DE2551144A1 - Stable ethylene polymers dispersed in unsaturated polyester solns. - and prepd. with addn. of organic thixotropic agents contg. amide gps. - Google Patents

Abstract

Prepn. of room temp.-stable dispersions of finely divided ethylene polymers in solns. of alpha, beta-ethylencially unsatd. polyesters in copolymerisable vinyl- or vinylidene cpds. is claimed. Novelty comprises adding organic thixotropic agents, (I), contg. CONH- or pref. OCONH gps., to a compsn. contg. by wt. w.r.t. sum of components (A)-(C), (A) 20-70 (30-50)% alpha, beta-ethylenically unsatd. polyester, (B) 70-20 (60-40)% copolymerisable vinyl- or vinylidene monomer, (C) 3-30 (5-20)% ethylene polymer and (D) 0.001-20 (0.5-3)% dispersants. Use of dispersions for prepn. of moulding compsns. and pre-pregs. for moulding under press. is claimed. Mouldings can be used in furniture and car industry. Prepn. of dispersions is simplified and requires no complicated mixers. Fluid dispersion can be admixed with fillers and strengtheners and stored. Mouldings have low linear shrinkage and a smooth surface. An example describes prepn. of a stable suspension of ethylene copolymer pptd. in a polyester soln. in styrene, in presence of ethylene/vinyl acetate copolymer dispersant and of a thixotropic agent prepd. by adding 57 g isopropanol to 174 g 65/35 2,4-/2,6-toluylene diisocyanate.

Description

Process for the production of stable ethylene polymer

dispersions in unsaturated polyester resins The present application relates to a process for the preparation of dispersions which are stable at room temperature of finely divided ethylene polymers in solutions of CC, p-ethylenically unsaturated Polyesters in vinyl or vinylidene compounds which can be copolymerized with them.

Mixtures of unsaturated polyester resins with ethylene polymers are known. It has already been proposed to use polyester resins, polyethylene powder add to reduce the polymerization shrinkage (FR-PS 1 148 285). As However, it has been shown that moldings made from such polyester resin compositions occur have been produced, especially at temperatures above 1000 C severe signs of aging which, with increasing temperatures, result in internal segregation phenomena express: The polyethylene particles swell and only go one way with the polyester bad connection (DT-PS 1 241 983, column 1, lines 30-43), so that - as not expected otherwise - polyester crosslinked during curing with unsatisfactory Properties arise.

In DT-PS 1 241 983 it has now been proposed that the shrinkage-reducing To replace polyethylene with ethylene / vinyl acetate copolymers. During this Copolymers, if they have high vinyl acetate contents, with Styrene and polyester / styrene solutions are fully miscible, but these mixtures are naturally are highly viscous and consequently when incorporating filling and reinforcing materials Problems are caused by ethylene / vinyl acetate copolymers with a low Vinyl acetate content insoluble in styrene at room temperature and frame in styrenic Polyester solutions quickly build up, clump together and are then difficult to redisperse will. In order to avoid these undesirable phenomena, the insoluble Copolymers usually together with the filling and reinforcing materials incorporated, but then result from uncontrollable swelling and segregation the same difficulties associated with the polyethylene powder addition.

From DT-OS 24 08 898 a method is known according to which finely divided Ethylene polymer dispersions in systems containing unsaturated polyesters and vinyl aromatics can be prepared by the fact that the heated to 50 - 1200 C solutions of ethylene polymers and unsaturated polyesters in vinyl aromatics in the presence combined by dispersants in a zone of high turbulence, the resulting mixture removed from this zone and stirred intensively at elevated temperature until a low-viscosity, flowable state has developed. This method provides a steady state of swelling of the ethylene polymer, since it consists of the Solution in a vinyl aromatic is precipitated, and therefore guarantees an optimal Composite of the phases in the hardened state and thus improved properties molded articles made of such resins. To create a zone of high turbulence pumps are provided with rotors, preferably so-called centrifugal homogenizing machines recommended.

The object of the present invention was now to provide a new process for the production of stable ethylene polymer dispersions in unsaturated To develop polyester resins that can be compared with less technical effort Results comes.

Surprisingly, it has been found that complicated mixing units can be used can do without when working in the presence of certain thixotropic agents.

The invention therefore relates to a method for producing Room temperature stable dispersions of finely divided ethylene polymers in unsaturated Polyester resins from A. 20-70, preferably 30-50,% by weight, based on the total of components A - C, OG, 0-ethylenically unsaturated polyester; B. 70-20, preferably 60-40% by weight, based on the sum of components A-C, more copolymerizable Vinyl or vinylidene monomers; C. 3 - 30, preferably 5 - 20% by weight, based on the sum of components A - C, ethylene polymers and D. 0.001-20, preferably 0.5-3% by weight, based on the sum of components A-C, dispersants, thereby characterized in that organic thixotropic agents E, the CONH groups, preferably OCONH groups, contained, mixed in or incorporated into the polyester.

Suitable i, (3-ethylenically unsaturated polyesters A are customary Polycondensation products of at least one, ß-ethylenically unsaturated dibarboxylic acid usually with 4 or 5 carbon atoms or their anhydrides, optionally mixed with up to 90 mol%, based on the sum of the dicarboxylic acid components, at least an aromatic or saturated aliphatic dicarboxylic acid with 4 - 10 carbon atoms or a cycloaliphatic dicarboxylic acid with 8-10 carbon atoms or whose Anhydrides with at least one polyhydroxy compound, in particular dihydroxy compound, with 2 - 8 carbon atoms - that is, polyester, as described by J. Björksten et al, "Polyesters and their Applications ", Reinhold Publishing Corp., New York 1956.

Examples of unsaturated dicarboxylic acids to be used with preference or their derivatives are maleic acid or maleic anhydride and fumaric acid. Used can be e.g. B. However, also mesaconic acid, citraconic acid, itaconic acid or chloromaleic acid. Examples of the aromatic, saturated aliphatic and cycloaliphatic to be used Dicarboxylic acids or their anhydrides are phthalic acid or phthalic anhydride, isophthalic acid, Terephthalic acid, hexa- or tetrahydrophthalic acid or their anhydrides, endomethylenetetrahydrophthalic acid or their anhydride, succinic acid or succinic anhydride, adipic acid, sebacic acid.

To produce flame retardant resins, z. B. Hexachlorendomethylenetetrahydrophthalic acid (Hetsäure), tetrachloric or tetrabromophthalic acid can be used. Preferred to The polyesters used contain maleic acid residues, up to 25 mol% due to phthalic acid or isophthalic acid residues can be replaced. As dihydric alcohols, for. B. ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 2,2-bis (4-hydroxycyclohexyl) propane, bis-oxalkylated bisphenol A can be used. Ethylene glycol is preferred, 1,2 propanediol, diethylene glycol and dipropylene glycol.

Further modifications are possible by incorporating up to 10 mol%, based on the alcohol or acid component, monohydric alcohols with 1 - 6 carbon atoms, such as Methanol, ethanol, butanol, allyl alcohol, benzyl alcohol, cyclohexanol and tetrahydrofurfuric alcohol, Trimethylpropane, glycerol and pentaerythritol and of mono-, di- and triallyl ethers and benzyl ethers of trihydric and polyhydric alcohols with 3 - 6 carbon atoms according to DAS 1 024 654 as well as by incorporating monobasic acids such as benzoic acid or long-chain acids unsaturated fatty acids such as oleic acid, linseed oil fatty acid and ricinic fatty acid.

The acid numbers of the polyesters should be between 1 and 100, preferably between 20 and 70, the OH numbers between 10 and 150, preferably between 20 and 100, and the average molecular weights k between approx. 500 and 5000, preferably between approx. 1000 and 3000 (measured by vapor pressure osmometry in dioxane and acetone; if the values differ, the lower value is used as the correct viewed2 It is true that the content of the residues condensed into the polyester i, p-Ethylenically unsaturated dicarboxylic acids vary within wide ranges; there the parts produced from the molding compositions according to the invention after pressing be demolded hot and consequently a satisfactory heat resistance should have a content of residues, (3-ethylenically unsaturated dicarboxylic acids from 0.65-0.20 moles / 100 g unsaturated polyester preferred.

As copolymerizable vinyl and vinylidene compounds B are suitable the compounds commonly used in polyester technology, especially those with a -substituted vinyl groups or ß-substituted allyl groups, preferably unsubstituted Styrene itself, but also, for example, nuclear chlorinated and alkylated or alkenylated Styrenes, where the alkyl groups can contain 1-4 carbon atoms, such as. B. vinyl toluenes, tert-butylstyrenes, chlorostyrenes, divinylbenzene. The compounds mentioned can also up to 20 mol% by o (-Methylstyrene, vinyl esters of carboxylic acids with 2 - 6 carbon atoms, preferably vinyl acetate, vinyl pyridine, vinyl naphthalene, vinyl cyclohexane, Acrylic acid and methacrylic acid and their esters (preferably vinyl, allyl and methallyl esters) with 1 - 4 carbon atoms in the alcohol component, their amides and nitriles, maleic anhydride , its 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, Diallyl isophthalate, diallyl fumarate, allyl carbonates, diallyl carbonates, Triallyl phosphate and triallyl cyanurate are replaced.

The ethylene polymers suitable for the process according to the invention C can be produced by known tubular or stirred reactor processes. It are Athylenhomopolymers and those Äthylencopoly merisate, the Vinyl esters such as vinyl propionate, but preferred Vinyl acetate, in quantities from 0.5 - 20, preferably from 7 to 15, in special cases at least 8 - 10% by weight, included in polymerized form.

The melt index values measured according to DIN 53 735 at 1900 C and 2.16 kp load the shrinkage-reducing additives C are in the range from non-flowable to 1000; Ethylene polymer types with melt index values between 0.1 and 20 used.

Of course, they are suitable for the suspension according to the invention not only high-pressure polyethylene, but also using low-pressure or medium-pressure processes manufactured types of polyethylene, but also manufactured according to special processes Homopolyäthylene or ethylene / vinyl ster-Mi schpolymerisate.

The fineness of the suspended ethylene polymers is determined by the The addition of dispersants has a positive effect. Particularly effective dispersants D are in copolymerizable monomers or in polyesters or in a polyester / Monomer mixture soluble high molecular weight polymers. Preferred dispersants are Ethylene / vinyl acetate copolymers, which preferably have a content of 30-100% by weight Vinyl acetate and a Mooney viscosity of at least 8, preferably 15-65 Mooney, measured according to DIN 53 523 (64).

However, poly (meth) acrylic acid esters are also homomogeneous as dispersants and copolymers containing 1 to 24 carbon atoms in the alcohol component, such as z. B. decyl polyacrylate, or copolymers of ethylene with an ethylene content up to 60% by weight with (meth) acrylic acid esters containing 1 to 24 carbon atoms in the alcohol component contain, or with vinyl esters of organic nonocarboxylic acids with 1 to 19 carbon atoms or with their saponification products suitable. Very good dispersants are also graft polymers with the polymers mentioned as the graft substrate.

Furthermore, polyethers, such as polyethylene oxide and polypropylene oxide, are used as dispersants and copolymers of these two compounds, ethoxylated saturated and unsaturated Fatty acids with 4 to 30, preferably with 6 to 19 carbon atoms, their esters, the 1 to The alcohol component contains 24 carbon atoms, its amides and nitriles, fatty alcohols with 1 to 30, preferably with 4-16 carbon atoms, or with graft polymers these polymers are suitable as a graft substrate, as described, for example, in DT-AS 1 137 554 are described. Vinyl aromatics, such as vinyl toluene, are suitable as graft monomers & -Methylstyrene, tert-butylstyrene, chlorostyrenes, but preferably unsubstituted Styrene itself; Vinyl acetate, (meth) acrylic acid, its nitriles and esters, their alcohol component May contain 1 - 18 carbon atoms, such as B. methyl methacrylate or ethyl acrylate, (Meth) acrylonitrile, maleic anhydride, maleic acid halves and dies with 1 - 30, preferably 4 to 16 carbon atoms in the alcohol component. Of course you can both as graft substrates and as graft monomers as well as mixtures of the listed Connections are used.

Suitable dispersants are also cellulose derivatives, such as methyl cellulose, Ethylhydroyycellulose or cellulose esters, e.g. B. cellulose acetate, cellulose acetopropionate, Cellulose acetobutyrate or nitrocellulose.

Sometimes the entrainment can be avoided during the preparation of the dispersion of water that z. B. can be dissolved in the disperser, do not avoid completely. Frequently but this is not a disadvantage, on the contrary: often small amounts are used in a targeted manner Water, since this measure improves the stability of the dispersion can. The finished dispersion may contain up to 5% by weight of water; usually however, if the water content is below 1% by weight.

The thixotropic agents E to be used according to the invention are CONH groups load-bearing connections in question, as they are z. B. in the DT-AS 1 020 428, 1 106 015, 1,182,816, 1,217,611, 1,273,192, 1,569,331 and 1,745,347. In detail it is a) modified unsaturated polyester, preferably with OH numbers over 100 and with acid numbers up to 30, which result from the reaction of unsaturated linear or branched, hydroxyl-containing polyesters with monovalent or polyvalent ß, -unsaturated ether alcohols and polyisocyanates are available. As special Such modified unsaturated polyesters, their production, have proven to be suitable has been made in the presence of oxygen.

b) polyester amides, their mixtures of 3 parts by weight of polyester amide and 7 parts by weight of mineral spirits are inhomogeneous at room temperature and their content of polar groups is up to 35, preferably 14-30,% by weight, with below Inhomogeneous mixtures are understood to be those that have a second liquid or solid Show phase and as a result may show a cloudiness. Preferably be such polyester amides are used, which are made using polycarboxylic acids, polyamines with at least two primary amino groups and either hydroxycarboxylic acids or Polyalcohols or amino alcohols or mixtures of these hydroxy compounds prepared are.

Preferred polyester amides have an amide group / ester group ratio from 0.1 to 2.2 and softening points below 230, in particular below 200.0C.

c) polymeric amides with an average molecular weight k of 500 - 10,000, the residues of monoaminomonocarboxylic acids and / or diamines and dicarboxylic acids have and their hydrogen atoms located on the carbonamide nitrogen atoms wholly or partially by at least 4 carbon atoms and at least 1 oxa oxygen atom having mono or

Poly-oxaalkyl radicals are substituted. Examples of such Base polymers are PolylO-caprolactam and Poly-æ-capryllactam, also the polycondensates from tetra-, Hexa- or octamethylenediamine and succinic, adipic, corkic or sebacic acid. The thixotropic polymeric amides can be obtained therefrom by oxyalkylation will.

d) Polyurethanes with average molecular weights t of 250 - 5,000, in particular from 500 - 3,000, the 1st linked urethane-like, residues of divalent Carbamic acids and residues of divalent hydroxyl compounds and possibly additionally Residues of lower or higher value carbamic acids and / or residues of lower or higher value Have hydroxyl compounds, 2. of ethylenically unsaturated groups, residues Fatty acids containing more than 9 carbon atoms, residues of adducts from such fatty acids and isocyanate groups or groups that react like these are free or practically free and 3. form homogeneous and clear solutions when mixed with the polyester resin (A + B).

e) Cyclohexylamides of saturated higher fatty acids with at least 10 C atoms, such as capric acid, myristic acid, palmitic acid, stearic acid, oxystearic acid, behenic acid, or mixtures of these cyclohexylamides; z. B. The cyclohexylamides of the so-called "main sound" of paraffin oxidation are also suitable.

The thixotropic agents E can be used in the production of the inventive Dispersion simply mixed in, but if desired also by boiling with the Starting components of the unsaturated polyester A in its production in these condensed in or condensed onto it after its production - be it in the melt, in the solution in the copolymerizable monomer B or - most of the time the preparation of the dispersion according to the invention.

Suitable such thixotropic polyesters are, for. B. conversion products, those made from hydroxyl-containing unsaturated polyesters with a hydroxyl number of 10 - 300 and an acid number of 10 - 40 and predominantly one free isocyanate group carrying reaction products made from polyisocyanates and monohydroxyl compounds will.

Thixotropic agents, which are ideal for installation in or for condensing Suitable for unsaturated polyester A are the isocyanates. In detail, aliphatic, cycloaliphatic and aromatic monoisocyanates with at least 4 carbon atoms, such as z. B. dodecyl isocyanate, phenyl isocyanate, naphthyl isocyanate, cyclohexyl isocyanate and the C1 - C4 alkyl derivatives of the isocyanates mentioned, diisocyanates such as. B. 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1-methyl-cyclohexane-2,4- and -2,6-diisocyanate and the mixtures of these isomers, 2,4- and 2,6-tolylene diisocyanate and the mixtures of these isomers, naphthylene-1,5-diisocyanate, 4,4 "-diphenylmethane diisocyanate, xylylene-1,3- and 1,4-diisocyanate, higher molecular weight Polyisocyanates such as those obtained from polyisocyanates and compounds containing hydroxyl groups (See, for example, DT-PS 870, 400 and 909,186) can be obtained, as well as triisocyanates such as 4,4'-triphenylmethane triisocyanate and polyaryl polyalkylene polyisocyanates, such as by aniline-aldehyde (e.g. formaldehyde-J condensation and subsequent phosgenation be obtained, or di- or trimerized tolylene diisocyanate.

Among the polyisocyanates mentioned are diisocyanates and polyisocyanates preferred, whose functionality is iden by conversion with Zerewitinoff-H-ac, monofunctional Connections e.g. B. monofunctional alcohols and / or acids reduced to 2 or 1 can be.

Compared to inorganic thixotropic agents such as highly dispersed silica, certain qualities of kaolin, bentonite or Chalk, draw the agents E containing organic CONH groups have various advantages from: While in the case of inorganic substances there is a risk of sedimentation and thus a uneven thixotropy, therefore also an uneven distribution of the ethylene polymers, this phenomenon can occur in the case of the invention Substances E to be added, which dissolve in the polyester resin (A + B), naturally not occur, especially when E has been incorporated into polyester A.

In contrast to the inorganic thixotropic agents, with the agents E to be added according to the invention are still flowable without difficulty Set the state which, on the one hand, ensures optimal stability of the dispersion and on the other hand, a simple incorporation of filler and reinforcement materials as well as the usual packaging (e.g. in barrels) are permitted.

The dispersions according to the invention are preferably prepared so that one dissolves the ethylene polymers C in the monomers B with heating and when Cooling with stirring in the presence of polyester A, thixotropic agent E and dispersants D, fails again.

To protect the dispersions according to the invention from undesirable premature To preserve polymerization, it is recommended that 0.001 - 0.1 wt .-%, based on the dispersion A - E, polymerization inhibitors or Add antioxidants. Suitable aids of this type are, for example Phenols and phenol derivatives, preferably sterically hindered phenols, are present in both o-positions to the phenolic hydroxyl group alkyl substituents with 1 - 6 carbon atoms contain amines, preferably secondary arylamines and their derivatives, quinones, copper salts organic acids, addition compounds of copper (I) halides to phosphites, such as B. 4,4'-bis (2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4'-butylidene-bis- (6-tert-butyl-mcresol), 3,5-di-tert-butyl-4-hydroxyl-benzyl-phosphonic acid diethyl ester, N, N'-bis- (ß-naphthyl-p-phenylenediamine, N, N'-bis- (1-methylheptyl) -p-phenylenediamine, Phenyl-β-naphthylamine, 4,4'-bis (d4 a dimethylbenzyl) -di-phenylamine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyl) -hexa-hydro -s-triazine, Hydroquinone, p-benzoquinone, toluhydroquinone, p-tert-butylpyrocatechol, chloranil, Naphthoquinone, copper naphthenate, copper octoate, Cu (I) Cl / triphenyl phosphite, Cu (I) Cl / trimethyl phosphite, Cu (I) Cl / trischloroethyl phosphite, Cu (I) Cl / tripropyl phosphite, p-nitrosodimethylaniline. Further suitable stabilizers are in "Methods of Organic Chemistry" (Houben-Weyl), 4th edition, Volume XIV / 1, pp. 433-452, 756, Georg Thieme-Verlag, Stuttgart, 1961. Very suitable is z. B.

p-Benzoquinone in a concentration of 0.01-0.05% by weight, based on the dispersion A - E.

Usual additives that can also be used are inert inorganic fillers such as calcium carbonate, silicates, clays, lime, coal, organic and inorganic pigments, dyes, lubricants and release agents, such as zinc stearate, W absorber, etc.

At any point in time before curing, the inventive Customary amounts of dispersions, preferably 0.5-5% by weight, based on the dispersion A - E, polymerization initiators added. Suitable as such are, for example 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 t P. ikyl peroxides such as bis (tert.-butylperoxybutane), dicumyl peroxide, tert.-butylcumyl peroxide, Hydroperoxides such as cumene hydroperoxide, tert.- Butyl hydroperoxide, Cyclohexanone hydroperoxide, methyl ethyl ketone hydroperoxide, perketals, acetylacetone peroxide or azoisobutyrodinitrile.

Fibrous reinforcing materials that can be used - as usual - are inorganic Fibers such as metal, asbestos, carbon, especially glass fibers, and organic Fibers, e.g. B. cotton, polyamide, polyester, polyacrylonitrile or polycarbonate fibers can be used.

The dispersions 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, preferably magnesium and calcium, in amounts of 0.1-10, preferably 1.0-3.0% by weight, based on the dispersion A - E, can also be added, as well as accelerating or regulating chemical thickening Additives such as 0.1-0.5% by weight. Water or additives according to DT-OS 1 544 891, z. B. aliphatic carboxylic acids or partial phosphoric acids, or according to DT-OS 2.326.103 z. B.

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 on roller mills.

While smaller moldings from the dispersions, which may be

Contain filling and reinforcing materials, can be produced, the most efficient way to manufacture larger molded parts is to use thickened resin mats. These are made by iaii with the magnesium oxide described above containing, glass fiber-free molding compounds soaks glass fiber mats and their surface Protects on both sides with cover films. The foils prevent the evaporation of the Monomers B allow the mats to be rolled up and thus space-saving storage. After the resin mats have thickened after a maturing time of approx. 1 - 10 days, the cover film can be peeled off and the resin mats after being cut accordingly Hot-pressed to form low-shrinkage molded parts will.

The form and prepared from the dispersions of the invention Molding compounds can be pressed under a pressure of approx.

20 - 140 kp / cm2 at approx. 120 - 1600 C, depending on size and shape in approx. 0.5 - 5 min are cured, with homogeneously colored molded parts with minimal shrinkage and impeccable surface can be obtained.

In contrast to the method described above, in which together with the fillers and fibers ethylene polymer powder as shrinkage-reducing If additives are made up, the dispersions according to the invention have the advantage that the dispersed ethylene polymer particles as a result of precipitation from a solution with a reproducible, steady state of swelling, or at least this by storage in thixotropic dispersion and consequently an optimal Bonding of the phases as well as optimal mechanical properties in the hardened state result in the molded body.

The moldings produced with the aid of the dispersions according to the invention have very low linear shrinkage, as opposed to the low depth of sink marks of material thickening, invisible fiberglass structure and extremely smooth Surfaces on. They can therefore be used advantageously wherever where molded parts with high dimensional accuracy and flawless surfaces are required (Furniture sector, car industry).

The following examples illustrate the invention. Percentages mean Weight percent. The viscosity information is based on measurements in a falling ball viscometer according to Höppler at 200 C.

Production of the styrenic solution of an unsaturated polyester (Designation: UP 1) The unsaturated polyester is produced in a known manner Way by melt condensation at 1800 C under a nitrogen atmosphere until it is reached desired acid number. The polyester melt is then at 1200 C with hydroquinone added and then dissolved 65% in styrene.

The composition of the starting components of the polyester as well as the The key figures for the styrenic solution are listed in a table.

g maleic anhydride 1570 phthalic anhydride 592 propylene glycol-1,2 1262 Dipropylene glycol 670 Hydroquinone 1.14 Key figures of the styrene solution: solid content 65 * viscosity (20 ° C) 1500 cP acid number 20 mg KOH / g making a buildable Thixotropic agent (designation: Tix A) in a 0.5 1 3-necked flask are under Nitrogen to 174 g of Desmodur T 65 (a mixture of 65 parts by weight)

2.4 - 35 parts by weight 2,6-tolylene diisocyanate, commercial product from Bayer) 57 g of isopropyl alcohol were added dropwise with stirring.

The temperature rises quickly and is maximized by cooling 750 C held. After the addition of isopropanol is complete, the mixture is stirred at 750 ° C. for a further 1 hour and then cooled the adduct to room temperature.

Examples 1 to 3 In a 2-13 neck flask, the following are made The components listed in the table are weighed at room temperature, the mixture heated to 800 ° C. with stirring (approx. 600 rpm) and at this temperature for 4 hours held. During this time a fine dispersion is formed, consisting of two liquid ones Phases. It is cooled to room temperature while stirring, whereby at approx. 650 C the dispersion turns into a suspension, which consists of a styrenic polyester solution precipitated polyethylene. The suspension is filled into powder bottles d 1 l and stored at room temperature. The assessment of the suspension is given in the table noted. The examples show, compared with those designated in each case with a) to c) Comparative examples clearly the Vos part of the suspensions according to the invention.

Polyethylene A is a medium pressure ethylene / vinyl acetate copolymer with 9 * vinyl acetate and a melt index of 12.5, measured according to DIN 53.735.

Dispergator A is an ethylene / vinyl acetate copolymer with 45% vinyl acetate and a Mooney value of 20, measured according to DIN 53.523, L 4.

Dispergator B is an ethylene / vinyl acetate copolymer with 70 'vinyl acetate and a Mooney value of 54, measured according to DIN 53.523, L 4. Example No. 1 b 1 c 1 1 a 2 2 a ggggg UP 1 1080 1080 1080 1080 1080 080 1080 Styrene 504 504 504 504 504 504 Polyethylene A 216 216 216 216 Æ 216 216 Dispergator A --- --- 36 36 --- --- Dispergator B - --- - --- 36 36 Tix A 36 --- 36 --- 36 --- Benzoquinone 0.05 0.05 0.05 0.05 0.05 0.05 Separation: immediately immediately no 10 minutes no 24 hours

Production of a Harziatte from the suspension according to the invention according to Example 3: 100 parts by weight. the suspension according to Example 2 with the following The aggregates listed are mixed homogeneously with a dissolver and mixed with the resulting Paste ii specified proportions a glass silk mat drunk, the mat with Cover foils protected on both sides and stored at room temperature for 7 days.

Composition of the resin saturation: parts by weight 100.00 suspension according to Example 3 100.00 Calcium Carbonate 1.50 Magnesium Oxide 4.00 Zinc Stearate 1.65 Iron Ocide Black 3.35 iron oxide red 0.75 tert-butyl porous benzoate 52.80 glass silk mat Manufacturing of a molded body: after the resin mat has been stored for 7 days at room temperature the cover sheets peeled off, which is very easy and without any damage to the Mat works because it has a dry, tack-free surface. 125 g of the thickened HarzBatte become a plate (12 x 12 cm) with a diagonal rib and a Nub pressed for 5 min at 1450 C with 120 kp / cm2. The linear percentage shrinkage, measured over the diagonal rib of the hardened plate, is only 0.043%.

The plate is colored homogeneously, has a high-gloss finish and does not show any distortion.

Claims (4)

PåtontansDrüche: 1. Method of making more stable at room temperature Dispersions of finely divided ethylene polymers in unsaturated polyester resins from A. 20-70% by weight, based on the sum of components A - C, α, ß-ethylenic unsaturated polyester; B. 70-20 wt .-%, based on the sum of the components A - C, copolymerizable vinyl or vinylidene monomer; C. 3 - 30% by weight, based on on the sum of components A - C, ethylene polymers and D. 0.001 - 20% by weight, based on the sum of components A - C, dispersants, characterized that organic thixotropic agents E containing CONH groups, mixed in or can be built into the polyester. 2. The method according to claim 1, characterized in that organic Thixotropic agents E containing OCONH groups, mixed in or in the polyester to be built in. 3. Dispersions of finely divided ethylene polymers that are stable at room temperature in unsaturated polyester resins from A. 20-70% by weight, based on the sum of the Components A - C ,, ß-ethylenically unsaturated polyester; B. 70-20 wt .-%, based to the sum of components A - C, copolymerizable vinyl or vinylidene monomers; C. 3 - 30 Gan, -96, based on the sum of components A - C, ethylene polymers and D. 0.001 - 20% by weight, based on the sum of components A - C, dispersants, characterized in that it according to the method according to claims 1 and 2 have been manufactured. 4. Use of the dispersions according to claim 3 for the preparation of Molding and molding compounds.