NL8004033A - EASILY FORMABLE POLYURETHANE COMPOSITION. - Google Patents

Description

'49 577 / Bos / AS - 1 -

Carl Freudenberg, at

Weinheim / Bergstrasse, Federal Republic of Germany. Easily moldable polyurethane compound.

The invention relates to an easily moldable polyurethane composition using an internal release agent.

Polyurethanes are known and are widely used as tough and elastic materials, in particular for the production of molded parts. The reaction components can be cast in the desired shapes and cured therein. It is also customary to press rollable polyurethane elas-10 tomers or a thermoplastic deformation afterwards. For example, moldings of any kind can be manufactured by injection molding, extrusion or by the hollow body blowing method.

Virtually all methods require the use of a release agent to avoid selection of the molded parts on the wall of the mold. The most common method consists of carefully filling the molds with a thin film of the release agent before filling in the polyurethane composition. More commonly-2 "JX wise, waxes, soaps or oils are used. These so-called.

"external" release agents are useful, however they must be applied in a separate treatment step. During this time, the mold fails in production. The precise dosing of the release agent 25 is often difficult, because the release agent is applied by spraying or ironing and in complicated shapes, for example with fine engraving of the mold, it does not completely fill it up.

Because of the difficulties previously described, which occur in particular with polyurethanes, while other plastics, for example polyolefins, can be effortlessly released from the mold even without a release agent, 800 4033 - 2 - "internal" release agents have been developed, which usually consist of fatty acid derivatives. fatty acid derivatives are added in a relatively large amount to the polyurethane composition and ensure a good release of the part to be manufactured from the mold, however, the usefulness of such internal release agents in an automatic production of molded parts is limited to the extent that after repeated use contamination of the mold cycles and thus an interruption of the automatic process is necessary, moreover, the mechanical value level of the molded parts produced is influenced by the relatively high amounts of internal release agents, such internal release agents for polyurethanes are described, for example. n in the German "Offen-15 legungsschriften" 23 07 589 and 23 19 648.

The object of the invention is to develop an internal release agent which is particularly suitable for polyurethane compositions and which makes it possible to produce molded parts automatically over a longer period of time, without causing contamination of the mold and without influencing the mechanical values. This object is achieved by an internal release agent which has an oligomeric composition and which typically has a grouping affinity to the urethane groups of the polymer of high molecular weight. Such affinity groupings are urethane and / or urea or thiourea or thiurethane groups, respectively.

Therefore, the easily moldable polyurethane composition of the invention consists of a mixture of the high molecular weight urethane polymer and, as an internal release agent, a small amount of at least one oligomeric product on the urethane and / or urea basis of the formula 1, 2 or 3 of the formula sheet, wherein A, A ', B, B' and R are independently selected from hydrogen atoms, alkyl groups of 1-35 carbon atoms, aryl groups of 6-14 carbon atoms, and substituted aryl esters, wherein the substituents halogen- 800 4 0 33

i U

- 3 - atoms, alkyls with 1-35 carbon atoms, arylalkyl-1-thio radicals with 6-14 carbon atoms in the aryl and 1-35 carbon atoms in the alkyl moiety, arylthio radicals with 6-14 carbon atoms or aralkyl radicals with 7-15 are carbon-5 atoms, X represents a sulfur or oxygen atom and Y and II 'are independently selected from alkylene radicals with 1-35 carbon atoms, arylene radicals with 6-14 carbon atoms, alkarylene radicals with 7-30 carbon atoms, aralkylene radicals with 7-20 carbon atoms, 10 - (CH2) 1_4-0- (CH2) 1_4- and - (CH2) 1_4 »S- (CH2) 1-4 radicals or polyesters, polyethers, polycarbonates or polybutadienes with molecular weights of 400- 4000, and wherein further at least one of the radicals A, B and R is a residue other than a hydrogen atom and wherein a and b as well as 0-1 are chosen such that the sum of a and b is at least 1.

The oligomeric products are added in amounts of 0.01-10.0 parts by weight per 100 parts by weight of the high molecular weight urethane polymer. An amount of 0.1-2.0 has been found to be optimal for most applications.

Starting components for the high molecular weight polyurethane compositions are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described by W. Siefken in Ann. 562, pp. 75-136, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate as well as wrap-around mixtures of these isomers, 1-iso-cyanato-3,3,5-dimethyl-5-isocyanatomethylcyclohexane (German "Auslegeschrift" 12 02 785, US patent No. 3,401,190), 2,4- and 2,6-hexahydrotoluylene diisocyanate-35-cyanate as well as any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene-diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers, 800 4 0 33-4-diphenylmethane- 2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ', 4 "triisocyanate, polyphenyl-polymethylene polyisocyanates, such as these by aniline-formaldehyde condensation and subsequent f obtained and described, for example, in British Pat. Nos. 874,430 and 848,671, m- and p-isocyanatophenylsulfonisocyanates according to U.S. Pat. No. 3,277,138, carbodiimide groups containing polyisocyanates such as those in German Pat. .162), diisocyanates, such as are described in U.S. Pat. No. 3,492,330, allophanate-containing polyisocyanates, such as, for example, in British Pat. No. 994,890, Belgian Pat. No. 761,626, and Netherlands Patent Application 7102524 laid open to public inspection. are described, isocyanurate groups-containing polisocyanates, such as those in, for example, U.S. Pat. No. 3,001,973, German Pat. Nos. 1,022,789, 1,222,067 and 20 1,027,394, as well as in German Offenlegungsschrift No. 19 29 034 and 20 04 048 disclosing urethane-containing polyisocyanates, such as these For example, in Belgian Pat. No. 752,261 or in U.S. Pat. No. 3,394,164, acylated urea groups containing polyisocyanates according to the

German Patent 1,230,778, polyisocyanates containing biuret groups, such as are described, for example, in German Patent 1,101,394 (U.S. Pat. as disclosed, for example, in U.S. Pat. No. 3,654,106, ester groups having polyisocyanates, such as those referenced in British Patents Nos. 965,474 and 35, 11) 72,956, in U.S. Pat. No. 3,567,763 and in German Pat. No. 1,231,688 of the above isocyanates with acetals according to German Patent Specification 1,072,385 and polymeric fatty acid residues containing polyisocyanates according to United States Patent Specification 3,455,883.

800 4033

¥ A

- 5 -

It is also possible to use the distillation residues resulting from the technical preparation of isocyanates, which are optionally dissolved in one or more of the aforementioned polyisocyanates.

Furthermore, it is possible to use any mixtures of the aforementioned polyisocyanates.

Particularly preferred are generally technically readily accessible polyisocyanates, for example the 2,4- and 1,6-tolylene diisocyanate as well as any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those by aniline formaldehyde condensation and subsequent phosgenation are prepared ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups possess the polyisocyanates ("modified polyisocyanates").

Starting components which can be used according to the invention are further compounds with at least two hydrogen atoms which can react with isocyanates and have a molecular weight of generally 400-10000. By compounds, in addition to amino groups, thiol groups or carboxyl groups, this is preferably understood to mean polyhydroxyl compounds, in particular compounds having 2-8 hydroxyl groups, especially those having a molecular weight of 800-10000, preferably 1000-6000, for example at least 2, usually 2-8, but preferably 2-4, hydroxyl-containing polyesters, polyethers, polythioethers, polyacetals, polycarbonates and polyester amides, as known per se for the preparation of homogeneous and of foamed polyurethanes.

The suitable polyesters having hydroxyl groups are, for example, conversion products of polyhydric, preferably divalent and optionally additionally trivalent alcohols with polyvalent, preferably divalent, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of low alcohols or their mixtures for 800 4033-6-the hardening of the polyesters can also be used. The polycarboxylic acids can be of an aliphatic, cycloaliphatic, aromatic and / or heterocyclic nature and optionally, for example, by halogen atoms. substituted and / or unsaturated.

As examples, mention can be made of succinic acid, adipic acid, turmeric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro-10 phthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetrahydric anhydride fumaric acid, dimer and trimer fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, terephthalic acid dimethyl ester, and terephthalic acid bisglycol ester. Polyhydric alcohols include, for example, ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanedio1- (1,6), octanediol (1 , 8), neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerine, tri-20-methylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2, 4), trimethylol ethane, pentaerythritol, quinitol, mannitol and sorbitol, methyl glycoside, further diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols. The polyesters may partly have terminal carboxyl groups. Copolyesters from lactones, for example cap-caprolactone or hydroxycarboxylic acids, eg been-hydroxycaproic acid, can be used.

Also the polyethers which are suitable according to the invention, at least 2, usually 2-8, preferably 2 or 3 hydroxyl groups, are those which are known per se and are produced, for example, by polymerization of epoxides such as ethylene oxide, propylene Oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, for example in the presence of BF 3 / or by the application of these epoxides, optionally mixed or successively, on starting components with reactable hydrogen atoms, such as water, alcohols, 800 4033 * 4 - 7 - ammonia or amines, for example ethylene glycol, propylene glycol (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylene diamine. Sucrose polyethers, such as these are described, for example, in the German "Auslegeschriften" 11 76 358 and 10 64 938, are also suitable according to the invention. Often such polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OHIO groups. Polyethers modified by vinyl polymers, such as those formed, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers (U.S. Pat. Nos. 3,383,351, 3,304,273, 3,523,093, 3,110,695, 15 German Patent 1,152,536) are suitable, as are polybutadienes having OH groups.

Among the polythioethers can be mentioned in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, amino carboxylic acids or amino alcohols. Depending on the co-components, the products are polythiomethethers, polythioether esters or polythioether ester amides.

Examples of suitable polyacetals are the compounds to be prepared from glycols, such as diethylene glycol, triethylene glycol, 4,4'-diethoxydiphenyldimethylmethane, hexanediol and formaldehyde. Suitable polyacetals can also be prepared according to the invention by polymerizing cyclic acetals.

Polycarbonates which are known per se as hydroxyl groups are suitable, which are known, for example, by reaction of diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with di-aryl carbonates, for example diphenyl carbonate, or phosgene can be prepared.

The polyester amides and polyamides include, for example, the products which are essentially linear condensates, which are obtained from polyvalent saturated and unsaturated carboxylic acids, their anhydrides and polyhydric saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.

Representatives of these compounds to be used according to the invention are described, for example, in "High Polymers, Part XVI, Polyurethanes, Chemistry and Technology", Interscience Publishers, New York, London,

Band I (1962) biz. 32-42 and biz. 44-54 and Band II (1964) biz. 5-6 and 198-199, as well as in "Kunststoff-Handbuch", 10 Band VII, Carl-Hanser-Verlag, Munich (1966), for example on the biz. 45-71.

. It is of course possible to use mixtures of the above-mentioned compounds with at least two isocyanate-reactable hydrogen atoms with a molecular weight of 400-10000, for example mixtures of polyethers and polyesters.

Also suitable as starting components according to the invention are compounds with at least two isocyanate-reactable hydrogen atoms with a molecular weight of 32-400. Also in this case, these are understood to mean compounds having hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups, preferably compounds having hydroxyl groups and / or amino groups, which serve as chain extension agent or cross-linking agent. These compounds usually have 2-8 isocyanate-reactable hydrogen atoms, preferably 2 or 3 reactable hydrogen atoms.

Also in this case, mixtures of different compounds with at least two isocyanate-reactable hydrogen atoms with a molecular weight of 32-400 can be used. As examples of such compounds can be mentioned: ethylene glycol, propylene glycol (1,2) and (1,3), butylene glycol (1,4) and - (2,3), pentanediol- (1,5 ), hexanediol (1,6), octanediol (1,8), neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol- (1,2,6) ), trimethylol ethane, pentaerythritol, quinitol, mannitol and sorbitol, diethylene glycol, tri-800 4 0 33 - 9 - ethylene glycol, tetraethylene glycol, polyethylene glycols with molecular weight up to 400, dipropylene glycol, polypropylene glycols with molecular weight up to 400, dibutylene glycol molecule-5 weight up to 400, castor oil, 4,41-dihydroxydiphenylpropane, di-hydroxymethylhydroquinone, 1,4-phenylene-bis- (>-hydroxyethyl ether), ethanolamine, N-methyl ethanolamine, diethanolamine, N-methyl diethanolamine, triethanolamine, 3-aminopropanol and ester diols of the general formulas 10 4 and 5 of the formula sheet, wherein R is an alkylene - represents arylene residue with 1-10, preferably 2-6, carbon atoms, x 2-6 and y 3-5 means, for example,--hydroxybutyl---hydroxycaproic acid ester, -hydroxyhexyl- X -hydroxybutyric acid ester, adipic acid bis-15 (^ -hydroxyethyl) ester and terephthalic acid bis (p-hydroxyethyl) ester.

As a chain extender, compounds such as 1-mercapto-3-aminopropane, optionally substituted amino acids, for example glycine, alanine, valine, serine and lysine, as well as optionally substituted dicarboxylic acids, for example succinic acid, adipic acid, phthalic acid, can also be used according to the invention. -hydroxyphthalic acid and 4-aminophthalic acid are used.

Furthermore, monofunctional compounds in amounts of 0.01-10% by weight, based on polyurethane solids, can be used as so-called chain-breakers relative to isocyanates. Such monofunctional compounds are, for example, monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearyl-30 amine, pyrrolidine, piperidine and cyclohexylamine, mono-alcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, the different amyl alcohols, cyclohexol ethylene glycol monoethyl ether, etc.

According to the invention, however, polyhydroxyl compounds can also be used, in which polyaducts or polycondensates of high molecular weight are present in finely dispersed or dissolved form. Such modified polyhydroxyl compounds are obtained when polyaddition reactions (e.g. 800 40 33-10 - conversions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between formaldehyde and phenols and / or amines) directly in situ in the above, compounds containing hydroxyl groups expire. Such methods are for example in the German "Auslegeschriften" 11 68 075 and 12 60 142, as well as in the German "Offenlegungsschriften" 23 24 134, 24 23 984, 25 12 385, 25 13 815, 25 50 796, 25 50 797, 25 50 833 and 50 5062. However, it is also possible, according to US Pat. Nos. 3,869,413 and German "Offenlegungs" 25 50 860, to mix a finished aqueous polymer dispersion with a polyhydroxyl compound and subsequently remove the water from the mixture.

When modified polyhydroxyl compounds of the above type are used as starting components in the polyisocyanate polyaddition process, in many cases polyurethane plastics with substantially improved mechanical properties are produced.

The oligomeric products are only added in small quantities to these starting materials. The oligomeric urethanes or urea compounds are prepared in a manner known per se. They are reaction products from monofunctional isocyanates with mono- or polyfunctional alcohols and / or amines. The release agents can also be used with foamable polyurethane compositions.

The internal release agents proposed according to the invention must comply with the general formulas described above. As a urethane-based release agent, 1,6-hexanedistearyl diurethane has proved particularly suitable.

Examples of particularly preferred substances are, for example, conversion products from monoisocyanates, such as monoisocyanates with 6-18 carbon atoms, for example stearyl isocyanate and / or palmitine isocyanate, optionally as a mixture with monoalcohols. As monoalcohols, especially alcohols with 6-18 carbon atoms have proved useful, for example 800 4 0 33

t V

- 11 - image stearyl alcohol or palmitic alcohol. Double bonds containing alcohols, such as, for example, oleyl alcohol, are also expedient. Conversion products from monoisocyanates with monoamines with 6-18 carbon atoms are further expedient.

A further mixture which has been found to be useful consists of reaction products of monoisocyanates with polyalcohols. As polyalcohols are, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-10 butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1.12 dodecanediol, hydroquinone bis-hydroxyethyl ether, glycerine, trimethyl propane, hexanetriol, pentaerythritol or the like. Polyethylene glycols with a molecular weight of 100-4000 are also preferred, in addition polyhydroxyl compounds with molecular weights between 650 and 6000, for example hydroxyl-containing polyesters, polyethers, polyester amides, polyacetals, polycarbonates, polycaprolactones and hydroxyl groups.

Mixtures of the alcohols among each other and mixtures of the oligomeric urethanes can also be used.

A further embodiment of the invention resides therein, polyamines such as, for example, ethylene-diamine, 1,6-hexanediamine, 1,4-tetramethylenediamine, 1,11-undecane-methylenediamine, 2,4- and 2,6-hexahydro-tolylene diamine, optionally use mixtures of the aforementioned substances, such as 4,4-diaminodiphenylmethane, p-xylylenediamine or hydrazine and substituted hydrazines, 3-amino-30-1-methylaminopropane or dipropylene triamine as starting materials.

According to the invention, conversion products from polyisocyanates and the above-described monoalcohols and monoamines are further proposed. Especially preferred are the technically readily accessible isocyanates, such as, for example, hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, modified 4,4'-diphenylmethane diisocyanates, 2,4- and 2,6-tolylene diisocyanate and mixtures of these substances and 800 4 0 33 - 12 - dimer fatty acid diisocyanates.

The oligomeric urethanes and urea compounds proposed as internal release agents according to the invention are then fully and incompletely used by conventional preparation methods. The internal release agents are incorporated into the high molecular weight polyurethane composition in a self-contained manner. A particularly suitable method consists in dissolving or dispersing the internal release agents in the starting compounds for the high molecular weight polyurethane compositions. If this is not desired or not possible, these can also be introduced during the thermoplastic processing of the polyurethane composition during the plasticizing operation. In many cases, an amount of 0.5-2.0 parts by weight, based on 100 parts by weight of the high molecular weight polyurethane polymer, already yields excellent results.

The invention is further elucidated with examples, in which all parts and percentages are parts by weight and percentages by weight, unless stated otherwise.

The following examples describe the preparation of oligomeric urethanes. The preparation methods described in the examples are applicable to oligomeric urethanes, ureas and thiourethanes.

The mono- or polyisocyanate and the active hydrogen-containing compound are mixed together and heated to higher temperatures, expediently at 130 ° C.

After a reaction time of about 30 minutes, the product is poured onto a cold plate and allowed to solidify. After it has been made small, the conversion product can then be used without further ado.

Table A lists the release agents used in the examples, which are continuously indicated in large letters for better overview.

Table A.

8004033 - 13 - 0 o -P in ö * · ρ σ \ Tt'cn '& o ^ T ^ c ^ cOr-i

Qj Ο'ιΟΟΙΠΗΟΟιΟΟ

4J rH Η ιΗ H

rH

§ w I o <Ö 01

> iH

ü H

0> h 01 -P Η · Η

H S

U (d - »id OiO

0) \ ns s s = S = = = Ρ H ·· ui> iin -, P vo h d, O Φ? s +>,

οι -P

C ^ J '- fÖ - id -P β o rö id er »(d>) m β o CN *

rH

m H ** O

h «» * 3 * m o h ü

* O H ^ O v I

rf! O i rH O]>) iH r-i rP H

ö>, H 1 I H I o 5 «O

φ pH O rH rH rH ** H ö O

pqtH Cr »· ΗΟΟΗΟΌΦκΉ pQ m Ü Ίί -Η · Η!> t · Η β Φ Η <0 ο Φ grOO-POidHtp fh -Ρ Φ βββββίΰ> (· Η Μ Η φφβφΦΟ, β'Ο 01> 1 Ο, ΦΦΛΦΦ -ΡΟ ο> χ: ο-ρ-ροχόφη ö -Ρ ρββφΦΟΦΟ-Ηχ: β φ & Λ Λ β, β Φ Ό -Ρ Οι -Ρ - -Η Η 3 g = = = = = = = β φ Η

rH

φ Φ

^ CN VOOO ^ OOCNr-M

φ VD r »<J> CTiOHOOCN

U Η ιΗ ΟΙ Η I — 1

rH

φ Φ Φ Η e 01 ο Η θ ’Η Φ β

I (<pquQHPnOKH

β Η 800 4 0 33 - 14 -

CO CO CM r * LD

<s \ cm ^ and r-m

H <H. CO CM

! ! I 1 H d <d fi

t> i <D> i <D

I -P CU O Φ I

O * H iH O H O

co 6 -s> i w> i co

• rl 1-1 O A * H i3 * P

Η Π3 Π + J Ή Η H

> 1 & 4 * 0) Ό fi O> 1 p \ m g i (ö 4J p = = cd h co td co -cd l td CD> t X - A (1)

+) P 1 0) I-) * · -P “-P

ratdc .d i o cm co <l> -P g -p ^ -s4j ^ td. i-i -id -—. «- *

H td P H (d H> i H (d Η H

o ^ td o e o d o fi o o = S «d g td go gtd g, g

P £ 3> t <W> i -P

CM td td rt O Η p rl O <Htd - 'fd> i' -O '-'Q - O - (0 - co wo and do td O co -H o + 4 ^ -ri lo td m in <Ti > i cn co · η tntd r · '· π o> io \ o

Ld O · Ρ ι-H T3 CM d IH ^ Ö CM O CM CM

• 1 d <! I +4 Φ

I -P

PI I 3 «

Hl ''

Sj rH i — I iH

I 0) I I H r-j EH I Μ Η H o o

I CT> O O A 5 H

öl I d -H -r) o 5 2

H I (D Ό Td o X A

O I g Ö β η O O

> i tdtdtd = = »A o p i d td td η η η φ I <D X + j> 1> 1 td

> I O O 0 P A H

A A td +4> 1 d o oo (d σι m 4-J l h

> LD ^ 01 CN O

• r * “>« * —s

rH «H

2 Q

g = = e - -

CM i-I

m * 'S' O o o o o co

O rt <«3« t '»CO O

r-t IT) m in CM | H CM

mhgso cp α 800 4 0 33 - 15 - rt Μ <N Ο ^ in σι cn + »fd rd fi <ö> 1 0 0 01 • HH> 1 k = = 5 (d Φ +> 01 tn in oo σι σι σ> cm m tn ih • I Ö row I (dl cd - JI Qj Ή Λ

0 I 0 1 H VO O

Sik Η 0-0 3 1 Οι 0 C to®

Ö I Η · Η φ ^ CM

10 Ό -Η

Cn 1 Η = I <0 r * · Η I ik Μ (d ra 3 0 Λ 1 +1 +) Q)> 1 + 1 ö 3 ar bi k i a> «Λ 0> · ffl 1 S ® Jh n

> I -Η -P Η M Q

^ k 3 0 0 6 -μ Λ Λ - in tn co cm η n co o ιΗ r-i in

Pi. CO Η D

ο η η ζ η 7 7 - 16 -

The polyurethane mixture composed according to the invention, which contains an internal release agent, is prepared as described below.

Example 1.5 In a stirred vessel, 100 parts by weight of a polyester from adipic acid and a mixture of ethylene glycol and butanediol (1: 1), as well as 20 parts by weight of the release agent C were heated to 120 ° C. After dewatering for 1 hour in vacuo, 850 parts by weight of 10 MDI (4,4'-diisocyanodiphenylmethane) was added. The mixture was stirred for 30 minutes. After this time, 240 parts by weight of butanediol were stirred over 30 seconds with further stirring. and the reaction product was poured onto a plate preheated to 110 ° C and left at this temperature for 15 hours.

After the polyurethane had cooled, it was granulated and sprayed into test plates on a commercially available hose injection molding machine. The test plates were annealed at 110 ° C for 12 hours. The mechanical properties (measured values) are listed in Table B.

Example II (comparative test).

Entirely the same polyurethane composition as in Example I was prepared without release agent C. The mechanical properties are again shown in Table B.

Under the conditions described in Example 1, 100 parts by weight of polycaprolactone (molecular weight 2000), 600 parts by weight of MDI (4,4'-diisocyanodiphenylmethane), 159 parts by weight of butanediol and 20 parts by weight of release agent F were used as starting materials. . The test results 30, as in the subsequent comparison test, are again included in Table B.

Example III.

The polyurethane composition was prepared as in Example 1. The following starting materials were used: 1000 parts by weight of polycaprolactone (MG 2000)

600 "MDI

. 159 "butanediol

20 "release agent F

800 4033 - 17 -

Example IV (comparative test).

The mixture shown in Example III was processed without release agent F.

TABLE B.

5 Example

Mechanical properties I II III IV

Hardness (Share A) 96 95 89 90 T Spine elasticity (%) 30 29 33 34

Tensile strength (N / irm ^) 37 36 29 27 10 Elongation at breaking load (%) 467 480 501 490

Wear 25 28 15 * 18

It can be seen that the mechanical properties of the starting materials are not affected by the addition of the release agent. The release agent can therefore be used without objection independently of the use of the polyurethane compositions.

Example V.

The release agent N was added to the mixture described in Example III.

Example VI.

The release agent O was added to the mixture shown in Example III.

Example VII.

The release agent Q was added to the mixture shown in Example III.

Example VIII.

The release agent S was added to the mixture shown in Example III.

Example IX.

To the mixture shown in Example III, the release agent was added.

An evaluation of the polyurethane mixtures according to Examples III-IX took place by manufacturing molded parts on a conventional injection molding machine. The mold was thereby equipped with an automatic ejection system. The detachment could therefore be judged by determining the detachment cycles with the different polyurethane compositions. There is always optimum release agent when the mixture can be released almost unlimited from the mold.

As can be seen from Table C, the test could always be interrupted after 200 cycles, because further measurements after 10 so many number of mold release cycles no longer change the result of the test. The compositions shown in Examples III and V-IX are therefore virtually unlimitedly moldable. The composition of Example IV (comparative test without internal release agent) yielded only 5 mold release cycles. An external release agent was necessary here, TABLE C.

Polyurethane composition according to Number of automatic cycles Example 20 III aborted after 200 cycles IV after 5 cycles external release agent necessary V after 200 cycles aborted VI after 200 cycles aborted 25 VII after 200 cycles aborted VIII after 200 cycles aborted IX after 200 cycles

In Examples III and V-IX, the mold was visually assessed after 200 cycles. No contamination of the mold was found.

Conclusions.

800 4033

Claims (9)

1. Easily moldable polyurethane composition, characterized in that the composition contains a high molecular weight urethane polymer and an internal release agent containing a small amount of at least one oligomeric product on a urethane and / or urea basis of the formula 1 , 2 or 3 of the formula sheet, wherein A, A ', B, B' and R are independently selected from hydrogen atoms, alkyl groups of 1-35 carbon atoms, aryl groups of 6-14 carbon atoms, and substituted aryl esters, the substituents being halogen atoms alkyl radicals of 1-35 carbon atoms, arylalkylthio radicals of 6-14 carbon atoms in the aryl and 1-35 carbon atoms in the alkyl moiety, arylthio radicals of 6-14 carbon atoms or aralkyl radicals of 7-15 carbon atoms, X are sulfur or oxygen atom and Y and Y 'are independently selected from alkylene radicals of 1-35 carbon atoms, arylene radicals of 6-14 carbon atoms, alkarylene radicals of 7-30 carbon atoms , aralkylene radicals of 7-20 carbon atoms, 20 - (CH2) 1-4-0- (CH2) 1-4- and - (CH2) 1-4-S- {CH2) 1-4 radicals or polyesters, polyethers, polycarbonates or polybutadienes with molecular weights of 400-4000, and wherein further at least one of the radicals A, B and R is a residue other than a hydrogen atom and wherein a and b as well as 0-1 are chosen such that the sum of a and b is at least 1. 2. Composition according to claim 1, characterized in that the urethane and / or urea-based oligomeric products are present in an amount of 0.01-10.00 parts by weight per 100 parts by weight of the high molecular weight urethane polymer. to be. Composition according to claim 2, characterized in that the urethane and / or urea-based oligomeric products in an amount of 800 40 33-20 - 0.1-1.5 parts by weight per 100 parts by weight of the urethane high molecular weight polymer. 4. Composition according to any one of claims 1-3, characterized in that 1,6-hexanedistearyl diurethane is used as the oligomeric product 5 on a urethane basis. 5. A composition according to any one of claims 1 to 3, characterized in that 1,6-hexanedistearyl urethane, distearyl urethane or oleyl stearyl urethane are used as the oligomeric product on urethane. Composition according to any one of claims 1 to 3, characterized in that the oligomeric product on urethane basis is the reaction product of 2 moles of stearyl alcohol and 1 mole of tolylene diisocyanate. 15 Composition according to any one of claims 1 to 3, characterized in that the reaction product of 1 mole of trimethylolpropane and 1 mole of stearyl isocyanate is used as the oligomeric product on a urethane basis. 20 Composition according to any one of claims 1 to 3, characterized in that the reaction product of 1 mole of trimethylolpropane with 2 moles of stearyl isocyanate is used as the oligomeric product on a urethane basis. ♦ 25 Composition according to any one of claims 1 to 3, characterized in that the reaction product of 1 mole of polybutadienol (functionality 2.3) with 2.3 moles of stearyl isocyanate is used as the oligomeric product on a urethane basis. 800 4 0 33