DE1569553A1 - Manufacture of urethane polymers - Google Patents

Description

Wyandotte Chemicals Corporation! Wyandotte _f Michigan, V.St.A "

Manufacture of urethane polymers

The invention relates to a method of manufacture of polymers and in particular a process for the production of solid urethane polymers Ia part form »

j? ür v ^r örsohi «<lene Anwönäungsjgwöcfca is desired ®b , tifear polyurethane» In i? orm clielcristax ⁵ particles with a relatively small grain size can have _o I) && usual processes

lliWg vaiass solahßn polymers ia 'Teiloheafona ü «i hitherto in it, a polyclinic to marry ₅ the in

hw faise zw & Example üuvQh a one-step procedure or a prepolyester procedure had been filled in for years »Biaaei Maänflhms does not eat completely satisfactorily, - # @ il di © by winning the Veriaaalaa. high tea temperature and the polymers will inevitably affect them. In addition, a material is obtained in this way, the grain size being distributed over a wide range of areas.

.... . . BATH ORIGINAL

009819/1733

required effort for the applicability of this measure ale proved too big.

US Pat. No. 2,830,037 describes the production of a polyurethane by reacting polytetramethylene ether glycol described with a diisocyanate in an aliphatic hydrocarbon ale reaction medium. The polytetramethylene ether glycol is mixed with the hydrocarbon solvent to form a uniform liquid solution warmed up. The biisocyanate becomes this lion with formation of a liquid prepolymer containing NCO end groups. Then water or another chain extender is added to the solution and a fee fee polymer is added is cast in fora of small pearls. This mode of operation only leads to the formation of polymers in the form of small ones Perlen · suffered jsdooh filr dl · production of polyurethanes ait a relatively narrow range of grain size distribution not applicable. In the face of a Flüseig-PlUasig-Roaktion but Hera tell Luig of the polyurethane there is a tendency to coagulate and only to form large agglomerates instead of small Elnxeltellohen.

There is therefore a need for a method of making a polyurethane in particulate form with relatively fine particles Grain size.

“BAD OBlQiNAU

009819/1733

The invention relates to a method for the division of solid polyurethanes, a precursor being suspended in a liquid medium in the form of solid particles, the a polyester or a polyether or a prepolymer of a polyester or a polyether with an organic isocyanate is »and this solid precursor with a chain extender is exchanged.

According to a preferred embodiment, in a liquid aliphatic or alicyclic hydrocarbon suspended in a solid, particulate reactant (a) a polyester based on glyool / dibasic carboxylic acid or (b) a polyether polyol that undergoes condensation of an alkylene oxide with a glycol or a polyvalent one Alcohol with 3 to 8 hydroxyl groups or an organic one AmIn with at least 2 hydroxyl groups was obtained, or (c) is a prepolymer formed by reacting one of the reactants (a) or (b) obtained with an organic polyisooyanate and this solid reactant reacted with a chain extender that is an organic Polyocyanate or water or an organic compound with at least two functional groups 1st which are bonded to hydrogen atoms capable of reacting with isocyanates.

BADORiOINAt "" ",,,"., 33

The inventive method is generally applicable and only requires that a solid reactant in one Reaction medium is dispersed in which he and the reaction product ultimately formed are insoluble, and that he is reacted therein with a chain extender. In the context of the invention are thus solid polyester or Polyethers or solid reaction products of the same with isocyanates d. H. Prepolymers dispersed in a liquid medium and converted into various polyurethanes using a chain extender.

A particulate polyurethane is thus produced by reacting solid particles with a chain extender using a reaction medium in which the solid particles and the polymer formed are insoluble. A solid organic polyol or the solid reaction product of a polyol and an isocyanate, d. H. a prepolymer suspended in a liquid hydrocarbon old with a grain size that is about corresponds to the desired particle size for the finished polymer, and then reacted with a chain extender or crosslinking agent to form the desired polymer.

An essential feature of the invention is "that the finished polymer becomes a ·" the reaction participant in the form of a liquid chain

009819/1733

BATH ORIGINAL

extended. This is in contrast to the method of US Pat. No. 2,830,037, where a Polyol dissolved in an aliphatic hydrocarbon and thus carried out a liquid-liquid reaction with the diisocyanate will. In the process according to the invention, the polyol itself is in the form of fine particles and reacts in solid state with the liquid isocyanate. In contrast to the liquid-liquid process according to the patent mentioned The method according to the invention thus makes use of a reaction between a liquid and a solid Material. By using this procedure, a polymer having a predetermined grain size can be obtained without difficulty with consistent results.

Organic polyesters are useful as solid reactants and polyethers having at least two hydroxyl groups and Prepolymers containing NCO or OH end groups, which by Implementation of a polyester or polyether with an organic polyisocyanate were obtained. From these fabrics a suspension of solid particles in a liquid medium is then produced and an appropriate chain extender, e.g., a polyisocyanate or an active hydrogen containing compound.

The reaction medium in which the polymer is used to form

_BAD oBSGVNAt 00 9819/1733

The leading implementation can be any *. Be a liquid in which the dispersed substance and the ρ formed polymers are practically insoluble. Saturated f. Alioyclisohe aliphatic and hydrocarbons have been found to be particularly suitable calibration Dispergienaedien. In addition, these substances are easily accessible and have a favorable boiling point. The highly suitable for the purposes erfindungsgeeäßen saturated hydrocarbons are liquid at the Reaktionatemperatur and have boiling point "la τοη range about 35 to 300 ⁰ O, rorsugsweia · 100-150 ⁰ C. The usable substances 5 tois about 20 Kohlenetoffatome. These include pentane, hexane, hexene, heptane, octane, honane, decane, undecane, dodecane, biooean, cyolopentane, oyolohexane, oyolohtxene, oyoloheptane as well as isomers and oemisohe from these substances. Saturated Og - Oq hydrocarbons are preferably used. These hydrocarbons are easy to use, since they are produced when oil is used. The saturated hydrocarbons used as Diapergler & Ediu * can contain small amounts of other hydrocarbons, such as aromatics and olefins, and the commercial products are mostly mixtures of such substances.

The method according to the invention is preferably carried out in two ways Stages carried out. First of all, a dispersion of de * '

009819/1733

solid reactant in the hydrocarbon medium. This step can be carried out over a wide range of temperatures, the limits of which depend mainly on the fixed point of the solid reactant. This dispersing step can expediently be carried out by heating the solid reactant until a melt is formed and then adding it to the hydrocarbon medium at a temperature below the fixed point of the solid reactant. This temperature may be between about 0 and 150 ⁰ C. As soon as the melt comes into contact with the hydrocarbon, solidification occurs with the formation of discrete particles. The addition is preferably carried out with the aid of strong shear forces in order to ensure the formation of relatively fine particles, see below. One can use a Waring mixer or devices with more specific shear action, BB a "dispersator" ₉ a "homomixer" or a "Cowles diaeolver".

laughing at the establishment of the siepereion of the firm reaction participant a chain extender is introduced into the dispersion with stirring. The chain leader lies under the Xte & ction conditions preferably in liquid State before. However, it is also possible to use a solid-liquid mixture of the chain lengthener or a mixture of the demand

009819/1733

BATH ORIGINAL

rers with plasticizers to increase its solubility or to use a solid chain extender that is partially or completely soluble in the dispersing medium. The reaction is carried out at temperatures »which are high enough to keep the chain extender in an at least partially solubilized state, but low enough to prevent the dispersed reactant from becoming sticky or sticky» In general, the temperature is depending on the % m each used solid reactants and chain extender between £ twft 0 and 15O ⁰ C..

^ Another possible way of working can be the chain »Longer before the formation of the dispersion to the melt

4 1 'S

^ add the solid reactant. The formed overall '■ j mfoch. However, solid reactants and chain extenders are added to the dispersing medium before

and chain lengthening increase the viscosity of the melt §Ls at one point where mixing and moving are difficult . This mode of operation has the advantage that only

Mixture added to the hydrocarbon reaction medium

Λ - · ■

· * J '■ -

^ needs to be. ^

■ -ί Be |. A wide range of possible ways of working becomes fluid £ Dispersion of the solid reactant in the dispersing

* β »

r *

009819/1733

Medium produced «This mixture is then cooled to solidify the solid reaction participant in particulate form.

A fourth possible way of working can be the solid reactants mechanically into particles of the desired Size wedded. The particles are then used as such or in admixture with a chain extender added to the hydrocarbon reaction medium.

In any of the working methods described above, a catalyst can be used to accelerate the reaction. The catalyst can be added to the melt of the solid Reactant or to the hydrocarbon reaction medium or to be added to both. Catalysts useful in accelerating these reactions are general known. For example, metal salt and tertiary amine catalysts are often used for the polyol-isocyanate reaction used. These include, among others, lead naphthenate, stannous octoate, Dibutyltin dilaurate, bismuth octoate, trimethylpiperazine and 2,2,2-diazabicyclooctane.

It is also possible to use a one-step procedure wherein a polyol, a diisocyanate and a chain extender as defined above at the same time as the coal

009819/1733

hydrogen reaction medium can be added. A metal salt catalyst is used in conjunction with this procedure used and the Polyolisooyanatumetzung takes place before Chain extension instead.

After contacting the solid reactant "of the chain extender and if desired the catalyst in the hydrocarbon medium, the reaction mixture is kept Hinuten 5 to about 25 hours with constant stirring at temperatures of 40-100 ⁰ C. The mixture is then filtered and the polymer can be dried in vacuo to remove any traces of dispersant that may still be present before it is sieved and sorted according to size.

The process according to the invention gives polymers in particle form with different particle size distributions. The grain size can range from as small as less than a few H9 microns (100 mesh) to 2000 microns (10 mesh) or even bigger. The grain size distribution can be calibrated Adjust so that a preponderance of the polymer is in a relatively narrow range of about 590 microns (30 meeh) lies. The grain size depends directly on the size of the particles dta disperse feeten reaction participantsa mb, which in turn is constrained by various factors. This includes the feat "used in the respective pail"

009819/1733

- 1 S -

Reaction partiiemers, daa dispersants, which are used for the production the equipment used for the dispersion, the duration and speed of the movement, the speed of addition and those between the introduction of the solid reaction part nehiaera elapsed time in the dispersant to perform agitation. The one to achieve the desired grain size The necessary classification of these factors can be determined empirically very easily and is one based on this Measure familiar to the technical field.

As already mentioned, the process of the invention comprises the reaction of solid polyester or polyether polyols with isocyanates in a liquid hydrocarbon medium to give the desired polymer or the chain extension of a solid BTCO- or OH-terminated prepolymer in the hydrocarbon medium with an appropriate extender. The polyesters and polyethers that can be used are those with at least two hydroxyl groups and a fixed point of about ⁰ ° C. and above.

The polyesters that can be used are obtained by converting polyvalent ones Alcohols e.g. glycols or triols with a white carboxylic acid or an anhydride of such Acid s.B. Succinic acid, maleic acid, glutaric acid, adipic

fiaelic acid,
acid »pematine acid , / sebacic acid, malonic acid, fumaric acid,

0 09819/1733 BAD

Phthalic acid and terephthalic acid. Any glycol can be used to form the ester, for example ethylene, propylene, diethylene, triethylene, butylene, hexamethylene and beeamethylene glycol. Linear polyesters made from the abovementioned substances and branched substances which are obtained by using a trifunctional alcohol or a trifunctional acid such as citric acid, glycerol and trimethylopropane in the reaction can be used. In general, linear hydroxyl-terminated polyesters having a pest point of ⁰ G and above are preferred. The molecular weight can range from about 300-10,000, preferably from 750-3,000. The polyesters containing hydroxyl end groups are obtained by using an excess of the alcohols, as a result of which terminal hydroxyl groups are formed preferentially over carboxylic acid groups. The manufacture of various solid polyesters, for example from adipic acid and ethylene or propylene glycol, is described in U.S. Patent No. 2,760,953 and Canadian Patent No. 539,641.

Within the scope of the method according to the invention, it is also possible solid polyester amides as the solid reactant be used. These products are made by conversion of dibasic carboxylic acids or their anhydrides with

D09819 / 1733

BATH

bifunctional compounds having at least one esterifiable hydroxyl group and at least one hydrogen-containing amino group or a di- or polyhydroxy compound and a di- or polyamine compound are obtained. As the bifunctional compound, one can thus use an amino alcohol or ßeraiselie aua diamines and ßlycols. use. Any glycol or acid or its anhydride as described above is suitable for the reaction. Aa & nop © ntanol ₉ aminomethylhexanol, 4-hydroxyethyl-4-alkylethyldiphenylethanolamine and aminohexanol. Diamines that can be used include those with at least one hydrogen atom on each aiainosticketoffatoa, for example ethylenediamine _f hexamethylenediamine, * hexamethylezidlamine and phenylenediamines Ee iet polyeeteraa ± 4e lait © in @ generally a considerable proportion of algae hydroxyl groups, those in which there is a substantial proportion of algae hydroxyl groups, those in which there are ametanic or carboxyl acid groups. au use «·, Such substances are made by setting the. Quantitative proportions, the reaction participants in the catfish that there is an excess of hydroxyl-containing glycol or amino alcohol. A process for preparing * 'are useful Poljsssteramlde la elnaelnea In d®r ÜSA Pstentsciirift-2133922 indicated.

A preferred formulation is a polyethylene polyol

00-981 9 / -1 733

-H-

with less than two hydroxyl groups anateile of the polyether compound used. The polyethers contain hydrocarbons groups of ether bonds separated from each other (-0-). The ethers that can be used contain at least two Terminal hydroxyl groups and can be linear or branched and have molecular weights from 400 to about 50,000.

A polyether with a molecular weight of 1000 "to 35,000 and a melting point of over ⁰ ° C. is preferably used.

To Beiapielen of useful polyether include Polyalkylenätherglyoole of! Formula

H (OR) _n OH,

in which R «denotes a polymethylene group, preferably having 2 to 4 carbon atoms, and η denotes an integer of such a size that the molecular weight of the polyether is 400 to 10 ohms. The preferred ethers have a molecular weight of about 1,000 to 7,000; These include, inter alia, polyethylene ether glycols, Polytriae thy lenätherglycol · and polytetramethylene ether glycols with plague points of over ⁰ ° C. Furthermore, one can use an alkylene oxide or a mixture of alkylene oxides chain-extended glycol · and polyflyools. So you can use as a polyether

009819/1733

BATH ORIGINAL

Ethylene oxide chain-extended propylene glycol or poly-. use propylene glycol. Examples of polyethers that can be used and their reactions with diisooyanates can be found in U.S. Patents 2,492,955 and 2,929,800.

Other polyethers that can be used are such as by Condensation of a polyhydric alcohol with an alkylene oxide can be obtained. These include polyethers of formula

0 EH

HEOR [θ EH] _n

0 EH

where B, together with the oxygen bound to it, heats a polyhydric alcohol with 3 to about 10 carbon atoms, E is a polyoxyalkylene chain, preferably. Polyoxyethylene or polyoxypropylene, which can be the same or different in the individual repetitions and where at least 50 weight ^ of each chain represent polyoxymethylene groups, and η is an integer from 0 to 3. Bas uas backbone-forming polyvalent alkenol can glycerol, 1,1,1-trimethylolpropane, pentaerythritol, sorbitol, hexane triol-1,2,6-, and the like "and the

0098 19/1733

BATH ORIGINAL

Alkylene oxide reactants include ethylene, propylene and butylene oxide. Of the above substances, block polymers with a pest point of at least ⁰ ° C are preferably used, which are obtained by successive condensation of polyhydric alcohols with propylene oxide and reaction of the intermediate with ethylene oxide. The ratio of ethylene oxide to propylene oxide should be about 1: 1. The polyhydroxy compound to be reacted with an alkylene oxide can also be ain sulfide, for example sucrose, glucose, mannitose or oC-methylgluooside.

Another group of substances belonging to the polyethers which can be used according to the invention is that of certain tertiary amines containing hydroxyl end groups. This includes substances with a fixed point of O ⁰ C and above and the following formula:

HE ■
TT-R-

wherein H is an alkyl group having 2 to 6 carbon atoms and E denote polyoxyalkylene chains which are identical to or different from one another. These substances have Molecular weights in the range of 400-35,000

009819/1733 bad original

Compounds have the formula y (OH.C ₂ ) (OH ₆ C,) _V

4 ο>> k N — GH -CH -

y (OH ₄ C ₂ ) _x (OH ₆ C ₃ K " ² " ² " ^X (C ₃ H ₆ O) _x (C ₂ H ₄ O) _y H

wherein the total molecular weight is about 7,500 to 35,000 and the oxyethylene groups make up 40 to 95 $> of the entire molecule. These include for example the products obtained by the successive condensation of about 40 to 80 moles propylene oxide and 70 to 500 moles of ethylene oxide with one mole of ethylene diamine, wherein the Oxyäthylenanteil constitutes at least about 40 $>} of the total molecules.

Another group of amine-based polyethers are those of the formula

^ N-Y

in which S are identical to or different from one another Polyoxyalkylene chains, Y denote an alkyl group with 1 to 8 carbon atoms or the radical -EH, in which E

BATH ORIGINAL 00 9819/1733

has the meaning given. The preferred substances are obtained by condensing an alkanolamine, e.g. methyldiethanolamine or triisopropanolamine, one after the other with propylene oxide and ethylene oxide, to an end product with a molecular weight of 1000 to 7000 in the case of a difunctional ether and from 1000 to 25,000 in the case of a trifunctional compound, an oxyethylene content of at least 40 i » and a plague point of not below O ⁰ C received»

Another group of substances that can be used as a solid reactant is that of the phosphoric acid-alkylene oxide adducts. These phosphorus-containing poly-oils can be incorporated into the polymer to make it fire-resistant or to impart other desirable properties to it. For example, in the case of an oil source acidification, a polymer may be desired that has one undergoes hydrolytic degradation. Certain phosphoric acid-alkylene oxide adducts are hydrolyzable and can with Advantageously used for such a purpose. To the Useful products include adducts of phosphoric acid, phosphonic acid, pyrophosphoric acid and tripolyphosphoric acid with ethylene oxide, propylene oxide, butylene oxide and styrene oxide. Preferably using τοη ethylene oxide products obtained because they usually have higher freezing points. You 3toff mentioned above are all *

009819/1733 'BADORtQiNAL

Commonly known and processes for their preparation are in U.S. Patents 2,372,244, 3,094,549, and 3,099,676.

Any of the aforementioned substances or mixtures thereof can be used in the. Implementation of the method according to the invention can be used as the fixed response participant. A dispersion of these solid substances with several active hydrogen atoms is reacted with an organic polyisocyanate, preferably a diisooyanate, to form the desired polyurethane. Examples of useful isocyanates are m-Phenylendiisooyanat, tolylene-2,4-diiaooyanat ₅ 2,6-tolylene diisocyanate, H '-. <Ämathylen-1 _t 6-äiieooyanat' _{tetramethylene-1,4-diisocyanate-1,4-9} Cycloheian äiieocyanatj Uaphtaalin-1,5-diisocyanate, 1 ~ © Methoxyph nyl-2,4-diieocyanatβ Biph®nylmetßan _f-4 4'-diisocyanate, 4,4 ^f -Bipaenyldiieocyanat, 3.3 -Bimethyloxy ^I 4,4 ^I - biphenyl diisocyanate, 3,3'-Dimethy1-4 »4 * -biphenyldiisöcyanat, 3 , 3 * -Dimethyldiphenyliaeethan ~ 4,4 '-diisocyanat, Polyme thylenpolyphenylieooyäaat and mixtures thereof.

The isocyanate is reacted with the polyol in a NOO / OH ratio of about 0.7 s 1 to 1.5: 1, preferably close to 1 t 1. Theoretically, this results in a polymer with a maximum molecular weight. However, 2s can be a big one

BAD ORIGINAL 00981 -9/1733 ■■

1569S53

Excess leoeyanate can be used, then this Excess tends to remain in the hydrocarbon phase, from which it can be recovered and returned to the cycle. The subsequent hardening is through Heating to elevated temperatures of about 40 to 100 C during 5 minutes to about 25 hours.

Another possible way of working is to use the dispersion of a solid prepolymer in the hydrocarbon medium. In this procedure, one of the polyols described above is reacted with a solid prepolymer containing hydroxyl end groups. The polyol and the isocyanate are reacted in such a ratio that an OE / NCO ratio of about 1.4: 1 and above is present. The solid prepolymer obtained is dispersed in the hydrocarbon medium and then reacted with a diisocyanate in such a way that an NGO / OH ratio of 0.7: 1 to 1.5 * 1 *, preferably about 1 to 1, is present.

Another option is to have an HCO endgroup Prepare containing prepolymers, which is then dispersed in the aliphatic hydrocarbon and chain extended therein. In this procedure, a polyol is used an Ieooyanat In an HC0 / OH ratio of about 1.4 «1

00 m 19/1733

BATH ORIGINAL

"to 2.5 t 1 ₉ ^ orzugsweise about 2 s 1 s @ © taasg tsto- Bas göMMots

is lsi $ <sm & obX © ms @ saek ⁿ si & @ ££ m © ä & Pii iia ° pergated and with a®? © la ü2stiv @ © U @ t3® © J? ®t © ffat © ia receiving connection IsQ-fetQiavos'MssgQS'to Β ©>? Am © drills ³⁵ ©! Stlv @ ® Hydrogenatöa "fce-sielrö © i © Ii auf W ^ s © © s-st © ffStOSe ₀ .ü% ® si © M" bsi äer Prüfe © nsela! © rswitisioffo ^ a © i © la Bö »49s S * 3181 (1,927)

Fabric © g®M> T

_{9 &} wi ©

Nitrogen © athsIt © M® St @ ff © _? wi ©

II © a ecliwisnksa »TfosjBugsweis ©

Followeaöi® SsaisgSel® © i? Mat © r® the lirfteiiasge a & ao ei ©

"beaear &aJtai" «» feaa aiolsts aaasres am ^ ggeiaa £ ιΊ ₀

M®ng «n conditions on over ,

example 1

A mixture of 200 parts hexane and 1.1 parts BIe-inaphthenet was prepared. 66.8 parts of a continuous addition of propylene and ethylene oxide

BATH ORIGINAL

009819/1733

- 22 - ■

Ethylenediamine produced nonionic surfactant (! TETRONIC 908) and 33.2 parts of a polyethylene glycol with a molecular weight of about 6000 (PLORACOL B * -6000) were heated to 70 ° C to form a melt.

TETRONIC 908 is an amine-based tetraol with one Molecular weight of about 27,000 and an oxyethylene. ^f

holds from about 80 to 90 weight ^. This means as well PIlIRACOL S-6000 are from Wyandotte Chemieale Corporation available. 1.8 parts of tolylenediiamooyanate was added to the Melt added and the resulting mixture became the Hexane catalyst solution, which was at room temperature, given. The tent resulting from the mixing of the Ieooyanats with the Polyolohaelze to the addition of the obtained It should be kept as short as possible Ensure, among other things, that no weight-loss crosslinking or chain lengthening takes place before the addition to the heptane solution · In the proportions given above eioh the relative molar ratios of the reactants to 1 mole Tetronio, 2 moles pluraool and 4 moles Diocyanate corresponding to 4 hydroxyl equivalents per Tetronic and pluraool and 8 equivalents of diisooyanate. The addition of the polyol without salt was carried out in about 2 minutes, whereby the aliphatic carbon dioxide medium was agitated in a Waring mixer. During this time there was education

of fine particles can be recognized. The reaction meaeae was

BATH ORIGINAL 008119/1733

then led into a 3 ~ ifels-k © lljea over j, ö © 2? with @iaea Heismantel ₉ flne: ra ©! sete: stranding 2 'uad reflux cooler was ₀ Bas Geiaisch. «ofde ^ ies ¹ Stiaaden. "Maintained at β0 ^Θ 0. The polymer formed was filtered and dried at room temperature in a Vs & uu & escslos & tor. Ee had a melting point of about ISI ¹³ G and a grain size of about 420-297 microns (40-50 aesfejL You water absorption of the polymer was 2430 f> determined, i.e. the polymer absorbed more than 24 times its own weight in V / asaer,

Example 2

With the procedure described below, an attempt was made to divide into solid particulate polymer by means of a known procedure. G of '66 "8! Tetronic 908 vma 33" 2 g fluraöol S-6000 dtircli heating at 80 ⁰ C was prepared Sclsaelze. This Sehmels © au was 200 g nonane _s Ulm 1 g Pluronic I "-101 contained and woräen maintained at 80 ⁰ C, possibly. (The Pluronica are non-ionic surfactants obtained by adding ethylene oxy and polypropylene glycols. At this temperature, a liquid dispersion of the polyol in Konan was obtained. 1.1 g of toluene boeyanate, mixed with 10 g of nonane, was then added to this mixture and contained 0.1 g of stannous octoate as a catalyst. About 30 seconds after the addition of the solution containing toluene diisocyanate

BATH ORIGINAL 009819/1733

As a result, the mixture agglomerated to form a sticky mass.

Example 3

A mixture of 200 g of heptane and 0.1 g of Büßinaphthenat was prepared. A melt of 66.8 g Tetronic 908, and 33.2 g Pluracol E-6000 was prepared by heating these materials to 70 ⁰ C. 30 g of acetone were added. given to the melt. The resulting mixture at a temperature of 50 ⁰ C was added (marine blade) within 3 Hinuten while mixing with a paddle stirrer to the heptane-catalyst löeung of 25 ⁰ C. During this time, particles approximately 840 microns (20 mesh) in size formed. A solution of 1.8 g of tolylene diisocyanate and 10 g of heptane was added to the 2-phase system formed. They addition took place within 3 minutes at a mixing temperature of about 37 ⁰ C. The mass was transferred to a 3-necked flask as described in Example 1, transferred and held for 5 minutes at 37 ⁰ C. After filtering and drying, a polymer with a melting point of about 190 ° G and a water absorption capacity of 2500 % was obtained.

BATH 00 9818/1 * 33

Example 4

66.8 g Tetronic 908 and 53.2 Pluracol E-6000 were performed by heating to about 65 ⁰ C in a melt. Dieeer to melt a prepared at room temperature mixture of 1.0 g Pluronic £ -101, 100 g of nonane, 1.8 g of tolylene diisocyanate, and I ₁ Ig lead naphthenate was added. Pluronic L 101 is a non-ionic surface-active agent which is produced by the successive condensation of propylene and ethylene oxide with propylene glycol. Ee has two terminal hydroxyl groups, a molecular weight of about 5600 and an oxyethylene content of about 10 #. The polyol membrane was added to the nonane over a 5 minute period with mixing with a Waring Miaher. The Miechtemperatur was about 45 ⁰ C. During the addition, were calibrated discrete particles. The mixture was transferred to a 3-neck flask, and heated for 2 hours at about 50 ⁰ C. 350 microns (25 - - 45 meeh) by filtration polymer particles having a grain size of about 710 were obtained with a melting point of 192 ⁰ C. ·

Example 5

83.7 g of Tetronic 908 and 41 »3 g of Pluraool Ε ^ βΟΟΟ were heated ^{to ttw * 70 0 G.} The old melt became a dispersing medium which contained 225 g of n-heptane, 0.18 g of lead naphthene & t

009813/1733

and 2.14 g of toluene diisocyanate and calibrated at a temperature of about 25 ⁰ C was. The addition was made with mixing in a Waring blender and fine particles formed during the addition. The reaction mixture was transferred to a 3-Halekolben and with continued EUhren one hour at 5O ⁰ C, heated for one hour at 80 ⁰ C and finally 2 hours at 92 ⁰ C. A solid polymer in particle size was obtained with a grain size of about 250 mitrons (60 meeh) and a water absorption capacity of 2090 pounds.

Example 6

A ^ ohnelse of 66.8 g Tetronic 908 and 33.2 g Pluraool 1-6000 of 70 ⁰ C were given approximately 48 ⁰ G 15g acetone kit a temperature door sound. This mixture was added to 200 g of n-heptane containing 0.1 g of blelnaphtaenate while being mixed with a Waring misoher. The 2-phase dispersion formed by Me contained fine-grained particles. Then a solution of. 1.8 3 Toluylendiieoojanat in 10 g heptane within 3 minutes su the Polyol-Heptan-Diepereion sugeeetst. The product was transferred to a 3 Hale flask and warmed to 60 ⁰ O for half an hour. A polymer consisting of discrete particles with a grain size of about 250 microns (60 mesh) was obtained

_ ORIGINAL BATHROOM

0091If / 17 ??

Water absorption capacity of 2050 i> on vias.

Example 7

In the preparation of the polymer described below, 900 g of heptane containing 0.9 g of blelnaphthenate were used as the dispersing medium. 400.9 g Tetronic 908 and 199 g Pluracol E-6000 were heated to 65 ⁰ C and treated with 60 g of acetone at room temperature. This mixture was then added to the cooled to 1O ⁰ C heptane. The addition was carried out while the mixture was kept in motion with the aid of a "diepersator". Fine-grain polymer particles were formed. B & oh transferring to a 3-necked flask, the mixture was admixed with 10.8 g of toluylene diisocyanate in 20 g of heptane with continued stirring. The heating was still a Stunde.bei 50 ⁰ C, a citunde at 6O ⁰ C and finally one hour at 75 ⁰ C continued. A particulate polymer was obtained by filtering the mixture and drying in vacuo.

Example 8

600 g of a polyol mixture composed of 400.9 g of Tetronic 908 and 199β1 g of Pluraool E-6000 were heated to 65.degree. Acetone at room temperature was added to this mixture until the temperature was 58 ^° C. This

009819/1733

BAD ORiQiNAL

Mixture was added to a cooled to 1O ⁰ C mixture of 900 g of heptane and 0.9 g of lead naphthenate. Mixing was done by keeping the mass agitated with the aid of a "homomixer", thereby obtaining a pesticide dispersion of the polyol mixtures. The dispersion was transferred to a 3-necked flask and, with continued stirring, 10.8 g of tolylene diisocyanate in 10 g of heptane were added over the course of 3 minutes. The mixture was heated for half an hour at 45 ⁰ C and a half hours at 55 ⁰ C for half an hour at 75 ⁰ C and a half hours to 79 ° C. By filtering off the mixture, a solid partially ohen-shaped polymer was obtained.

Example 9

0.9 g of lead naphthenate were added to 1200 g of heptane, and the mixture was cooled to 6 C ^0. A melt of 535 g of Tetronic 908 and 265 g Pluracol E-6000 60 ⁰ C BU was added 80 g of acetone from room temperature. A dispersion was prepared by adding this Gemisohs to the heptane solution, the necessary agitation being generated with the aid of a "Cowles Dissolver". Thereafter, 14.4 g of tolylene diisocyanate in 20 g of heptane was added to the mixture with continued stirring. The Miβοhung was transferred to a 3-Halekolben and heated for 2 1/2 hours at 45 ° C and one hour at 7O ⁰ O. The polymer

009819/1733

was separated from the mixture by filtration and dried in vacuo.

As already mentioned, polymers with different particle size distributions can be produced by the process according to the invention. One of the essential factors in adjusting the grain size is the mixing or shearing mechanism used to prepare the dispersion of the solid reactant. The grain size distribution of the polymers prepared according to Examples 7-9, with a "Dispersator", a "homomixer" and a "Cowles Dissolver" was applied is indicated in the following table _f.

000019/1733

Table I. Grain size distribution of the polyurethane polymers

Lens size in microns (mesh) polymer according to example 7 polymer according to example 8

Residue fraction on Seven with 250 (60) 177 (80) 177 (80) different mesh sizes in 9.8 5.8 - .) 2000 (10) 840 (20) 420 (40) 29.6 20.0 11.5 8.6 46.4 29.4 8.4 30.5

Polymer according to Example 9

29.3

35.0

22.6

7.8

5.3

cn ι cn ^ ₁

In the table above are the relative size distributions of the 3 polymers as the percentage retained by sieves of different sizes of the respective polymer. As can be seen, most of the particles in each pail were smaller than 2000 microns; (10 mesh). In a preferred embodiment using the "homomixer" the main part was the particles in the range of 2000 - 177 microns (10 - 80 mesh),

The polymers produced by the process according to the invention are suitable for use in the usual fields of application of polyurethanes, for example as coatings, adhesives and for dividing molded articles. Some of the polymers are particularly suitable as Flüesigkeitsverlustzusätze the souring of oil wells.

000 * 19/1733

Claims (3)

- 32 claims 1. Process for the production of solid polyurethanes by reacting precursors such as polyols with chain extenders such as isocyanates in liquid media such as aliphatic or alioyolic hydrocarbons, characterized in that a polyester or polyether or a prepolymer of a polyester or polyether is used as a precursor used with an isocyanate in the form of solid particles. 2. The method according to claim 1, characterized in that as the solid precursor (i) a polyester of a glycol and a two-baaieohen carboxylic acid or (Ii) a polyether polyol or (iii) a prepolymer aua (1) or (Ii) and one organic polyisocyanate and, as a chain extender, an organic polyoxyanate or water or an organic compound with at least two hydrogen atoms capable of converting an Ieooyanat. 3. The method naoh claim 1 or 2, characterized in that AmQ is used as a chain extender, an organic diisocyanate. 4 · Method according to Claim 3, characterized in that 009119/1733 BAD OBiGlNAL a polyether polyol having a molecular weight is used as the precursor of at least 500 and a freezing point not below about 0 C is used. 5. The method according to claim 3 »characterized in that the precursor is a prepolymer containing OH end groups used, öas by reacting an organic polyol with an organic diisocyanate in an OH / NCO ratio greater than about 1.5: 1. 6. The method according to claim 1 or 2, characterized in that that a precursor containing NOO end groups / Prepolymer used by reacting an organic polyol with an organic diisocyanate in an NCO / OH ratio from etv / a 1.4 to 2.5: 1 was obtained. 7. Process according to one of Claims 1 to 6, characterized in that the reaction mixture is kept at 40-15O ⁰ C for about 1/12 to 25 hours. 3. The method according to claim 1 or 2, characterized in that the solid particulate precursor is formed by training a melt of a mixture of a polyethylene glycol with a molecular weight of about 6000 and the Product of the successive condensation of ethylene diamine with propylene oxide and ethylene oxide with a molecular 00 * 811/1733 BATH ORIGINAL weight of about 27 OOO, wherein about 80 of the molecule consist to 90 # of oxyethylene, Z _u this mixture handoff to the aliphatic hydrocarbon with stirring or shaking, and reacting the dispersed therein particulate solid substance with an organic diisocyanate in a ffCO / OH ratio of about 1: 1 produces sufficient amount and the reaction mixture about 4 hours at temperatures of 40 - 150 cured ⁰ G. 9 «Method according to claim 8, characterized in that a polyurethane with a particle size distribution in the range from 2000 to 177 microns (10-80 aesh) is obtained. 0 088 1 · / 1733 «* O« oinal