comprlsing ~ree polyol, ~ree polymer and gra~t polymer/polyol complexes. Preferably such polymer/polyols have average molecular weights ranging from about 300 to about 5100 and hydroxyl numbers o~
about 375 to 22. The preferred polymer/polyols are !
those o~ acrylonitrile and polyoxyalkylene glycol.
~ oth aliphatlc and aromatic organlc di-isocyanates can be used in accordance with the process Or this lnvention to react with the dihydric starting materials to rorm the lnstant thermoplastic polyurethane polymer products. Such diisocyanates are well known in the art and ~orm part of what is commonly re~erred to as the hard segment of the polyurethane product.
Illustratlve examples of same lnclude tetramethylene-1,4-dllsocyanate, hexamethylene-1,6-dilsocyanate, p- -phenylene dilsocyanate, m-phenylene dllsocyanate, 1-chlorophenylene-2,4-dli~ocyanate, naphthalene-1,5-dilsocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-dlisocyanate, dlchlorodlphenyl methane dilsocyanateJ

4,4'-diphenylmethane dllsocyanate, 2,4'-dlphenylmethane diisocyanate, dimer o~ dlphenylmethane diisocyanate, 4,4'-diphenyl dilsocyanate, cyclohexylene-1,4-di-9.

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10~5~5 isocyanate, and the llke. Of course lt ls obvlous that mixtures of two or more Or such dllsocyanates can be employed 1~ deslred and such ls o~ten common ln vlew o~ the ract that lsomeric mlxture~ o~ ~ald di-lsocyanates are normally formed during their commerclal productlon. Dlphenylmethane dllsocyanates, especially ; 4,4'-dlphenylmethane dilsocyanate, and mlxtures thereo~
are preferred.
Any s~ltable organlc di~unctlonal chaln extending agent havlng two actlve hydrogen contalnlng groups reactlve wlth lsocyanate groups can be used ln accordance wlth the process of thls lnventlon. Such agents are conventlonal and are well known in the art as witnessed e.g. by U.S. Patents 2,620,516; 2,621,166;
2,729,618 and 3,214,411. Illustratlve examples o~ such dlfunctlonal chain extenders lnclude dlhydroxy compounds such as ethylene glycol, propylene glycol, butylene ~ -glycol, 1,4-butanedlol, butenedlol, butynedlol, -xylylene glycols, amylene glycols, l,~-phenylene-bis-~ hydroxy ethyl ether, 1,3-phenylene-bls ~ hydroxy ethyl ether, bls-(hydroxy methyl-cyclohexane), 1,6-hexanedlol, thiodlglycol and the llke; dlamines lncludlng ethylene diamine, propylene dlamine, cyclo-hexylene dlamlne, phenylene dlamine, tolylene dlamine, xylylene diamine, 3,3'-dlchlorobenzldlne, 3,3'-di-nltrobenzldlne, and the llke; and alkanolamlnes such as ethanolamlne, aminopropyl alcohol, 2,2-dimethyl propanolamlne, 3-amlnocyclohexyl alcohol, p-amino-benzyl alcohol, and the llke. Pre~erably the chain extender ls a stralght chaln saturated aliphatlc glycol cont~lnlng from 2 to 10 carbon atoms, especlally 1,4-butanedlol.
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The lnter~aclal agent~ employed ln the practlceOr the novel proce4s or thls lnvention are organlc polymers whlch have a reduced v18c081ty value Or from about 0.01 to about 5.0 and hlgher, sald lnterfaclal agent belng characterlæed (1) by a solvatable con-` stituent (1) whlch ls solvatable ln inert, normally-llquid,saturated hydrocarbons, (il) which ls essentially lncompatlble wlth the sort segment Or the partlculate polymeric polyurethane product, and (lil) whlch has an average molecular welght Or up to 500,000 and (2) by a non-solvatable constltuent (1) which ls non-solvat-able with æuch lnert, normally-liquldJ saturated, hydrocarbon~ (11) whlch ls compatlble wlth the . of~
sort segment/sald partlculate polyurethane polymers, and (111) whlch has an average mo}ecular welght Or at least about 1000 and i8 at least about 0.05 to about 10 tlmes the average molecular welght o~ the solvatable con-stltuent.
The lnterfaclal agents, as lndlcated above, are organlc polymers and most desirably lnclude block and gra~t copolymers whlch are belleved to become assoclated lntegrally wlth the partlculate polymerlc polyurethane product primarlly through the non-solvatable constitu~nt Or the lnterraclal agent. The "block or gra~t" copolymers, as used hereln, have the structure normally implled by such term, that ls, they comprlse copolymers in which the constltuents are ; present not as random monomer unlts but as a chain Or one polymer to whlch is attached one or more chalns of another polymer. The chalns Or polymer may comprlse 11 .

, ~Q~5285 9170 one monomer or a random arrangement of two or more monomers.
The interfacial agents may be preformed and then added to the reaction medlum, and any catalyst normally employed in the formatlon of the polyurethane polymers may be used in the novel process.
As indlcated above, the novel process is efrected ln the presence Or an inert organic vehlcle in whlch the dihydroxy-containlng compound, chain ~ 10 extendlng agent and interracial agent are dlsperslble j and in which the resulting partlculate polyurethane polymer is lnsoluble. Any relatlvely non-polar,inert, organlc vehicle which ls a llquld under the polymeri-zation reaction conditions may be employed in the novel process. Illustrative inert organlc vehicles whlch are contemplated are the normally-llquld hydro-; carbons including the acyclic and alicyclic saturated ~ hydrocarbons such as pentane, hexane, heptane, octane, - dodecane, cyclopentane, cyclohexane, cycloheptane, the alkyl-substituted cycloalkanes, decahydronaphthalene, varlous normally-liquid petroleum hydrocarbon ~ractions, various high boiling mineral oils, and the llke.
Mixtures of lnert organic vehicles can be employed, and mixtur~s of the a~oresaid illustrated organlc vehicles with a small amount Or an aromatlc liquid may be tolerated. Preferably the vehicle is a saturated aliphatic hydrocarbon, especially decane.
Once having determined the nature and choice Or the particulate thermoplastic polyurethane polymer and inert organlc vehlcle ln the light of the fore-12, . . -:. , . : . .

~04~28S
golng teachlngs, one can select the lnterfacial agent havlng the sultable constltuent~.
The solvatable constltuent of the lnterfaclal agent may range ln slze from that Or a conventional surfactant up to an average molecular weight of about one mlllion. While the specirlc amount ls not narrowly critlcal lt should be at least æu~ficient to insure solublllty of that segment of the lnterfacial agent in the polymerlzation medlum, i.e. the inert organlc vehicle employed. Thus lt ls readily appreciated that at low average molecular weights relatlvely large proportlons of solvatable constituents may be required and even then the disperslon of the inter~acial agent may be somewhat coarse. Consequently, it is generally deslrable that the solvatable constituents have an average molecular welght o~ at least about lO00, pre~erably ~rom about 5000 to ~00,000.
Thus the nature o~ the solvatable constituent ~ -o~ the lnterfaclal agent is governed by the nature o~
the lnert organlc vehlcle. In contrast to the dispersed dlhydroxy contalnlng compound, the solvatable con-stltuent should be Or a slmllar degree of polarity as the inert organlc vehlcle. This ls relatlvely easy to determine slnce lf, for example, a normally-liquld saturated aliphatic hydrocarbon ls chosen as the organlc vehlcle, then the solvatable constltuent can comprlse a saturated allphatlc hydrocarbon chaln.
The non-solvatable constltuent of the inter-faclal agent most generally has an average molecular weight of at least about 1000 and ls at least about 0.05 to about 10 tlmes the total molecular welght o~
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the solvatable constituents. Desirably the non-solvatable constltuent has an average molecular weight of at least about 2500 and ls at least about 0.1 to about

5.0 times the total molecular weight of the solvatable constltuen*s. As lndlcated previously, the non-sol-vatable constituent (as well as the particulate poly-urethane polymer) must be essentially insoluble ln the inert organic vehicle and compatible with the so~t segment of the particulate polyurethane polymer product.
Most polymers, however, have only llmited compatiblllty with other polymers, and conse~uently it ls generally pre~erred that the non-solvatable constituent be o~ the same materlal as the soft segment o~ the particulate polyurethane polymer or closely related thereto. For example, while hlghly compatible polycaprolactone has been ~ound to be the preferred non-solvatable con-stituent of the lnterfa¢lal agents, especlally for dlhydroxy eyclic ester startlng materials, sald capro-lactone is not compatible with polytetramethylene glycol starting materlals and such lncompatlbillty negates the produ¢tion o~ the desired particulate polymer product. Thus, 1~ polytetramethylene glycol were employed as the startlng materlal it would pre~erably requlre an interfacial agent based on poly-tetramethylene glycol.
A simple test o~ compatibility lnvolves mixing the polymers of interest (about 50/5-0 weight per cent blend/and heatlng the blend to the temperature o~ the reactlon. The compatibility (solubility) of the blend is then observed a~ter thorough mixing. Compatible systems wlll become clear and form one phase under these 14.

. ' '~ ' ` ' ' '1' " ' ' ' . ', ' ' , . , ' :,' lO~SZ85 conditions, whlle incompatible systems remain cloudy and form two dl8tin¢t pha~es.
Preformed block or graft copolymeric inter-~acial agents can be prepared by conventional methodS
whlch are well-documented ln the llterature.
In general, the interfaclal agents contemplated ln the present lnventlon have reduced vlscoslty values of at least about 0.01, most deslrably from about 0.05 to about 5, and preferably rrom about 0.1 to about 3Ø
As ls well known ln the art, reduced viscoslty value ls a measure or lndlcatlon of the molecular weight of polymers. Consequently, the molecular weights of the lnter~aclal agents and the polyurethane polymer products can be lndlcated by thelr reduced vlscosity values.
The expresslon "reduced vlscosity" is a value obtained by dlvldlng the speclflc viscosity by the concentration of polymer (lnter~acial agent or polyurethane polymer) in the solutlon, the concentration belng measured in grams Or polymer per lO0 milllliters Or solvent. The speclrlc vlscoslty ls obtained by dlvldlng the dl~ference between the vlscosity of the solutlon and the vlscoslty of the solvent by the vlscoslty of the solvent. Unless otherwlse noted, the reduced viscosity values hereln referred to are measured at a concentratlon of 0.2 gram of polymer ln lO0 mllllliters Or solvent ~e.g., cyclohexanone, benzene, ¢hloroform, toluene, dimethyl~ormamide, or other common organic solvents) at 30C.
Illustrative classes of the interfacial agents that can be employed in the practice of thls lnventlon lnclude the block copolymers o~
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C6-C30 alkyl ~,~ -alkenoate and vlnyl halide, the block copolymer~ o~ C6-C30 alky ~ ,~ -alkenoate and a polyoxyalkylene gly¢ol~ the block copolymers Or C6-C30 alkyl ~,~ -alkenoate and a cycllc ester and the graft copolymers of C6-C3o alky ~ , ~ -alkenoate, a vinyl monomer and a cycllc ester.
Illustrative examples o~ such monomerlc alkenoates that may be used to make up the solvatable constltuent o~ the inter~acial agents of this lnvention are n-hexyl acrylate, octyl acrylate, lsodecyl acrylate, dodecyl crotonate, lsodecyl methacrylate, vinyl stearate, myrlsty} methacrylate, stearyl methacrylate, stearyl 2-hexenoate, lauryl methacrylate, pent~cosyl meth-acrylate, and the like, lncludlng mixtures o~ such acryIates and copolymers Or such acrylates, e.g. the ; copolymer of n-hexyl acrylate and lsodecyl acrylate.
As polnted out above, lt ls preferred that the alkyl chains of any speclfic alk~onoate employed be long enough to lnsure solublllty Or that segment of the lnterfaclal agent ln the polymerlzatlon medium ak the deslred rea¢tion temperature. The pre~erred alkenoates are lauryl methacrylate, lsodecyl acrylate and the copolymer of n-hexyl acrylate and lsodecyl acrylate.
Illustratlve examples Or such vinyl halldes ;-that may be used to make up the non-solvatable constituent of the blocked alkenoate/vlnyl hallde copolymer lnterfacial agents ln¢lude vinyl chlorlde, vinyl bromlde, vlnyl lodlde, vlnyl fluorlde, allyl ¢hlorlde, and the like, especlally preferred is vlnyl chlorlde.
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., . . , ~ -9170 - c ~045285 Illustrative examples of such polyoxyalkylene glycols that may be used to make up the non-solvatable constltuent o~ the block alkenoate/polyoxyalkylene glycol copolymer lnterfacial agents lnclude those .
glycol compounds including polytetramethylene glycol mentloned above.
The gra~t alkenoate, vinyl monomer, cycllc ester copolymer lnterfacial agents can be those pre-pared by elther Or two conventlonal methods. For example, such gra~t copolymers can be prepared by co-polymerlzlng ln solutlon the alkenoate monomer wlth the vlnyl monomer followed by rurther polymerization with the cyclic ester as disclosed in Belgium Patent 778,473 or those prepared by reactlng the vinyl monomer with the cyclic ester and then copolymerlzing ln solutlon the vlnyl monomer terminated cyclic ester polymer wlth the alkenoate monomer.
Illustratlve examples o~ such vlnyl monomers that may be used to help make up the graft copolymer ?o lnter~aclal agents are those of the general formula ~, .
H2 C=CCOR ' R
whereln 8 can be hydrogen or an alkyl radlcal having ~rom 1 to 3 carbon atoms and R' can be ~OCnH2nOH, CnH2nNH2' ~NHCnH2nH~ ~NHCnH2nNH2, -ocnH2nNHRlI or ~NHCnH2nNHR " where n has a value of 1 to 5 or hlgher and R" is an alkyl radical of 1 to 10 carbon atoms.
Pre~erably such vinyl monomers comprise rrom about 0.3 mo~e per cent to about 10 mole per cent of the ; gra~t copolymer. Suitable vlnyl monomers that may be ;`

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mentloned are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate J 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylateJ 5-hydroxypentyl acrylate, 2-hydroxyethyl : ethacrylate, aminomethyl acrylate, 2-aminoethyl acrylate, 2-amlnoethyl methacrylateJ 2-(N-methylamlno)ethyl acrylate, 2-(N-methylamino)propyl acrylate, 2-(~-butylamino)ethyl methacrylate, 5-(N-methylamino)pentyl acrylate, 2-(N-decylamino)ethyl acrylate, N-(2-hydroxy-propyl)acrylamlde, N-(aminomethyl)acrylamide, 2-(N-methylamlno)ethyl acrylate, 2-(N-ethylaminopropyl) acrylamide, and the llke. The prererred vinyl monomers are the hydroxyalkyl acrylates and hydroxyalkyl meth-acrylates.
Illustrative examples Or the cyclic ester monomers that can be employed as the non-solvatable constltuent Or the lnterracial agents of this invention are lactones and o~a-lactones whlch may be represented by the ~ormula O
"
I C- 0 , -~
(R~C~R)x (~-C-R)y wherein each R taken lndlvidually can be hydrogen or an :
alkyl radical and whereln not more than three of sald R groups can be alkyl, z can be zero or 1J X and y are lntegers having a value Or 1 to 4, when z is zero the sum of x + y is 4 to 7 and when z ls 1 the sum Or x + y + z is rrom 4 to 7. Suitable cyclic esters that may be mentloned are deta-valerolactone, epsilon-caprolactone, zeta-enantholactone, eta-caprylolactone, monomethyl-deta-valerolactone, monomethyl-epsllon- -18.

lOgS28S
caprolactone~ dimethyl-deta-valerolactone, triethyl-deta-valerolactone, 1,4-dloxane-2-one, dlmethyl-1/4-dloxane-2-one, and the llke. The pre~erred cycllc ester monomers are the caprolactones, especially epsllon-caprolactone.
The most preferred o~ all the lnter~acial agents that can be employed ln the practlce of this lnventlon are the graft copolymers of C6-C30~ , ~ -alkenoate and vinyl monomer termlnated cycllc ester.
These graft copolymers can be conveniently prepared by conventlonal process procedures well known ln the art such as by reactlng the cyclic ester wlth the vinyl monomer to form a vlnyl monomer terminated cyclic ester whlch 18 then copolymerlzed ln solutlon wlth the alkenoate to produce the de~lred gra~t copolymer. For ~ example, the process may be lllustrated by the following ,~ formula equatlons:

(R2C)x -- C = O R O
I , 11 , .
O + CH2 = C-C-X-H >
(O)z (CR2)y R O O R O

CH2 = C-c-xfc(cR2)xto~z(cR2)y-o~H + CH2 = C-C-OR"' R R O O
. ..
H2-c)~cH2-ctc-xfc-(cR2)x~otz(cR2)y-o~H .
O = C-O-R"' where R, x, y and z are the same as de~lned above, and 19 .

, .
.. . . ...
., - : . . - ~ .

1045~85 X 1s CnH2n~~ ~Cn~2nNH~~ -NHCnH2nO-, -NHCnH2 NH-, ~nH2nN~ or -NHCnH2nNR '- where n and R'l are the same as derlned above and R'll i8 an alkyl ~adlcal o~
~rom 6 to 30 carbon atoms. The polymerization reactions are preferably carried out ln the presence of catalysts or lnitlators which are well known in the art, such as tln catalysts, peroxide catalysts, and the like.
Stannous octoate is the preferred catalyst for the cycllc ester-vlnyl monomer reactlon, while dlbenzoyl peroxlde ls preferred for the polymerlzation rea¢tion wlth the alkenoate monomer. The polymerlzatlon reactlons may be conducted at temperature from about ;I~ 40C to 250C or higher, pre~erably about 150C and at - -'! subatmospherlc, atmosPherlc or super atmospheric pressures. Such polymerizatlons can be carried out in the absence or presence of an inert solvent although it 18 generally preferred to employ an inert solvent such as an aromatic hydrocarbon e.g. benzene, toluene, and the llke, for the graft polymerization reactlon. The reactlon times wlll vary depending upon the part~cular reactant~, catalyst, pressure, temperature, slze of batch and such other obvlous variables. ~hese conditlons are known to those famlllar with such polymerization technology and such condltlons can easlly be selected or determined in order to produce the deslred graft copolymer. Of course lt ls also to be understood that lndivldual monomer reactants as well as mlxtures of such reactants can be employed.
Examples of such speclfic block alkenoate/
vlnyl hallde copolymers that may be mentioned are the 20.

,~, j . , ~04S ~ S 9170 block copolymers o~ lauryl methacrylate and vinyl chlorlde; of vlnyl stearate and vlnyl chlorlde; of myristyl methacrylate and vinyl chloride; of stearyl methacrylate and vlnyl chlorlde; o~ stearyl 2- ;
hexenoate and vinyl fluoride; of octyl acrylate and vinyl chlorlde; of pentacosyl methacrylate and vinyl chlorlde; o~ lsodecyl acrylate and vlnyl chloride; of a copolymer Or n-hexyl acrylate (77.5%) - lsode¢yl acrylate (22.5%) and vinyl chlorlde; and the like.
Preferably such copolymers are the block copolymers Or C6-C30 alkyl ~, ~ -alkenoate and vinyl chloridej especlally the block copolymer of lauryl methacrylate and vlnyl chlorlde.
Examples of such speclfic block alkenoate/
` polyoxyalkylene glycol copolymers that may be ` mentloned are the block copolymers of lauryl meth-acrylate and polytetramethylene glycol, of isodecyl acrylate and polytetramethylene glycol, of isodecyl methacrylate and polytetramethylene glycol; of lso-decyl methacrylate and polytetramethylene glycol; of lsodecyl acrylate and polyoxypropylene glycol, and the llke. Preferably such copolymers are the block p y r Of C6 C30 alkyl ~, ~ -alkenoate and poly-tetramethylene glycol, said glycol havlng been derlved conventlonally from tetrahydrofuran.
Examples of such speclfic block alkenoate/
cyclic ester copolymers that may be mentloned are the block copolymers o~ poly (vlnyl sterate) and poly (epsilon-caprolactone); of poly (lauryl methacrylate) and poly (epsllon-caprolactone); of poly (stearyl ` 21.

,~
;~ . - ..... , .
- ~ .. . .. .

~170 ; methacrylate) and poly (eta-caprolactone); o~ poly (lsodecyl acrylate) and poly (epsllon-caprolactone);
of poly (myrlstyl methacrylate) and poly (delta-valerolactone); of poly (stearyl methacrylate) and poly (zeta-entholactone); of poly (stearyl 2-hexenoate) and poly (etacaprylolactone); of poly (octyl acrylate) and poly (methyl-delta-valerolactone);
of poly (lauryl methacrylate) and poly (methyl-epsilon-caprolactone); o~ poly (isodecyl methacrylate) and poly (dimethyl-epsllon-caprolactone); o~ poly (dodecyl crotonate) and poly (epsilon-caprolactone); Or poly (n-hexyl acrylate (77.5%)-lsodecyl acrylate ~22.5%) copolymer) and poly (epsilon-caprolactone); o~ poly (pentacosyl methacrylate) and poly (methyl-deta-- valerolactone); o~ poly (stearyl methacrylate) and poly (2-keto-lj4 dioxane); and the like. Preferably such copolymers are those o~ C6-C3o alky ~ , alkenoate and caprolactone, especially epsilon-t caprolactone, the most pre~erred being the copolymer -~
20 o~ poly (n-hexyl acrylate (77.5%)-isodecyl acrylate (22.5%) copolymer) and the poly (epsllon-caprolactone).
Examples of such specl~ic gra~t alkenoate-vlnyl monomer/cycllc ester copolymers that may be mentloned are the gra~t copolymers o~ poly (vlnyl stearate/2-hydroxyethyl methacrylate) and epsllon-caprolactone; Or poly (lauryl methacrylate/2-hydroxy-propyl methacrylate) and epsllon-caprolactone; of poly (stearyl methacrylate/2-hydroxyethyl acrylate) and eta-caprolactone; of poly (lsodecyl acrylate/
30 2-hydroxyethyl methacrylate) and epsllon-caprolactone;

22.

. .

of poly ( lsodecyl acrylate/2-hydroxyethyl acrylate) and epsilon-caprolactone; of poly (isodecyl meth-acrylate/2-hydroxyethyl acrylate) and epsllon-caprolactone; of poly (isodecyl methacrylate/2-hydroxy-ethyl methacrylate) and epsilon caprolactone; o~ poly-(myrlstyl methacrylate/hydroxymethyl acrylate) and deta-valerolactone; of poly (stearyl 2-hexenoate/2-hydroxyethyl acrylate) and zeta-entholactone); o~
poly (octyl acrylolate/2-~mlnoethyl acrylate) and eta-caprylolactone; of poly (lauryl methacrylate/2-(N-methylamlno) ethyl acrylate) and methyl-epsilon- ~ ;~
caprolactone; of poly (dodecyl crotonate/2-hydroxy propyl acrylate) and dimethyl-epsilon-caprolactone; o~
poly (pentacosyl methacrylate/2-amlnopropyl acrylate) and methyldelta-valerolactone; of poly (stearyl meth-acrylate/5-hydroxypentyl methacrylate) and epsllon-caprolactone; of poly (lsodecyl acrylate/2-hydroxyethyl ; methacrylate) and 2-keto-1,4-dioxane; and the like.
PrePerably such copolymers are those of C6-C30 alkyl , 20 ~ , ~ alkenoate-hydroxyalkyl acrylate or hydroxyalkyl - :
methacrylate and caprolactone, especlally the copoly-mers oP poly (lsodecyl acrylate or methacrylate/2-hydroxyethyl acrylate or methacrylate) and epsllon-caprolactone.
Examples of such speclflc graft alkenoate and vinyl monomer termlnated poly-cyclic ester co-polymers that may be mentloned are the ~raft copolymers of vlnyl stearate and 2-hydroxyethyl methacrylate terminated poly-epsilon-caprolactone; of lauryl meth-acrylate and 2-hydroxypropyl methacrylate terminated poly-epsilon-caprolactone; oP stearyl methacrylate 23.

`~~ 9170 ~04S285 and 2-hydroxyethyl acrylate termlnated poly-eta-caprolactone; Or isodecyl acrylate and 2-hydroxy-ethyl methacrylate terminated poly-ep~ilon-caprolactone;
Or 160decyl acrylate and 2-hydroxyethyl acrylate termlnated poly-epsllon-caprolactone; Or isodecyl methacrylate and 2-hydroxyethyl methacrylate termlnated poly-epsllon-caprolactone; of isodecyl methacrylate and 2-hydroxyethyl acrylate terminated poly-epsllon-caprolactone; of myrlstyl methacrylate and hydroxy-methyl acrylate terminated poly-delta-valerolactone;
Or stearyl 2-hexenoate and 2-hydroxyethyl acrylate termlnated poly-zeta-entholactone; of octyl acrylate and 2-aminoethyl acrylate termlnated poly-eta-capro-; lactone; Or lauryl methacrylate and 2-(N-methylamine) ethyl acrylate terminated poly-(methyl-epsllon-capro-lactone); Or dodecyl crotonate and 2-hydroxypropyl acrylate termlnated poly (dlmethyl-epsllon-capro- ~-lactone); Or pentacosyl methacrylate and 2-amlnopropyl acrylate termlnated poly (methyl-deta-valerolactone);
o~ stearyl methacrylate and 5-hydroxypentyl meth-acrylate terminated poly-epsllon-caprolactone; Or lsodecyl acrylate and 2-hydroxyethyl methacrylate terminated poly(2-keto-~,4-dloxane); and the llke.
Prererably such copolymers are those of C6-C30 alkyl , ~ a~kenoate and hydroxyethyl acrylate or hydroxy-ethyl methacrylate terminated polycaprolactone, especially the grart copolymers Or lsodecyl acrylate or methacrylate and 2-hydroxyethyl acrylate or methacrylate terminated poly-epsilon-caprolactone.

24.

.
;: :

~-- 9170 ~04SZ85 Of course lt ls to be understood that the lnterfacial agen~s may be used in dry powder form or in solution ~orm and that any suitable inert organic solvent may be employed as a carrier ~or the inter-~aclal agent to ~acilitate handling i~ desired. For example, slnce inter~aclal agents containing cyclic esters as the non-solvatable constltu~nt are normally prepared in solution form using an aromatlc hydro-carbon solvent e.g. benzene, toluene and the like, lt is generally pre~erred to employ such inter~aclal agents in the solution ~orm in whlch they are made. The amount o~ solvent employed ls not narrowly critical although lt ls obvlous that lt should not be employed ln such a quantlty as to be detrimental to the production of the desired particulate thermoplastlc polyurethane product.
Thus, lt ls pre~erred that the solvent not be present ln an ~mount greater than 50 per cent by weight of the total dlsperslon medla. It ls normally preferred to employ graft copolymers of alkenoate, vlnyl monomer and cycllc ester ln a solvent solutlon ~orm contalnlng about 50 per cent by welght Or the graft copolymer.
It ls of course obvious that to lncrease the - of rate of reactlon/the novel process o~ thls lnventlon any catalyst or mlxtures thereof sultable ror the productlon of thermoplastlc polyurethane polymers çan be employed. Such catalysts are well known ln the art, such as tertlary amlnes and metal contalning catalysts.
Illustratlve examples of tertlary amlne catalysts lnclude N,N-dlmethylethanolamlne, trl-ethanolamlne, trllsopropanolamlne, N-methyldi-ethanolamlne, N-ethyldlethanolamlne, trlethylamlne, 25.

: , ~ , .- . - ,. : , . ' ,~ , ' :

i045Z85 tributylamine J trloctylamlne, NJ N~ N I ~ N I -tetra-methylenediamine, N,N,N',N'-tetramethyl-1,3-butane diamlne, bls(2-dlmethylamlnoethyl)ether, hexadecyldl-methylamine, N,N-dimethylbenzylamine, trimethylamlne, N,N-dimethyl-2-(2-dimethylaminoethoxy) ethylamine, trlethylenedlamlne (i.e., 1,4-dlazabicyclo~2.2.2]
octane), N-methylmorpholine, oxyalkylene adducts of the amlno groups Or primary and secondary amines, and other such amlne catalysts whlch are well known in the art.
Such conven~ional metal catalysts include both lnorganlc metal ¢ompounds and metal compounds whlch contaln organic groups. Partlcularly userul catalysts are the organo-tin compounds, such as stannous acylates and the dlalkyl tln salts o~ -carboxyllc aclds. Illustratlve examples as such catalysts lnclude stannous acetate, stannous octoate, stannous oleate, dlbutyltln dlacetate, dibutyltin dilaurate, dlbutyltln maleate, dllauryltln dlacetate, dioctyltln dlacetate, and the llke. Especlally pre-rerred catalysts are stannous octoate and dlbutyltin dllaurate.~
or course lt ls ~nderstood that when employed the amount Or catalyst need only be a catalytic amount and ln general, the partlcular catalyst employed, the nature o~ the startlng materials, and the llke, wlll largely determine the optimum catalyst concentratlon. Normally catalyst concentratlons o~
~rom about 0.001 welght per cent to about 0.5 welght per cent based on the starting materials present in 26.

`,, . . ' , , , ' ~

~045Z85 the reaction medlum will be sufflclent ~or most purposes although hlgher or lower amounts may be employed if desired. Generally a catalyst concentra-tion of rrom about 0.02 to about 0.1 welght per cent i5 pre~erred.
The concentratlon o~ the inter~aclal agent can vary from about 0.1 welght per cent, to about 10 welght per cent, and higher, based on the total weight o~ the starting materials. A practical concentration is ~rom about 1.5 to about 5.0 welght per cent of lnterfac~al agent wlth about 3 welght per cent belng pre~erred.
The novel polymerization reaction of this invention can be conducted over a wide temperature --~ range such as from about 60C to about 180C with about 140C being the most prererred temperature.
The optlmum temperature to employ may, of course, be slgnl~lcantly influenced by the stablllty of the resultlng polymeric product and the boillng polnt o~
the lnert organlc vehicle.
The novel process o~ thls lnventlon is .
conducted ~or a period o~ tlme su~flcient to produce the partlculate polymerlc product. 0~ course, the reactlon tlme wlll vary dependlng upon the operatlve temperature, the nature of the startlng materlals, lnterfaclal agent, and catalyst i~ employed, the choice o~ the inert organic vehicle, and other obvlous ~actors. The reactlon time can vary ~rom several mlnutes to several hours, e.g., up to 24 hours, and more, dependlng on the varlables lllustrated above.
The most deslrable operatlve condltions can easily be 27, .
.. . . .
,: . . .

-arrived at by routine experlments to achieve a practical and commercially acceptable reaction rate.
Pre~erably the polymerization reactlon is ef~ected in the llquld phase in an essentially non-aqueous reaction medium. It is desirable also to ef~ect the polymerizatlon reactlon under an lnert atmosphere, e.g., nltrogen and pressure does not appear to be a critlcal ~actor.
Any suitable technique can be employed in the production o~ the thermoplastlc polyurethane poly-mers of the lnstant invention, such as variations lnprocess conditions and manlpulative steps known in the art. Conventional equlpment and material generally used ln the art can also be employed. The order of addltion o~ the dihydroxy containing compound, dl-lsocyanate, chaln extendlng agent, lnter~acial agent, lnorganlc vehicle and catalyst to the reactlon zone does not appear to be critical however lt ls obviously generally preferred to avoid premature reactlon between the dilsocyanate and the other ingredlents. A
convenient method generally employed ls to add the dihydroxy containlng compound and the ~nain extendlng agent to the lnert organic vehicle (medium) and disperse them therein at an approprlate elevated temperature, e.g. 60C to 140C, uslng the inter-faclal agent. The catalyst and dilsocyanate are then added to the dlspersed mlxture and the polymerizatlon allowed to proceed wlth stirring for a given period o~
tlme at the prescribed reactlon temperature. A sus-penslon of particulate thermoplastlc polyurethane polymer is obtalned whlch is allowed to cool to amblent temperature. The solid polyurethane partlcles obtained 28.

~045285 settle rapldly but are readily redlspersible ln the lnert reactlon medium. Sald partlcles are easlly lsolated by any obvious slmple procedure, e.g.
filtration. Residual hydrocarbon and unreacted materlals can be removed lf desired by any conventlonal technlque such as washlng, air drying and heating under reduced pressure.
~ he relatlve amounts of the dihydroxy containing compound, the chaln extendlng agent and the organlc dilsocyanate employed ln accordance with the above descrlbed process for producing particulate thermoplastlc polyurethane polymers ln accordance wlth thls invention are not nanrowly critical. The relative amounts of these three components can be the same amounts requlred to produce conventional thermoplastic ~-- polyurethane polymers and such relative amounts are well known in the art. For example in theory one NCO
group is eqùlvalent to one Or the functlonal groups, e.g. OH, o~ the dlhydroxy containlng compound or the chaln extendlng agents. Thus the amount of dllsocyanate employed ls dependent upon the amount of the dlhydroxy containlng compound and the chaln extending agent and ` ln order to obtaln a maximum degree of polymerization and efrlciency lt is preferred that the amount Or dllsocyanate be equlvalent or as near to equivalent as possible to the dlhydroxy containing compound and the chaln extending agent ~o that there are essentially no ~ree lsocyanate and functlonal groups, e.g. OH, remalnlng ln the reactlon product. Of course lower or hlgher amounts of dllsocyanate may be employed, but such ls not generally preferred. Illustratlve examples 29, , . . .

` 9170 ~ 04S285 of the more preferred molar ratlos of dihydroxy contalnlng compound, dilsocyanate and chaln extending agent are 1:2:1, 1:3:2 and 1:4:3.
The amount Or inert organlc vehicle employed ln the novel process can vary over a wlde range.
Practical and economlc conslderation, however, will dictate the quantlty o~ vehlcle that is utilized.
Preferably the amount of inert organic vehicle employed will be such that the particulate thermoplastic poly- ;
urethane polymeric product wlll comprise from about ~lve welght per cent solids to about 80 weight per cent in the reactlon product mlxture. While lower or higher amounts of sollds can be present, at the lower end o~ the above range one has a very fluid mixture whereas at the higher end of said range the mixture ~-becomes dlf~icult to stir. Most preferred is a reactlon mixture contalnlng about 50 welght per cent so~llds o~ the partlculate thermoplastic polymerlc product.
~a Unllke prior art processes ln whlch the resultlng thermoplastlc polyurethane polymers often-.
times end up as a monolithlc mass, the practice o~ the present process results ln the production of novel thermoplastlc polyurethane polymers which are obtalned as a dispersion of dlscrete partlcles o~ relatively uniform slze in the polymerlzatlon reactlon medium.
The process economles o~ obtainlng polymer in discrete particle form ln an inert organic vehicle ln contrast .
to a monolithic mass are obvious both with respect to the novel Dolymerizatlon process as well as in the handling and utlllzatlon of the novel polymer product 30, .

obtained therefrom. For example, the practice of the lnstant process results ln excelle~t process control of the polymerlzation reaction and the product deslred.
In terms of powder coatlngs the lnstant process of this invention also avolds pollution and toxlclty problems that may be present wlth varlous different types of solvent based ~ystems The per cent converslon to the particulate polymer ls hlgh and recovery ~rom the reactlon product mlxture ls relatlvely slmple.
The novel thermoplastlc polyurethane polymer ls obtalned ln dlscrete, ~ree-~lowlng, non-agglomeratlve partlcle form ln the lnert organic vehlcle and ln high purlty. As lntlmated previously lt ls belleved that the lnterraclal agent ls assoclated lntegrally wlth the 1 . ..
partlculate polymer product prlmarlly through the non-solvatable or anchorlng constituent o~ sald agent.
Thus the powdered partlculate thermoplastic polymer product consisting essentially o~ spherlcal partlcles generally on the order o~ about 10 to about 300 microns ln dlameter, but whlc~ may be sa~ller or larger, can easlly be recovered ~rom the reactlon mlxture by simple ~lltratlon or decantation, ~ollowed by drylng under ; reduced pressure and m~ld temperatures, e.g. about 50C.
The partlculate polymer is also readlly dispersible in inert normally liquid saturated hydrocarbons.
Sald thermoplastlc polyurethane polymers have a wide range o~ utllity already well known in the polyurethane elastomer art as witnessed by the above cited prlor art.
For exampleJ the products prepared in accordance with this inventlon are suitable ln all types of appllcatlons where an elastomerlc product is deslred such as in the 31.

10~5285 production o~ rubber shock mounts, gaskets, elastomeric rllaments ~or garments, llners for upholstery, sport-lng goods, e.g. basketballs, rootballsJ etc., and the like. One Or the obvlous advantages Or the lnstant lnventlon ls that the particulate polymer product o~
the present lnventlon doe~ not have to undergo further treatment be~ore lt can be utillzed ln appllcatlon technlques heretorore employed with other powdered - polymers such as, ~lame coatlng, heat substrate coatlngs, rotatlonal and ln3ection molding, calenderlng, powder blendlng with other polymers, slntered shaped artlcles and coatlngs, and the llke. The partlculate thermopla8tlc polyurethane polymers also lend them-selves to use as fllters and to Pluldlzed bed coatlngs and claddlngs, as well as to electrostatic coatlng .
;~ technlquee and the llke.
The ~ollowing examples are lllustratlve Or the present lnventlon and are not to be regarded as llmltative. It 18 to be understood that all parts, percentages and proporatlons re~erred to hereln and ln the appended clalms are by welght unless otherwlse lndlcated.
Example 1 396.o grams Or epsllon-caprolactone were charged to a 2 llter stirred flask and heated to 150C.
o~ 2-hydroxyethyl acrylate Then 4.0 grams/were added and the polymerlzatlon allowed to proceed Por 3 hours at`l50C. The hydroxyethyl acrylate termlnated poly-epsllon-caprolactone copolymer obtalned had a reduced vlscoslty o~ 0.25 dl./g.
measured as a solutlon Or 0.2 grams ln 100 ml. o~
benzene at 30C. Sald copolymer was cooled to about 110C. and dlluted wlth 800 grams o~ toluene. The temperature was malntalned at 100C.and a solutlon o~
0.0396 grams Or dlbenzoyl peroxide ln 396.o grams o~
lsodecyl acrylate was added dropwlse over a perlod o~
one hour. A~ter stlrrlng ~or an addltional two hours a toluene solvent solutlon contalning about 50 per cent by welght Or the graft lsodecyl acrylate/hydroxyethyl acrylate termlnated poly-ep~ilon-caprolactone copolymer lnterraclal agent was obtalned whlch was cooled and 10 bOttled.
Exam~le 2 A resln kettle was equipped wlth a stlrrer, thermometer and re~lux condenser. 126.2 grams of decane as the lnert organlc vehi~le, 96.72 grams (0.05 mole) o~ a dlethylene glycol lnitlated poly-epsllon-¢aprolactone polyol havlng an average molecular welght Or about 2,000 and a hydrox~ number Or about 56.1, 4.5 grams (0.05 mole) Or 1,4-butanedlol as a chaln extender, and 7.56 grams o~ the grart lsodecyl acrylate/hydroxyethyl acrylate terminated poly-epsllon-caprolactone copolymer lnterraclal agent solutlon o~
Example 1 were added wlth stlrrlng and heated to about 140C. Then 0.025 grams Or stannous octoate were added to the dlspersed mixture followed immedlately by 25.02 grams (0.1 mole) o~ MDI, a 4,4'-dlphenyl- ~ ~
methane dlisocyanate product of Mobay Chemlcal Company. ~ -Solld partlculate thermoplastlc polyurethane polymer started to form al~ost lmmedlately and the reaction was allowed to proceed for one hour at about 140C.
The reactlon product mlxture (about 50% total sollds) having the suspended partlculate polymer partlcles was 33.

.- :

~ 9170 ~045i~85 allowed to cool to room temperature whlle stirrlng and the solid product partlcle~ allowed to settle.
The decane was decanted, the product washed wlth hexane, rlltered and vacuum drled. There was obtained a rine, uniform particulate polymer o~ thermoplastlc polyurethane which was ~ree-rlowlng, non-agglomerative and readlly redisperslble in the decane. The yleld was essentlally 100 per cen~ and the powdered, particulate polymer product had a reduced viscosity o~ 0.97 dl./g. as measured on a solutlon of 0.2 grams ln 100 ml. of dimethylrormamide at 30C. A plaque was molded ~rom the essentially non-crossllnked partlculate thermoplastic polyurethane polymer product at 180C.
and a pressure o~ 4000 p~i. and the molded product was round to have a tensile strength of 5600 psl. and an elongatlon value o~ 725 per cent.
By way of comparison a thermoplastlc poly-urethane polymer was prepared ln the same manner, uslng the same ingredlents, amounts and condltlons, except that the decane and interraclal agent were omltted.
A plaque molded ~rom this conventlonally produced thermoplasti¢ polyurethane polymer at 180C. and a pressure o~ 4000 psl. exhibited a tensile strength of 5041 p8i. and an elongatlon value o~ 600 per cent.
Exam~l~
~ he procedure o~ Example 2 was repeat~d using 143 grams Or decane, 96.72 grams (0.05 mole~ of a diethylene glycol inltlated poly-epsllon-caprolactone polyol having an average molecular welght of about 2000 and a hydroxylnumber of about 56.1, 9.01 grams (0.1 mole) Or 1,4-butanediol, 8.59 grams o~ the grart 34.

~0 45 ~ 5 isodecyl acrylate/hydroxyethyl acrylate termlnated poly-epsilon-caprolactone copolymer lnterraclal agent solutlon Or Example 1, 0.03 grams of stannou~ octoate and 3~.54 grams (0.15 mole) of MDI. A ~lne, unlform partlculate polymer of thermoplastlc polyurethane ln a yleld Or about 100 per cent was obtained from the reactlon product mlxture (about 50 per cent total sollds). ~he powdered partlaulate polymer product obtalned was free-M owlng, non-agglomeratlve and readlly red1Rperslble ln the decane and had a reduced vls009ity 0~ 1.07 dl./g as measured on a solutlon of 0.2 grams ln 100 ml. o~ diemthylformamlde at 30C.
A plaque molded from the essentlally non-crosslinked particulate thermopla~tlc polyurethane polymer product ln the same manner as Example 2 exhlblted a tenslle stren~th of 6812 p8~. and an elongation value Or 536 per cent.
By way o~ comparison a thermoplastlc poly-urethane polymer wa~ prepared ln the same manner using the same lngredlents, amounts and condltlons, except that the decane and lnterfaclal agent were omltted. A
plaque molded from thls conventlonally produced thermo-plastlo polyurethane polymer at the same temperature and pre~sure as that for the above partlculate product exhlblted à tenslle strength o~ 6600 psl. and an elongatlon value o~ 587 per cent.
ExamDle 4 The prooedure of Example 2 was repeated uslng 160.3 gram~ Or docane, 96.72 grams (0.0~ mole) of a diethylene glycol ln~tiated poly-epsllon-caprolactone polyol ha~lng an average molecular welght of about .;: , .

~04SZ85 2000 and a hydroxylnumber o~ about 56.1, 13.52 grams (0.15 mole) of 1,4-butanedlol, 9.6 grams o~ the graft lsodecyl acrylate/hydroxyethyl acrylate termlnated poly-epsilon-caprolactone copolymer lnterraclal aeent solutlon of Example 1,0.032 gra~6 of stannous octoate and 50.05 grams (0.2 mole) of MDI. A ~lne, unl~orm partlculate polymer Or thermoplastic polyurethane ln a yleld o~ about 100 per cent was obtained ~rom the reactlon product mlxture (about 50% total solids).
The powdered, pa~tlculate polymer product obtalned was rree-~lowlng, non-agglomeratlve and readily redlsperslble in the decane and had a reduced viscosity o~ ~ dl./g.
as measured on a solution Or 0.2 grams in 100 ml. Or dlmethylrormamlde at 30C. A plaque molded from the essentlally non-cros~llnked partlculate thermoplastlc polymer product in the same manner as Example 2 exhlblted a tenslle strength Or 7566 psi. and an elongatlon value of 463 per cent.
By way o~ comparlson a thermoplastlc poly-urethane polymer was prepared ln the same manner uslng the same lngredlents, amounts and conditlons, except that the decane and lnterraclal agent were omltted.
A plaque molded ~rom thls conventlonally produced thermoplastlc polyurethane polymer at the same tempera-ture and pressure as that ror the above particulate product exhiblted a tenslle strength Or 7409 psi. and an elongatlon value Or 510 per cent.
Exam~le S
A r~sln kettle was equlpped with a stirrer, thermometer, and rerlux condensor. 170 grams Or decane, 105.33 grams (0.05 mole) Or a polyethyleneglycol/

36.

iO4S28S
adlpate copolymer havln3 an average molecular welght of about 2100 and a hydrox~ number Or about 56, 13.52 grams (0.15 mole) o~ 1l4-butanedlol, and 10.2 grams o~
the grarb lsodecyl acrylate/hydroxyethyl acrylate - termlnated poly-ep~ilon-caprolactone copolymer lnter-raclal agent solutlon o~ Example 1, were added wlth stlrrlng and heated to about 140C. Then 0.034 grams of stannous octoate ~ere added to the dlspersed mixture rollowed lmmediately by 50.05 grams to.2 mole) o~ MDI.
Solid partlculate thermoplastic polyurethane polymer ~tarted to rorm almost immediately and the reactlon was allowed to proceed to completion at about 140C. The reactlon product mlxture (about 50% total sollds) havlng the ~uspended partlculate polymer partlcles was allowed to cool to room temperature whlle stlrrlng and the solld product particles allowed to settle. ~he . - .
decane was decanted, the product washed with hexane, rlltered and vacuum dried. ~here was obtained a flne, . . .
unirDrm particulate polymer Or thermoplastl¢ polyurethane which was rree-rlowing, non-agglomeratlve and readlly redlsper6ible ln the decane.
Exa~le 6 The procedure Or Example 2 was repeated usln 163.7 grams Or decane, lOO.I5 grams (0.05 mole) Or a polyoxypropylene glycol polymer having an average molecular welght o~ about 2000 and a hydroxylnumber Or 54.7-57.5, 13.52 grams o~ (0.15 mole) Or 1,4-butanediol, 9.8 grams Or the grart isodecyl acrylate/hydroxyethyl acrylate terminated poly-epsllon-oaprolactone copolymer inter~a¢ial agent solutlon Or Example 1, 0.03 grams o~
stannous o¢toate and 50.05 gram~ (0.2 mole) of MDI.

, `
... . .

1045~ 9170 A flne, uni~orm particulate polymer of thermoplastlc polyurethane in a yleld o~ about 100 per cent was obtalned whlch could easlly be lsolated ~rom the reactlon product mlxture (about 50~ solids) by filtratlon. The lsolated powdered, partlculate polymer product obtained had a reduced vlscoslty o~
0.452 dl./g. as measured on a solution o~ 0.2 grams ln 100 ml. o~ dlmethyl ~ormamide at 30C.
Exam~le 7 The procedure o~ Example 2 was repeated uslng 127.0 grams Or decane, 88.9 grams (0.03 mole) ~r a polyoxypropylene glycol polymer havlng an average molecular weight o~ about 2000 and a hydroxyl number o~ 54.7 - 57.5 and containlng 20 weight per cent of ~inely dlvided polyacrylonitrile, 8.11 grams (0.09 mole) o~ 1,4-butanediol, 5.76 grams o~ the gra~t isodecyl-acrylate/hydroxyethylacrylate termlnated poly-epsilon-caprolactone copolymer lnter~aclal agent solutlon of Example 1, 0.019 grams Or stannous octoate and 30.03 grams (0.12 mole) o~ MDI. An orange powdered, partlculate polymer of thermoplastic polyurethane was readlly lsolated and obtained. A molded plaque produced ~rom the essentlally non-crossllnked pa~ticulate thermoplastlc polyurethane polymer product exhlblted a tenslle strength of 786 psl. and an elongation value o~ 199 per cent.
Exam~le 8 150 parts of acetone, 71.1 parts of vinyl chloride, 28.9 parts of lauryl methacrylate and 1.5 3o parts of benzoyl per~xlde were charged to an autoclave and heated to 51C. ~or 154 hours. The resulting 38.

~ .

slurry was washed thoroughly wlth isopropanol, centri-fuged and drled ~or 64 hours at 30C. and 2.0 mm. H~.
~here was obtalned a lauryl methacrylate/vinyl chlorlde copolymer lnter~alcal agent (about 90~ converslon) product.
Said lnterraclal agent was a dry whlte powder and had a reduced v16coslty o~ 0.29 dl./g. as measured on a solutlon Or 0.2 grams ln lO0 ml. o~ benzene at 30C.
Example ~
A resln kettle equlpped wlth a stlrrer, ther-mometer and rerlux condensor was charged wlth 200 grams (0.1 mole) o~ a dlethylene glycol lnitlated polyepsllon-caprola¢tone polyol havlng an average molecular welght o~
about 2000 and a hydrox~ number o~ about 56.1, 17.4 grams (0.1 mole) o~ l,lO-dlhydroxy n-de¢ane as a chaln extender, 401.1 grams Or an lnert organlc vehlcle mlxture consisting o~ about 70-75% saturated C6-C10 allphatlc hydrocarbons and 25-30~ C6-C10 aycloallphatlc hydrocarbons sald mlxture havlng a bolling polnt o~ 153-180C., 8.02 grams o~ the lauryl methacrylate/vlnyl chlorlde copolymer inter~acial agent Or Example 8 and 0.54 grams Or stannous octoate.
~he mlxture was heated to 90C. and 50.0 grams (0.2 mole) o~ MDI were added. Arter contlnuing the reactlon wlth stirrlng ~or 3 hours at 120C., the particulate powdered thermoplastlc polyurethane product was flltered ~rom the resultant reactlon mlxture (about 60% total sollds), washed with hexane and drled at room temperature.
The re5ultant ~ree-rlowlng, non-agglomeratlve partlculate thermoplastlc polymer product obtalned had a reduced viscosity Or 0.62 dl./g. as measured on a solutlon o~ 0.2 3 grams in 100 ml. o~ dlmethyl rormamide at 30& . A photo-mlcrograph Or the partlcles revealed them to be spheres 39.

' ' .

with a range Or 10 to 200 mlcrons. A molded plaque prepared rrom the partlculate thermoplastlc poly-urethane polymer product exhlblted a tenslle strength o~ 1185 psl. and an elongatlon value of 550 per cent.
Exam~le 10 A particulate thermoplastlc polyurethane polymer was obtalned as a 45 per cent total solids dispersion in heptane using the lauryl methacrylate/
vlnyl chlorlde copolymer lnter~aclal agent Or Example 8, heptane as the inert organlc vehlcle, stannous octoate, and as the ureathane ~ormlng reactants a diethylene glycol lnltlated poly-epQilon-caprolactone polyol hav~ng an average molecular welght o~ about 2000 and a -- hydroxyl number o~ about 56.1, MDI and 1,4-butanedlol ln a 1/4/3 mole ratlo, the polymerizatlon reactlon - belng conducted at 90C. The powdered partlculate thermoplastlc polyurethane polymer product evldenced no conglomeratlon Or partlcles and although the particles settled out rapldly when stirrlng was stopped, they could be r~adlly redlspersed ln the heptane.
Example 11 An inter~acial agent block copolymer Or poly(n-hexyl acrylate-lsodecyl acrylate copolymer) and poly-epsllon-caprolactone havlng an average molecular weight Or about 15000and a reduced vlscoslty Or 0.3 dl./g. as measured on a solutlon Or 0.2 grams ln 100 ml. o~ benzene at 30C. was prepared by transesterirying at 140-150C. ror 20 hours wlth stlrrlng 33.5 grams of a oopolymer Or n-hexyl acrylate (77.5%) and lsodecyl acrylate (22.5%) wlth 22.3 grams Or poly-epsllon-caprolactone ln the presence Or 0.04 grams o~ p-toluene 40.

l~SZ85 sulronlc acld.
Example 12 In a manner slmllar to the procedure of Example 2, a partlculate thermoplastlc polyurethane polymer was prepared using 126.2 grams o~ decane, 96.72 grams (0.05 mole) o~ a dlethylene glyco~ lnltlated poly-epsllon-caprolactone polyol having an average molecular welght o~ about 2000 and a hydrox~ number o~ about 56.1, 4.5 grams (0.05 mole) Or 1,4-butanediol, 25.02 grams (0.1 mole ) Or MDI, 3.78 grams o~ the block copolymer o~ poly(n-hexyl acrylate-isodecyl acrylate copolymer) and poly-epsllon-caprolactone lnter~aclal agent of Example 11 and 0.025 grams o~ stannous octoate. The reactlon waQ carrled out at 130C. for three hours wlth moderate stlrrlng. The resultant partlculate thermoplastic polyurethane polymer product settled rapldly ~rom the reactlon product mlxture (about 50%
total sollds), but could be readily redlspersed ln the decane. The supernatant decane liquld was decanted and the solld particles wa~hed wlth hexane and drled at room temperature. ~he resultant particulate thermoplastlc polyurethane polymer obtalned was a rree-flowlng powder Or spherlcal shape and had a partlcle slze of 20 to 200 mlcrons. The reduced vls¢oslty o~ the partlculate polymer product was 1.17 dl./g. as measured on a solutlon o~ 0.2 grams ln 100 ml. of dlmethyl ~ormamlde at 30C. A molded plaque produced ~rom the partlculate thermoplastlc polyurethane polymer product was clear and uncolored.

41.

, Example 13 The procedure of Example 12 was repeated uslng mlneral oil as the lnert organic vehicle. There was obtalned particulate thermoplastlc polyurethane polymer as a fine free-flowlng p~wder having a reduced ~lscoslty of 1.05 dl./g. as measured on a solutlon of 0.2 grams in 100 ml. of dimethyl formamide at 30C.
Various modiricatlons and variatlons o~ this inventlon wlll be obvlous to a worker skilled ln the art and it is to be understood that such modiflcations and varlations are to be included wlthln the purvlew of thls appllcatlon and the splrlt and scope of the appended claims.

,~ , ' ., ~:

42.

Claims (18)

WHAT IS CLAIMED IS:

1. A process for producing a particulate thermoplastic polyurethane polymer which comprises contacting and reacting (a) an organic dihydroxy containing polymer selected from the group consisting of poly-ether diols, polyester diols and polymer/diols;
(b) an organic difunctional chain extending agent having two active hydrogen atoms reactive with the isocyanate groups of the diisocyanate compound;
(c) an organic diisocyanate compound;
the polyurethane forming ingredients of (a), (b) and (c) being present in such an amount that the molar amount of (c) is essentially equivalent to the molar amount of (a)+(b) so that the polyurethane contains essentially no unreacted hydroxyl groups and isocyanate groups; and (d) from about 0.1 to about 10 weight percent, based on the weight of the particulate polymer product, of an organic polymeric interfacial agent, which has a reduced viscosity value of from about 0.01 to about 5; said interfacial agent being characterized (1) by a solvatable constituent (i) which is solvatable in inert normally liquid saturated hydrocarbons;
(ii) which is essentially incompatible with the soft segment of the particulate thermoplastic polyurethane polymer product, and (iii) which has an average molecular weight of up to about 500,000 and (2) by a non-solvatable 43.

constituent (i) which is non-solvatable with such inert normally liquid, saturated, hydrocarbons, (ii) which is compatible with the soft segment of the particulate thermoplastic polyurethane polymer product, and (iii) which has an average molecular weight of at least about 1000 and is at least about 0.05 to about 10 times the average molecular weight of the solvatable constituent;
and wherein the interfacial agent is selected from the group consisting of block copolymers of C6-C30 alkyl.alpha., .beta.-alkenoate and a cyclic ester, and the graft copolymers of C6-C30 alkyl .alpha.,.beta.-alkenoate, a vinyl monomer of the formula wherein R is hydrogen or an alkyl radical having from 1 to 3 carbon atoms, R' is a radical selected from the class consisting of -OCnH2nOH-, -OCnH2nNH2, -NHCnH2nOH, -NHCnH2nNH2, -OCnH2nNHR" and -NHCnH2nNHR" where n has a value of 1 to 5 and R" is an alkyl radical of 1 to 10 carbon atoms, and a cyclic ester;
(e) in the presence of an inert organic vehicle in which the ingredients of (a), (b) and (d) are dispersible and in which the particulate thermoplastic 44.

polyurethane polymer product is insoluble, the amount of said vehicle being such that the particulate thermo-plastic polyurethane polymer product will comprise from about 5 weight per cent solids to about 80 weight per cent solids in the reaction product mixture;
Said reaction being conducted under essentially anhydrous conditions and for a period of time sufficient to produce the particulate thermoplastic polyurethane polymer.

2. A process as defined in claim 1, wherein a catalytic amount of a catalyst for the production of the polyurethane product is also present.

3. A process as defined in claim 2, wherein the dihydroxy containing polymer is a polyoxyalkylene glycol, wherein the diisocyanate compound is an aromatic diisocyanate and wherein the chain extending agent is a straight chain saturated aliphatic glycol containing from 2 to 10 carbon atoms.

4. A process as defined in claim 2, wherein the dihydroxy containing polymer is a polymer/diol, wherein the diisocyanate compound is an aromatic 45.

diisocyanate, and wherein the chain extending agent is a straight chain saturated aliphatic glycol containing from 2 to 10 carbon atoms.

5. A process as defined in claim 2, wherein the dihydroxy containing polymer is a hydroxy terminated polyester, wherein the diisocyanate compound is an aromatic diisocyanate and wherein the chain extending agent is a straight chain saturated aliphatic glycol containing from 2 to 10 carbon atoms.

6. A process as defined in claim 5, wherein the hydroxy terminated polyester is a polylactone diol.

7. A process as defined in claim 6, wherein the polylactone diol is a polycaprolactone diol.

8. A process as defined in claim 7, wherein the interfacial agent is selected from the class consisting of a graft copolymer of C6-C30 alkyl .alpha., .beta.-alkenoate, hydroxyethyl acrylate and polycaprolactone and a graft copolymer of C6-C30 alkyl .alpha., .beta.-alkenoate, hydroxyethyl methacrylate and polycaprolactone.

9. A process as defined in claim 8, wherein the inert organic vehicle is a saturated aliphatic hydrocarbon.

10. A process as defined in claim 9, wherein the dihydroxy containing polymer is a polyepsilon-caprolactone diol, wherein the chain extender is 1, 46.

4-butanediol, wherein the diisocyanate compound is 4,4' diphenylmethane diisocyanate and wherein the inert organic vehicle is decane.

11. A process as defined in claim 10, wherein the interfacial agent is selected from the group consisting of a graft copolymer of isodecyl acrylate, hydroxyethyl acrylate and polyepsilon-caprolactone, a graft copolymer of isodecyl acrylate, hydroxyethyl methacrylate and polyepsilon-caprolactone, a graft copolymer of isodecyl methacrylate, hydroxyethyl methacrylate and polyepsilon-caprolactone, and a graft copolymer of isodecyl methacrylate, hydroxyethyl acrylate and polyepsilon-caprolactone.

12. A process as defined in claim 11, wherein the interfacial agent is selected from the group consisting of a graft copolymer of isodecyl acrylate, hydroxyethyl acrylate and polyepsilon-caprolactone, and a graft copolymer of isodecyl acrylate, hydroxyethyl methacrylate and polyepsilon-caprolactone, wherein the catalyst is stannous octoate and wherein the amount of decane is such that the particulate thermoplastic polyurethane polymer comprises about 50 per cent solids in the reaction product mixture.

13. A process as defined in claim 12, wherein the interfacial agent is employed in the form of a solvent solution containing about 50 per cent by weight of the interfacial agent.

47.

14. A process as defined in claim 1, wherein the particulate thermoplastic polyurethane polymer is separated from the reaction product mixture and recovered as a dry, free-flowing, non-agglomerative powder.

15. A particulate thermoplastic polyurethane polymer produced according to the process of claim 1.

16. A particulate thermoplastic polyurethane polymer produced according to the process of claim 6.

17. A particulate thermoplastic polyurethane polymer produced according to the process of claim 9 .

18. A particulate thermoplastic polyurethane polymer produced according to the process of claim 12.

48.