DE2851337A1 - High impact unsaturated polyester moulding materials - based on terminally unsaturated urethane group free polyesters and a rubbery elastic polymer - Google Patents

Abstract

Moulding materials are comprised of (a) 5-77 pts. wt. terminal unsaturated, urethane group-free polyesters, (b) 20-80 pts. wt. of a copolymerisable vinyl or vinylidene cpd. and (c) 3-25 pts. wt. of a rubbery elastic polymer with a glass transition temp. of -90 to 10 degrees C. On hardening, a second phase forms as particles with an av. dia. of 0.1-100 mu. The compsns. are relatively low viscosity clear solns. or storage stable dispersions with good handling properties. The cured prods. have high impact resistance and due to the high compatibility between the resin and the rubber additive, the rubber particles cannot be leached out with solvent as with prior art materials based on polyesters with randomly-distributed unsaturated gps., so that the cured prods. have improved chemical resistance.

Description

Molding compounds based on unsaturated polyester,

Process for their manufacture and their use.

The present invention relates to molding compositions based on "Terminally unsaturated polyesters free of urethane groups, copolymerizable therewith Vinyl or vinylidene compounds and rubber elastic polymers.

Molding compositions made from polyesters with randomly distributed ethylenically unsaturated Structural units, copolymerizable monomers and rubber-like polymers are known (see DE-AS 1 166 467; 1 241 983; US patents 3 231 631; 3 688 178; 3,882,078; 3,857,812; 3 674 893).

Hardened molded bodies produced from these molding compounds have good dimensional accuracy, but not sufficient for all purposes -Impact toughness. In addition, the lack of compatibility between the rubber-like Component and the resin often cause problems with regard to the handling of the delivery form, which either consists of two components or must contain additional additives, which can be dissolved out when the hardened products come into contact with solvents, whereby the favorable chemical resistance of the cured unsaturated polyester resin compositions is prevented.

The invention relates to curable molding compositions composed of a) 5 to 77 parts by weight of a "terminally unsaturated" urethane-free polyester b) 20-80 parts by weight a vinyl or vinylidene compound copolymerizable therewith and c) 3 to 25 parts by weight a rubber elastic polymer with a glass transition temperature between -90 and + 100C, with hardening a second phase as particles with a should form an average diameter of 0.1 to 100 μm.

According to a preferred embodiment of the invention, the specific The fracture surface energy of the copolymer from a) and b) formed during curing (i.e. in the absence of c) a value> 0.5. 105, preferably between 0.5 . 105 and 1 o6, erg / cm2 (measured according to the method of L.J. Broutman, F.J.

Mc Garry at 250C, J. Applied Polym. Sci. 9, 589 f (1965)) the Molding compositions of the invention represent relatively low-viscosity clear solutions or storage-stable Dispersions are. When cured, they provide moldings with a considerably higher level Impact strength with practically unchanged heat resistance compared to the known compositions based on polyesters with randomly distributed unsaturations Structural units.

"Terminally unsaturated" polyesters free of urethane groups in the sense of the invention are those in which each of the first dicarboxylic acid residue of the counted from both ends of the linear polymer chain, an ethylenically unsaturated one Contains double bond, while the remainder of the molecule does not contain any further copolymerizable Ethylenically unsaturated double bond has more.

"Terminally unsaturated" urethane group-free polyesters are known (see DE-AS 2 052 961). Depending on their composition, they form after copolymerization rubber-elastic, leather-like or rigid with vinyl or vinylidene compounds, glass-like transparent body. The increase in impact strength is also due here Reduction of the heat resistance, strength and rigidity bought at the price.

The polyester a) and the rubber-elastic polymer c) must be whole meet certain conditions so the desired properties of the moldings produced from the molding compositions are achieved: The inventive Before curing, molding compounds form a relatively low-viscosity, clear mixture or a storage-stable dispersion and, after curing, a two-phase system with a Glass transition temperature between -90 and +1000 for aie rubbery phase and another glass transition temperature between 50 and 250 ° C for the resin phase, characterized by the position of the loss modulus maxima of the complex shear modulus in Dependence on the temperature at 1 Hz, or detectable by electron microscopy Particles with a mean diameter of 0.1 to 100 / µm.

The preferred embodiment, according to which the specific fracture surface energy of the copolymer of components a) and b)> 0.5. Should be 105 erg / cm², one obtains taking into account the constitution of a) and b) following a few simple rules: an increase in the crosslinking density in the a, / bapolymerisatt an increase in the proportion of aranatic and / or cycloaliphatic groups and a reduction in the number of atoms between the two double bonds in the polyester a) lead to a reduction in the specific fracture surface energy. Knowing this You can regulate - with given components, even just by defining them the mixing ratio a / b - in case of doubt after a small number of orienting Preliminary tests - produce the preferred embodiment effortlessly and reproducibly.

Preferred “terminally unsaturated polyesters free of urethane groups correspond to the formula I. where R1 is the divalent radical of a polyester which is reduced by two hydroxyl groups and does not contain any C, β-ethylenically unsaturated groups, X, Y and R are hydrogen or C1-C6-alkyl. These "terminally unsaturated" urethane group-free polyesters can be prepared by a multistage process, namely by reacting 1 mole of at least one organic dicarboxylic acid with 1.05-2.0 moles of at least one organic diol and then reacting 1 mole of the resulting diol Saturated polyester containing hydroxyl groups with the approximately equivalent amount, preferably 1.9-2.2 of at least one tC, ß-ethylenically unsaturated dicarboxylic acid anhydride, the corresponding unsaturated dicarboxylic acid or its half ester.

The molding compositions according to the invention can therefore be obtained by in the first stage 1 mol of at least one organic dicarboxylic acid with 1.0 - 2.0 moles of at least one organic diol, preferably in the melt at 150 - 220UC, if necessary in the presence of customary inhibitors, with elimination of water esterified and in the second stage 1 mole of the OH group-containing obtained in this way Pre-product with the approximately equivalent amount, preferably 1.9 to 2.2 mol1 at least a c>, ß-ethylenically unsaturated dicarboxylic acid anhydride, the corresponding unsaturated dicarboxylic acid or its monoester at about 60 to 1400C in the melt added or, as has been described for the 1st stage, implemented, and 5 - 77 parts by weight of the "terminally unsaturated" urethane-free polyester thus obtained a) with 20-80 parts by weight of a vinyl or vinylidene compound copolymerizable therewith b), 3 - 25 parts by weight of a rubber elastic polymer c) and optionally mixes other auxiliaries and additives.

As a hydroxyl group-containing linear polyester used for manufacture "Terminally unsaturated" polyesters are preferred, come polycondensation products of aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids with usually 2 - 16 carbon atoms or their ester-forming derivatives with at least a diol with usually 2 to 24 carbon atoms in question.

These linear polyesters should have an average molecular weight (number average Mn) from 200 to 3000.

Organic diols preferred for making the linear polyesters are e.g. dihydroxy compounds with 2 - 24 carbon atoms such as ethylene glycol, 1,2-propanediol and -1,3, diethylene glycol, dipropylene glycol, butanediol-1,2, -1,3 and -1,4, neopentyl glycol, 2-Ethylpropanediol-1,3, hexanediol-1,6, 2,2-bis- (4-hydroxycyclohexyl) -propane, bis-oxalkylated Bisphenol A, as well as linear polyesters containing hydroxyl groups, which are free of copolymerizable X are carbon-carbon multiple bonds; preferred dicarboxylic acids are e.g. Succinic acid, adipic acid, sebacic acid, phthalic acid, iso- and terephthalic acid, Hexa- or tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, tetrachlorophthalic acid, Hexachloro-endomethylenetetrahydrophthalic acid.

For the production of the "terminally unsaturated" urethane groups-free Preferred polyester compounds are αβ-ethylenically unsaturated dicarboxylic acid anhydrides or dicarboxylic acids with usually 4 to 10 0 atoms, for example maleic anhydride, Citraconic anhydride, maleic acid, fumaric acid, itaconic acid, mesaconic acid or chloromaleic acid or their half-esters.

Preferred copolymerizable vinyl and vinylidene compounds im For the purposes of the invention, the unsaturated ones customary in polyester technology Compounds that are preferably cL-substituted vinyl groups or B-substituted allyl groups wear, preferably styrene; but also, for example, nuclear chlorinated and alkylated respectively.

-alkenylated styrenes, the alkyl and alkenyl groups 1 - 4 or Can contain 2 - 4 carbon atoms, such as vinyltoluene, divinylbenzene, oC-methylstyrene, tert-butylstyrenes, chlorostyrenes; Vinyl esters of carbonic acids with 2 - 6 carbon atoms, preferably vinyl acetate; Vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, acrylic acid and methacrylic acid and / or its esters (preferably vinyl, allyl and methallyl esters) with 1 - 4 carbon atoms in the alcohol component, ire amides and nitriles, maleic anhydride, - half and diesters with 1 - 4 carbon atoms in the alcohol component, - half - and diamides or cyclic imides such as N-methyl maleimide or N-cyclohexyl maleimide; Allyl compounds such as allylbenzene and allyl esters, such as allyl acetate, diallyl phthalate, Isophthalic acid diallyl ester, diallyl fumarate, allyl carbonate, Diallyl carbonate, triallyl phosphate and triallyl cyanurate.

Preferred rubber-elastic polymers are, for example, those based on of natural rubber or synthetic rubbers, e.g. polymers made from conjugated Diolefins such as butadiene, dirnethylbutadiene, isoprene and its homologues or copolymers conjugated diolefins with polymerizable vinyl and vinylidene compounds, such as Styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, acrylates, methacrylates, e.g.

Acrylonitrile, butadiene rubbers, acrylate rubbers, chlorinated rubbers, Acrylonitrile / butadiene / styrene copolymers (ABS); also polyalkylene oxides, polylactones such as oolycaprolactone, polylactams such as polycaprolactam; saturated polyesters, polysilicones and polycarbonates, provided they are modified to have rubber-like properties own; but preferably rubber-like ethylene copolymers and rubber-like ones Polyurethanes.

Ethylene copolymers are sometimes used as copolymers of ethylene and vinyl esters of aliphatic saturated monocarboxylic acids with 1 to 18 0 atoms, especially vinyl acetate and vinyl propionate, with a vinyl ester content of 10 - 90 % By weight and a Mooney TJiskosity of at least 5 Mooney (measured according to DIN 53 523) and graft polymers based on these polymers.

Vinyl and vinylidene aromatics are preferably suitable as graft monomers such as vinyltoluene, α-methylstyrene, tert-butylstyrene, chlorostyrenes, are preferred but unsubstituted Styrene itself; Vinyl acetate, (meth) acrylic acid, their nitriles and esters, the alcohol components of which can contain 1 - 8 carbon atoms, such as methyl methacrylate or ethyl acrylate, (meth) acrylonitrile, maleic anhydride, Maleic acid half and diesters with 1-8 carbon atoms in the alcohol component, isoprene. Of course, they can be used both as graft substrates and as graft monomers Mixtures of the listed compounds are used.

The preferred polymers also include vinyl alcohol-containing polymers Products made by partial saponification of the ethylene / vinyl ester copolymers listed respectively.

the graft polymers can be produced and hydroperoxide groups containing products which can be produced by oxidation of the substances listed are.

The aforementioned graft polymers can be prepared by known processes getting produced.

For example, graft polymers made from ethylene / vinyl ester copolymers can be used with grafted units of a vinyl aromatic and (meth) acrylonitrile e.g. after the methods of British patent specification 917 499 or the German Offenlegungsschriften 1 964 479 and 2 137 780.

The preferred graft polymers to be used from ethylene / vinyl ester cooolymerisates with grafted units of a mixture of vinyl aromatics, (xeth) -acrylonitrile undLOlefins with 2-18 C-atoms can be prepared according to the procedures of the German Offenlegungsschriften 2 215 588 or 2 305 681.

As a vinyl ester for the production of the ethylene / vinyl ester copolymer graft base organic vinyl esters of saturated, possibly halogen, come through in particular Chlorine, substituted monocarboxylic acids with i - 18 carbon atoms in question. Namely may be mentioned: vinyl formate, vinyl acetate, vinyl propionate, vinyl chloropropionate, vinyl butyrate, Vinyl isobutyrate, vinyl caproate, vinyl laurinate, vinyl myristinate, vinyl stearate, vinyl benzoate, preferably vinyl acetate.

The ethylene / vinyl ester copolymers are made by known processes the high or medium pressure synthesis, if necessary in solvents such as tert-butanol.

Nuclear-substituted alkylstyrenes may be used as grafted vinyl aromatics with 1 - 5 carbon atoms in the alkyl radical such as 4-methylstyrene, ° 4-methylstyrene, halostyrenes such as 4-chlorostyrene or mixtures thereof, preferably styrene, mentioned.

The grafted-on monoolefins can have 2-18, preferably 2-8, carbon atoms own.

The following monoolefins may be mentioned by name: ethylene, propylene, Butene-1, butene-2, isobutylene, 2-methylbutene-2, 3-sflethylbutene-1, diisobutylene, Triisobutylene, pentene-1, 4-methylpentene-1, octadecene-1, cyclopentene. Propylene, 1-butene, isobutylene or mixtures thereof are preferred.

The elastomeric polyurethanes c) are preferably linear built up and have average molecular weights of 10,000 to 1,000,000, preferably 20,000 to 500,000 (determined by membrane osmometry).

The preparation can be carried out in a manner known per se by implementing a Connection with at least two isocyanate-reactive hydrogen toffatcoen, preferably a polyhydroxyl compound with a molecular weight above 600, optionally a compound having two isocyanate-reactive hydrogen atoms and a molecular weight below 600, and a polyisocyanate.

As to be used for the production of the elastomeric polymers c) Starting components are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates in Betrac; at, such as those described by W. Siefken in Justus Liebigs Annalen der Chemie 562, pages 75 to 136, are described, for example Ethylene diisocyanate, 1,4-tramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-methyl-2,4-diisocyanato-cyclohexane, 1-methyl-2,6-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DE-AS 1 202 785, US patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate 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, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2 4 '- and / or -4,4'-diisocyanate, 4,4 '-diphenylpropane diisocyanate, naphthylene-1,5-diisocyanate, triphenylmethane-4,4', 4 "-triisocyanate, Polyphenyl-polymethylene-polyisocyanates, as produced by aniline / formaldehyde condensation and subsequent phosaenation and e.g. in the British patents 874 430 and 848 671 are described, m- and p-Isocyanatophenylsulfonyl-isocyanate according to the American patent 3 454 606, perchlorinated aryl polyisocyanates, as it is e.g. in the German Auslegeschrift 1 157 601 (American patent specification 3,277,138), polyisocyanates containing carbodiimide groups, such as they in German patent specification 1 092 007 (American patent specification 3 152 162), diisocyanates as they are in the American patent 3,492,330, polyisocyanates containing allophanate groups, such as they e.g. in British patent specification 994 890, Belgian patent specification 761 626 and published Dutch patent application 7 102 524 are, isocyanurate groups containing polyisocyanates, such as those in the American U.S. Patent 3,001,973, in German patents 1 022 789, 1 222 067 and 1 027 394 as well as in German Offenlegungsschrift 1 929 034 and 2 004 048 describe polyisocyanates containing urethane groups, as e.g. in the Belgian patent specification 752 261 or in the American U.S. Patent 3,394,164, containing acylated urea groups Polyisocyanates according to German Patent 1,230,778, containing biuret groups Polyisocyanates, such as those described in German Patent 1 101 394 (American Patents 3,124,605 and 3,201,372) and in British Patent Specification 889 050 are described, polyisocyanates produced by telomerization reactions, as described, for example, in US Pat. No. 3,654,1067 ester groups containing polyisocyanates such as those in the British patents 965,474 and 1,072,956, in US Pat. No. 3,567,763 and in US Pat German Patent 1,231,688, reaction products of the above Isocyanates with acetals according to German Patent 1,072,385 and polymers Polyisocyanates containing fatty acid residues according to the American patent 3,455,883.

It is also possible to use the technical isocyanate production resulting distillation residues containing isocyanate groups, if appropriate solved in one or more of the aforementioned polyisocyanates to be used. Furthermore is it is possible to use any mixtures of the aforementioned polyisocyanates.

As a rule, those that are technically easily accessible are particularly preferred Polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers (TDI "), polyphenyl-polymethylene-polyisocyanates, as produced by aniline / formaldehyde condensation and subsequent phosgenation are produced ("raw, hDI"), and carbodiimide groups, Urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups containing polyisocyanates ("modified polyisocyanates").

Connections are also preferred starting components with at least two isocyanate-reactive hydrogen atoms with a molecular weight usually from 600 to 10,000 Amino groups, thiol groups or compounds containing carboxyl groups, preferably Polyhydroxyl compounds, in particular containing two to eight hydroxyl groups Compounds, especially those with two hydroxyl groups of molecular weight 800 up to 10,000, preferably 1,000 to 6,000, e.g.

at least two, usually 2 to 8, but preferably 2, hydroxyl groups comprising polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyamides and polyester amides, such as those used for the production of homogeneous and cellular Poly urethanes are known per se.

Preferred polyhydroxyl compounds with a molecular weight above In addition to polyester amides or polyacetals, 600 are in particular linear or predominantly linear polyesters and polyethers.

The possible hydroxyl group-containing polyesters are e.g. reaction products of polyvalent, preferably divalent and optionally additionally trihydric alcohols with polybasic, preferably dibasic Carboxylic acids. Instead of the free polycarboxylic acids, the corresponding Polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of C1-C6 alcohols or mixtures of these can be used to produce the polyesters.

The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. by halogen atoms, or be multiply substituted and / or unsaturated.

Preferred examples include: succinic acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, Terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, Glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimers and trimer Fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, dimethyl terephthalate and terephthalic acid bis-glycol esters. Preferred polyhydric alcohols are e.g. ethylene glycol, 2-ethylpropanediol-1,3, propylene glycol- (1,2) and - (1,3), diethylene- and dipropylene glycol, butylene glycol- (1,4), - (1,3) and - (2,3), pentanediol-1,5, hexanediol- (1,6), Octanediol <1.8), neopentyl glycol, cyclohexanedimethanol (1,4-bishydroxymethylcyclohexane), 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol (1,2,6) butanetriol (1,2,4), Trimethylolethane, pentaerythritol, methyl glycoside, also diethylene glycol, triethylene glycol, Tetraethylene glycol, higher polyethylene glycols, polypropylene glycols, dibutylene glycol and higher polybutylene glycols in question. The polyesters can have terminal carboxyl groups exhibit. Also polyesters made from lactones, e.g. £ caprolactone, or from straight-chain Hydroxycarboxylic acids with at least 5 carbon atoms, e.g. @ -hydroxycaproic acid, can be used.

The polyesters are produced under such conditions that their End groups consist at least for the most part of hydroxyl groups. aside from that Polyethers, such as propylene oxide or tetrahydrofuran polymers, are also suitable Polythioethers, such as condensation products of thiodiglycol with them self or other diols. These products generally have an average molecular weight from about 600-5000, preferably from 1000-2500.

Also the at least two in question according to the invention in the As a rule, two to eight, preferably two, hydroxyl groups are polyethers those of the type known per se and are made, for example, by polyaddition of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, e.g. in the presence of BF3, or through the addition of these epoxides, optionally in a mixture or in succession, of starting components with reactive ones Hydrogen atoms such as water, alcohols, ammonia or amines, e.g.

Methanol, ethanol, ethylene glycol, propylene glycol- (1,3) or - (1,2) Dihydroxy-diphenylpropane, butylene glycol- (1,) or - (2,3), hexanediol- (1,6), octanediol- (1,8), Neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, glycerine, Hexanetriol (1,2,6), butanetriol (1,2,4), trimethylolethane, pentaerythritol, phenol, Resorcinol, isononylphenol, hydroquinone, 1,2,2-tris (hydroxyphenyl) ethane, methylamine, Ethylenediamine, tetra- or hexamethylenediamine, diethylenetriamine, ethanolamine, di- and triethanolamine, aniline, phenylenediamine, 2,4- and 2,6-diaminotoluene and polyphenylpolymethylene polyamines, as obtained by aniline / formaldehyde condensation.

Often those polyethers are preferred that are predominantly (up to 90% by weight, based on all OH groups present in the polyether) primary OH groups exhibit.

Polyethers modified by vinyl polymers, such as those used e.g. arise from the polymerization of styrene and acrylonitrile in the presence of polyethers (American patents 3,383,351, 3,304,273, 3,523,093, 3,110,695, German Patent specification 1,152,536) are suitable.

Among the polythioethers are in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, Formaldehyde, aminocarboxylic acids or amino alcohols are listed. Depending on the co-components If the products are polythio mixed ethers, polythioether esters or Polythioether ester amides.

Preferred polyacetals include those made from glycols, such as diethylene glycol, Triethylene glycol, 4,4'-dioxydiphenyldimethylmethane, hexanediol and formaldehyde can be prepared Connections in question. Cyclic acetals can also be polymerized produce suitable polyacetals according to the invention.

Polycarbonates containing hydroxyl groups are preferred of the type known per se, e.g. by reacting diols such as propanediol- (1,3), Butanediol <1.4) and / or hexanediol (1.6), diethylene glycol, triethylene glycol or Tetraethylene glycol with diaryl carbonates, e.g.

Diphenyl carbonate, or phosgene can be produced.

Preferred polyester amides and polyamides include, for example from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyhydric saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures, predominantly linear condensates.

Polyhydroxyl compounds also already contain urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates like starch, are suitable. Addition products of alkylene oxides to phenol / Formaldehyde resins or urea / formaldehyde resins can be used according to the invention.

Representatives of these compounds to be used according to the invention are for example, in High Polymers, Vol.XVI, "Polyurethanes, Chemistry and Technology" by Saunders-Frisch, Interscience Publishers, New Kork, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5-6 and 198-199, as well as in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl Hanser-Verlag, Munich, 1966, e.g. on the pages 45-71.

Mixtures of the abovementioned compounds can of course be used with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 600 - 10,000, e.g. mixtures of polyethers and polyesters, can be used.

As Ausganos components optionally to be used according to the invention Compounds are also used for the production of rubber-elastic polyurethanes with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-600 in question. This is also understood to mean in this case Hydroxyl groups and / or amino groups and / or thiol groups and / or carboxyl groups containing compounds, preferably containing hydroxyl groups and / or amino groups Compounds that serve as xette extenders. These connections show generally 2 to 8, preferably 2, isocyanate-reactive hydrogen atoms on.

On compounds with at least two reactive with isocyanates Hydrogen atoms and a molecular weight below 600 (chain extender) are in addition to water or simple glycols, glycols with urea, urethane, carbonamide or ester groups and those with tertiary nitrogen atoms.

Also on the possibility of using glycols with aromatic Ring systems, for example 1,5-naphthylene-s-dioxäthylether or hydroquinone-ßdioxäthyläther, should be noted. Furthermore are also Diamines, such as o-dichlorobenzidine, 2,5-dichlorophenylenediamine or 3,3'-dichloro-4,4'-diaminodiphenylmethane as well suitable as amino alcohols, such as N-allylethanolamine, amino or oxycarboxylic acids.

Examples of such compounds include: water, ethylene glycol, Propylene glycol-t1,2) and - (1,3), butylene glycol- (1,4) and - (2,3), pentanediol- (1,5), Hexanediol (1,6), octanediol (1, B), neopentyl glycol, 1,4-bis-hydroxymethyl-cyclohexane, 2-methyl-1,3-propanediol, glycerol, trimethylolpropane, kexanetriol- (1,2,6), trimethylolethane, Pentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols with a molecular weight up to 600, dipropylene glycol, polypropylene glycols with a Molecular weight up to 600, dibutylene glycol, polybutylene glycols with a molecular weight up to 600, 4,4'-dihydroxydiphenylpropane, bis-hydroxymethyl-hydroquinone, ethanolamine, Diethanolamine, triethanolamine, 3-aminopropanol, ethylenediamine, 1,3-diaminopropane, 1-mercapto-3-aminopropane, 4-hydroxy or aminophthalic acid, succinic acid, adipic acid, Hydrazine, N, N'-dimethylhydrazine, 4,4'-diaminodiphenylmethane, tolylenediamine, methylene-bis-chloroaniline, Methylenebis-anthranilic acid esters, diaminobenzoic acid esters and the isomeric chlorophenylenediamines.

In this case too, mixtures of different compounds can be used with at least two isocyanate-reactive hydrogen atoms with a molecular weight of 32-600 can be used.

According to the invention, polyhydroxyl compounds can also be used, in which high molecular weight polyadducts or polycondensates in finely dispersed or dissolved form are included. Such modified polyhydroxyl compounds are obtained when polyaddition reactions (e.g. 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-mentioned hydroxyl groups having compounds can drain. Such methods are for example in the German Auslegeschriften 1 168 075 and 1 260 142 as well as the German Offenlegungsschriften 2324134, 34, 2 423 984, 2 512 385, 2 513 815, 2550796, 2 550 797, 2 550 833 and 2 550 862. However, it is also possible, according to US Pat.

German Offenlegungsschrift 2,550,860 discloses a finished aqueous polymer dispersion to mix with a polyhydroxyl compound and then out of the mixture remove the water.

The production of the rubber-elastic ones preferred for the invention Polyurethane elastomers can be made by using the polyhydroxyl compounds a molecular weight above 600 with less than that calculated on the end groups Amount of a diisocyanate reacts, the compound with two reactive hydrogen atoms and a molecular weight below 600 and the reaction with another Diiso- addition of cyanate leads to completion. But you can also proceed in this way that the polyhydroxyl compounds with an excess of diisocyanates over the to react with the end groups required amount and the amount of the compound with a molecular weight below 600 so dimensioned that an excess over the itself is present based on the amount of isocyanate groups still present.

Of course, you can also use the mixture of polyhydroxyl compounds a molecular weight above 600 and the compound with a molecular weight below React 600 with an excess of diisocyanates.

The molding compositions according to the invention can be prepared by dispersing the rubber-elastic Polymers in a mixture of the "terminally unsaturated" urethane group-free Polyester and the copolymerizable vinyl or. Vinylidene compound at 20 to 80 ° C. It is of course also possible to use the rubber-elastic To disperse polymers at 20 to 80 0C in the copolymerizable compound and this dispersion with the "terminally unsaturated" polyester dispersion to mix in the copolymerizable compound.

In order to prevent premature gelation, the inventive Customary amounts of molding compounds, i.e.

0.001 to 0.1% by weight, based on the sum of components a), b) and c) polymerization inhibitors are added, e.g., hydroquinone and alkylated Hydroquinones such as toluhydroquinone, dimethylhydroquinone, trimethylhydroquinone or p-tert.-butylhydroquinone, p-tert-butylpyrocatechol, p-benzoquinone, chloranil, naphthoquinone, copper compounds such as copper naphthenate or copper octoate, addition compounds of Cu (I) halides on phosphites, such as z * BO Cu (I) Cl / triphenyl phosphite, Cu (I) Cl / trimethyl phosphite, Cu (I) Cl / trischloroethyl phosphite or Cu (I) Cl / tripropyl phosphite, phenols or phenol derivatives such as 4,4'-bis- (2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris- (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene or 4,4'-butylidene-bis- (6-tert. -butyl-m-cresol), secondary arylamines, such as phenyl-ß-naphthylamine or 4,4'-bis- (α, α-dimethylbenzyl) -diphenylamine, Phenothiatine, p-nitroso-dimethylaniline and other stabilizers as described in "Methods of organic chemistry (Houben-Weyl), 4th edition, Volume XIV / 1, pp. 433 - 452, 756, Georg Thieme-Verlag, Stuttgart 1961 are described.

Before curing, the molding compositions according to the invention can be given the usual amounts, preferably 0.5-5% by weight, based on the sum of components a), b) and c), Polymerization initiators can be added, e.g.

Diacyl peroxides such as diacetyl peroxide, dibenzoyl peroxide, di-p-chlorobenzoyl peroxide, tert-butyl peroxide, peroxy esters such as tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-butyl peroctoate, dicyclohexyl peroxydicarbonate or 2,5-dimethylhexane-2,5-diperoctoate, Alkyl peroxides such as bis (tert-butylperoxybutane), dicumyl peroxide, tert-butylcumyl peroxide, Hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide, cyclo- hexanone hydroperoxide, Methyl ethyl ketone hydroperoxide, perketals, acetylacetone peroxide or azoisobutyrodinitrile.

The resin compositions produced according to the invention can contain up to 300% by weight, preferably 50-200% by weight, based on the sum of components a), b) and c), Absorb fillers and reinforcing agents. As such, inorganic materials are like Barite, calcium carbonate, silicates, clays, chalk, lime, coal, asbestos, glass, Metals and organic materials such as cotton, sisal, jute, polyester, polyamides, preferably in the form of fibers. Are preferred as reinforcing material Glass fibers in any form, especially in the form of mats, are used.

The masses can also be used to reduce the occurrence of hardening Polymerization shrinkage, generally known shrinkage-reducing additives added are like thermoplastic polymers, polycondensates or pole addition compounds.

The molding compositions according to the invention can be used as chemical thickeners known oxides and hydroxides of the metals of the 2nd main group of the periodic table (See also Hofmann, W. Rüdorff, Inorganische Chemie, 16th ed., Friedr. Vieweg & Sohn, Braunschweig 1956, periodic table p. 152), preferably magnesium and calcium, in Quantities of 0.1-10, preferably 1.0-3.0% by weight, based on the sum of the components a), b) and c) are added, also accelerating the chemical thickening or regulating additives, such as 0.1-0.5% by weight of water or additives according to DE-OS 1 544 891, e.g. aliphatic carboxylic acids or partial phosphoric acid esters, or according to DE-OS 2,326,103, e.g. an organic amide in effective amounts.

Mixing the various components of the molding compositions according to the invention is expediently carried out in kneaders, dissolvers or roller mills.

In addition, of course, if desired, inorganic or organic Pigments, dyes, lubricants and release agents such as zinc stearate, thixotropic agents, UV absorbers etc. are added in the usual amounts.

The molding compositions according to the invention can be pressureless or under pressure from 3 - 300 kp / cm² at approx. 70 - 180 ° C. Besides, the hardening is at 15-250C using accelerators such as amines, in particular aromatic amines or cobalt salts, possible. Moldings can be produced from the molding compositions of all kinds, such as containers, body parts, machine covers.

EXAMPLES In the following parts are parts by weight and percentages mean percentages by weight.

I. Rubber-elastic polymers A. Partially saponified ethylene / vinyl acetate copolymer the composition 13.6% ethylene units 67.7% vinyl acetate. units 18.7% Vinyl alcohol units (Mooney viscosity ML 4 '= 18; freezing temperature from differential thermal analysis with a heating time of 20 ° C / min .: 50C.) BßF: polyurethane elastomers Polyurethane polyester polyisocyanate chain extender Mn + freezing - ++ temperature ° C B 1000g adipic acid / 87 g isomer mixture ---- 63 800 -30 ethylene glycol- (80:20) from 2.4- and polyester of OH- 2.6-diisocyanatotoluene number 56 C 1000 g adipic acid / 81.2 g isomer mixture ---- 52 300 -43 butanediol-1,4-poly- (80:20) from 2.4- and ester of OH number 2.6-diisocyanatotoluene 52.4 D 1000 g adipic acid / 206 g 4.4'-diisocyanate 35.5 g butanediol-1.4 107 000 -28 propanediol-1.2 / ethyto-diphenylmethane lenglycol polyester the OH number 56.5 molar dio ratio 2: 8 E 1000 g adipic acid / 206 44'-diisocyanato- 33 g 1,4-butanediol 76 800 -34 1,6-hexanediol / neodiphenyl methane pentyl glycol polyester the OH number 56.2 molar dio ratio 2: 1 F 1000 g adipic acid / 163.5 g 4,4'-diisocyanate 16.8 butanediol-1,4 62 600 -39 butanediol-1,4-polynato-diphenylmethane ester der OH number 52.4 + membrane osmosis with dioxane as solvent, ++ differential thermal analysis with a Le A 19 277 heating rate of 20 ° C / min.

II. Molding compounds example? 332 g of isophthalic acid are mixed with 318 g of diethylene glycol Esterified at 1800C under nitrogen until the acid number is less than 2. Thereafter the temperature is lowered to 1000C and 196 g of maleic anhydride and 0.15 g hydroquinone added. The reaction is continued at 1000C until the difference from the total acid number and half-ester acid number is less than 5. Then will a 44% solution of the polyester obtained in styrene was prepared.

In this solution, 12% of the rubber-elastic polymer is under Passing air through at 60 ° C., dissolved or dispersed.

The resulting solution or dispersion becomes plates (20 x 20 cm) potted and after adding 3 parts of benzolyl peroxide paste (50% in dibutyl phthalate) Cured for 3 hours at 75 ° C. This is followed by an additional 15 hours of tempering at 900C. Standard small rods for measuring the impact strength are made from the plates obtained and the softening temperature cut.

The results are shown in Table 1.

Table 1 Delivery form cured product, rubber appearance, viscosity Impact softening load. Poly- (mPa.s) dependency temp. + Mer (kJ / m²) (° C) - clear 120 15 76 A clear 6800 50 76 B slightly cloudy 3650 49 75 C clear 3100 65 74 D slightly trUb 6400 71 72 + differential thermal analysis with a heating rate of 200C / min.

BeisDiel 2,332 g of isophthalic acid are mixed with 402 g of dipropylene glycol Esterified at 1800C under nitrogen until the acid number has dropped below 2. Then the temperature is lowered to 1000C and 196 g of maleic anhydride and added 0.15 g of hydroquinone. The reaction is continued at 1000C until the The difference between the total acid number and the half-ester acid number is less than 5. Afterward a 44% solution of the unsaturated polyester in styrene is produced.

Further processing as in Example 1. The table shows the results 2: Table 2 Delivery form rubber appearance viscose hardened product elastic polymer ity impact-softening (mPa.s) toughness temp.

(kJ / m²) (° C) - clear 50 11.4 77 E slightly cloudy 5200 71 77 Example 3,332 g of isophthalic acid are mixed with 156 g of neopentyl glycol and 150 g of diethylene glycol Esterified at 1800 C under nitrogen until the acid number has dropped below 2. The temperature is then lowered to 1000 C and 196 g of maleic anhydride and 0.15 g hydroquinone added.

The reaction is continued at 1000C until the difference in the total acid number and half ester acid number is less than 5. Then the unsaturated polyester 44% dissolved in styrene.

Further processing as in Example 1. The table shows the results 3.

Table 3 Delivery form cured product, rubber appearance, viscosity Impact strength softening load poly (mPa.s) ability temp.

mer (kJ / m²) (° C) - clear 100 15 76 E clear 8400 64 75 F clear 6600 62 76 Example 4 332 g of isophthalic acid are mixed with 229 g of 2-ethylpropanediol-1,3 and 85 g of diethylene glycol esterified at 1800C under nitrogen until the acid number has dropped below 2. this lowers the temperature to 100 ° C and 196 g maleic anhydride and 0.15 g hydroquinone were added. The reaction is at 1000C continued until the difference between the total acid number and the half-ester acid number is smaller than 5 is. The unsaturated polyester 44% is then dissolved in styrene.

Further processing as in Example 1; the results are shown in the table 4: Table 4 Delivery form cured product, rubber appearance, viscose impact softening load Poly- ty low-toughness (mPa.s) (kJ / m²) temperature.

- clear 250 11.8 76 D clear 6030 55 75 E clear 450Q 55 75 the Specific fracture surface energies for the copolymers from a) terminally unsaturated Polyesters and b) styrene are: Example erg / cm2 1 4.5 x 2 2.9 x 3 3.5 x 105 4 2.2 x 105

Claims (4)

Claims 1) Curable molding compound composed of a) 5 to 77 parts by weight a "terminally unsaturated" urethane-free polyester, b) 20 to 80 Parts by weight of a vinyl or vinylidene compound copolymerizable therewith and c) 3 to 25 parts by weight of a rubber-elastic polymer with a glass transition temperature between -90 and 100 C, with hardening a second phase as particles to form with a mean diameter of 0.1 to 100 / µm. 2) molding compound according to claim 1, characterized in that the specific The fracture surface energy of the copolymer from a) and formed during curing b) 2> 0.5. 1 105, preferably between 0.5 105 106 2 and, erg / cm. 3) Process for the production of molding compositions according to Claims 1 and 2, characterized in that in the first stage 1 mole of at least one organic Dicarboxylic acid with 1.05-2.0 mol of at least one organic diol preferably in the melt at 150 - 2200C, if necessary in the presence of the usual inhibitors, Esterified with elimination of water and in the second stage 1 mol of the OH groups thus obtained containing precursor with the approximately equivalent amount, preferably 1.9 to 2.2 mol, at least one α, ßäthylenisch unsaturated dicarboxylic acid anhydride, of the corresponding unsaturated dicarboxylic acid or its monoester at about 60 - 1400C added in the melt or, as described for the 1st stage, converts, and 5 - 77 parts by weight of the "terminally unsaturated" urethane group-free obtained in this way Polyester a) with 20-80 parts by weight of a vinyl or copolymerizable therewith Vinyliaenverbindungen b), 3 - 25 parts by weight of a rubber elastic polymer c) and if necessary mixes other aids and additives. 4) Use of the molding compositions according to Claims 1 and 2 for the production of molded bodies.