DE2229561A1 - HEAT-RESISTANT MOLDING COMPOUNDS - Google Patents

Description

DIAMOND SHAMROCK COEPOEAiEION
Cleveland, Ohio, V.St.A.

¹¹ thermosetting Molding compounds " V. St. .A., No. 153 874 Priority: 16 . June 1971,

The invention relates to improved thermosetting molding compositions.

In particular, the invention relates to thermosetting molding compositions based on a reinforcing agent, such as. B. fillers, Glass fiber and asbestos-containing resin system composed of an unsaturated polyester and a vinyl monomer and the merits and possible uses of these molding compounds.

In particular, the invention relates to those produced by the polymerization of vinyl chloride, vinyl acetate and an unsaturated acyclic at least one carboxyl group-containing monomers prepared thermoplastic polymer components of the above

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called molding compounds.

For the production of thermosetting reinforced plastic moldings Polyester molding compounds used generally consist of a mixture of unsaturated polyester and an olefinically unsaturated one Monomers, such as. B. styrene, vinyl toluene and methyl methacrylate, as a resin system in combination with reinforcement materials. The unsaturated monomer serves as a carrier substance for the polyester and provides unsaturated bonds that can be crosslinked with those of the polyester, three-dimensional, non-meltable copolymers react. In practice, the approach is a free radical forming compound added, which decomposes with heating and the copolymerization reaction sets in motion. Depending on the end use of the resin molding compound, there may be other additives, such as polymerization accelerators or inhibitors, mold release agents, stabilizers against UV radiation and flame retardants Funds included.

For some time now, these polyester molding compounds have been used for injection molding the premixed resin-glass fiber molding compound, for compression molding, Injection molding and for the manual process, d. H. Preform and mat press methods are used.

Using mats and preforms working two-molding method, high-quality moldings are excellent for Schnellherstel- development. Because with this method the number of reinforcing materials in question is somewhat limited

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is and necessarily many different and costly Forms for the preforms and punched-out mat raw materials must be used, this method is often used disadvantageous.

The application of dough pressing processes or processes using fiber-reinforced panels in the production of reinforced plastic moldings is simpler and more economical than the mat and pre-form lay-up methods, since none are costly Preform and mat blanks are required and a greater number of reinforcing materials and fillers can be used. The use of molding compounds for the dough pressing process of polyesters and for the process for the Production of fiber-reinforced panels enables the production of complex moldings while reducing the number of rejects a minimum.

In the dough pressing process, a chemical thickener is used the polyester molding compound prepared or premixed in a putty-like consistency before loading the mold.

Another Fonnmasr-e is for the production of moldings under Use of reinforced thermosetting plates is suitable (sheet molding compound). It is made by first removing the resin components and the additives without the reinforcement materials measures and mixes with each other. The resulting liquid to paste-like mass is on a carrier film, z. B. made of polyethylene, applied. The resin layer is made with

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the reinforcement, generally fiberglass or fiberglass mats, and then covered with a second resin-coated carrier film covered. The sandwich laminate is then sandwiched between nip rollers for trapped air and excess Resin freed and finally rolled up. These roles are ready to use. When using glass fibers as reinforcement material v / these plates are referred to as GPK plates.

In practice, a chemical picking agent is also added here in the course of the production of the molding compounds for the GPK sheets, so that the set resin molding compound has a sufficiently high viscosity for easy handling before it is used.

Certain known polyester resin compositions can be used both in the dough pressing process and in the process for the production of Use GPK plates. In most cases, however, these masses do not give satisfactory results because of them Moldings produced shrink and warp on cooling. Furthermore, these shaped bodies often have a wavy shape rough surface and sink marks, especially if the molded parts have a complicated shape and sections with irregular Have thickness. In order to prevent discarding, the moldings must either be removed from the Mold or in a special jig. These additional measures are time-consuming and costly.

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, An even bigger disadvantage is that the conventional Reinforced polyester resin molded parts produced have rough and v / ell-shaped surfaces, which are characteristic Reproduce the pattern of the reinforcing fibers. These characteristic rough surfaces are at least partial on the shrinkage of the resin binder material of the molding compound occurring during curing as a result of the polymerization and the crosslinking reaction between the resins.

However, surface smoothness is essential for the successful use of moldings in many areas of application, such as B. in the Automotive industry and household appliances, an essential one Precondition. Known measures for improving the surface of fittings used in such areas of application consist in the use of a resin-rich, so-called gelcoat (protective layer or fine layer) or in use fine glass fiber fleece. Without these measures, the surface of the moldings had to undergo a time-consuming dry polishing treatment be subjected. All of these measures naturally mean additional process steps and increase the overall production costs considerable.

Recently, improved, fortified unsaturations have been reported in the literature Polyester compositions described, for. In U.S. Patent 3,503,921, in Canadian Patent 820 399 and in British Patent 936 351. These Compounds contain a saturated thermoplastic polymer, such as polystyrene or polymethyl methacrylate, to improve the

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Processing properties .. It was found that also the Properties of the molded part produced, such as ζ. B. surface smoothness and shrinkage, by using these polymers in similarly improved. As these components are not compatible, they form a unit with the system When they become part of the resin, they must generally be viewed as fillers or additives added to the resin composition. at When the polyester cures, these polymers are visibly separated in the polyester and are obtained by suitable extraction processes separable from him.

It has now been found that one in an unsaturated, reinforced Polyester mass contained by polymerizing a mixture of vinyl chloride, vinyl acetate and an olefinic thermoplastic polymer obtained from unsaturated acyclic monomers having at least one carboxyl group before curing forms a non-separable single phase with the other resin components and evidently during curing becomes a compatible component built into the resin and cannot be separated from it.

The invention accordingly relates to improved thermosetting molding compositions, characterized by a content of

(a) 20 to about 60 parts by weight of a polymerizable unsaturated polyester,

(b) about 20 to 65 parts by weight of a polymerizable Vinyl monomers,

(c) about 2 to 25 parts by weight of a saturated thermo-

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plastic polymers produced by suspension polymerization a monomer mixture of vinyl chloride, vinyl acetate and an olefinically unsaturated acyclic monomer with 1 up to 2 carboxyl groups of the general formula I or II

_R l_ _{c R} 2 R ²¹ HC = C COOH

r3__ c - COOH H ₂ C - COOH

(I) (ID

where E is a hydrogen atom or a methyl, carboxyl or

Phenyl group means, E is a hydrogen atom or a carb

1 2

represents oxyl group, but R and E are not carboxyl groups at the same time are, R ^ is a hydrogen atom or a methyl group and R denotes a hydrogen atom or a hydroxyl group, in an aqueous medium at temperatures from 50 to 130 ° C was prepared in the presence of a polymerization initiator, and optionally

(d) common fillers and auxiliaries, reinforcing materials, Mold release agents, thickeners, pigments, initiators or accelerators.

A particularly suitable monomer is an unsaturated aliphatic one Mono- or DL-carboxylic acid. Such unsaturated acids corresponding to structural formula I above are maleic acid, Fumaric acid, citraconic acid, acrylic acid, methacrylic

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acid, crotonic acid and cinnamic acid. Itaconic acid and aconic acid hydrate are specific monomers according to structural formula II.

In the approach, together with the mineral fillers and a compound which forms free cadavers, initiation the reaction between the polyester and the vinyl component effective amounts of reinforcement material added. If necessary, other materials, such as stabilizers against UV radiation, Polymerization inhibitors, inhibitors, pigments, mold release agents and other commonly used additives, can be added. Approaches for the dough pressing process with a thickener and for the process for the production of GRP panels Of course, suitable molding compounds contain chemical thickeners.

When using the molding compositions according to the invention, molded parts with excellent surface smoothness are obtained In most cases sufficient for the direct application of protective coatings or decorative coatings such as paints or varnishes is. True-to-life molded parts with high dimensional accuracy are obtained.

The use of the molding compositions according to the invention also makes the application of a resin-rich gelcoat costly Surface grinding or other mechanical pre-treatments to achieve the desired smooth surface, e.g. B. for Painting and coating purposes, superfluous.

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Manufactured from the thermosetting molding compositions according to the invention Molded parts also have an extremely low level Shrinkage, the parts do not warp and show an overall excellent dimensional stability.

As described in more detail below, the thermoplastic Polymer component of the molding compositions according to the invention by suspension polymerization in an aqueous medium at a Temperature of 50 to 130 ° C produced, with a conventional Initiation mechanism using free radicals is used. As in the German Offenlegungsschrift 1 94-7 924, those of the reaction self-generated bridge or pressures beyond that can be used.

Because this polymer is manufactured without any chain transfer agents has a low molecular weight, it usually does not contain residual initiator fragments, the could affect its thermal stability.

Within the composition range given above, the amount used of each component of the resin molding materials can be used can be varied depending on the degree of surface smoothness and / or shrinkage desired in the end product. For example A small amount of shrinkage of the molding may be desirable for easy removal from the mold.

In the production of reinforced thermosetting molding compounds

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the resin system described above generally together with the reinforcement materials in the one given below Composition stated:

Besta n dteile of the projection system 100 parts by weight resin

Filler 0-250

Fiber reinforcement material 0-550

In addition, as required and customary, initiators, mold release agents, pigments and dyes, inhibitors, accelerators and chemical thickeners added.

Unsaturated polyesters generally useful are known in the art Way by reaction between one or more polyhydric alcohol (s) and one or more polycarboxylic acid (s) manufactured. The polymerizable ones preferably used in practice unsaturated polyesters from polyhydric alcohols and polycarboxylic acids are the so-called "linear" or "substantially linear" polyester, i.e. H. Polyester that has little or no cross-linking in the polyester molecules have, which can be demonstrated by their solubility in solvents such as acetone. This polyester are usually formed mainly by the esterification of a dihydric alcohol and a dicarboxylic acid. It you can also use polyhydric alcohols with more than two hydroxyl groups and polycarboxylic acids with more than two carboxyl groups used in polyester production. These

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However, components should be used in smaller quantities, so that in the manufacture of polyester the maximum the esterification reaction from hydroxyl and carboxyl groups can be achieved without the viscosity increasing too much as a result of crosslinking.

A typical "linear" polyester which can be used in accordance with the invention is produced in a known manner. The esterification reaction is practically carried out to the end (i.e. to one Acid number less than about 80), taking care to ensure that that no noticeable polymerization of the double bonds takes place. If the esterification reaction is generally carried out under an inert protective gas and oxygen on this Manner is excluded, inhibitors can be used to prevent significant polymerization of the polyester during the esterification reaction.

A typical example of an unsaturated one which can be used in the present invention Polyester is the reaction product of (1) <x, olefinically unsaturated dicarboxylic acids, such as fumaric, maleic, Itaconic, citraconic, mesaconic or chloromaleic acid or the corresponding anhydrides or mixtures of these carboxylic acids with (2) a dihydric alcohol, such as polymethylene glycols of the series ethylene glycol to decamethylene glycol, propylene glycol, Butylene glycols, polyethylene glycols of the series diethylene glycol to decaethylene glycol, dipropylene glycol and its higher homologues, neopentyl glycol, glycerol monoester with monocarboxylic acids (in α- or ß-position), such as

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Glycerol monoformic acid ester or glycerol monoacetic acid ester, Glycerine monoether with monohydric alcohols, such as glycerine monomethyl ether or glycerol monoethyl ether, or dihydroxyalkanes the series Dihydroxybutane "to Dihydroxy dec, in which the OH groups are linked to primary and / or secondary carbon atoms.

Some of the unsaturated dicarboxylic acid can be saturated by Dicarboxylic acid, e.g. B. oxalic acid, malonic acid, sebacic acid, Phthalic acid, isophthalic acid, terephthalic acid or tetrahydro ^ phthalic acids. Other components are used in the esterification reaction as needed.

Furthermore, the usual modification additives to achieve certain properties of the polyester product, such as. B. Solubility in various solvents and corresponding flowability, and that from the subsequent polymerization of the polyester obtained product, such as. B. infusibility, hardness and inert behavior, in the manufacture of the Polyester can be used.

Preferably used polyesters are e.g. B. from 0.8 to 1.2 moles of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and neopentyl glycol per 1.0 mole of maleic acid and / or fumaric acid, o-phthalic acid, isophthalic acid, tetrahydrophthalic acid and adipic acid or the corresponding acid anhydrides. Modified diethylene, dipropylene, Ethylene, propylene or neopentyl maleates or fumarates can

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are used as well as bisphenol-modified and halogenated or phosphorus-containing acids or glycols, which lead to chemically resistant and flame-resistant polyesters. These compounds are used for economic reasons and because of the properties of those made with these compounds End products preferably burned.

The unsaturated monomeric components of the resin system of the present invention heat-curable molding compositions contain at least ^ oe CH ₂ = C group capable of crosslinking with the unsaturated polyester. Any monomer of this type used in polyester systems is suitable for this purpose. Specific, because of their ready availability, reaction. The preferred monomers used for this purpose or other desirable properties are styrene, chlorostyrene, tert-butyl styrene, vinyl toluene, diallyl phthalate, vinyl acetate, methyl methacrylate and diacetone acrylamide. "Other vinyl monomers can also be used either alone or together with the monomers of the above group Ensuring a successful crosslinking reaction under the action of heat from 0.2 to Ί.6 and in particular from 0.3 to 1.5 parts of the monomer per part of polyester used.

As already mentioned, the thermoplastic polymer component of the resin system is made from the polymerization of vinyl chloride, vinyl acetate and an unsaturated acyclic one or two carboxyl group containing monomer. Preferably acid group-containing monomers used according to

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... 14 -

the structural formulas I or II are croton, fumar, itacon and Methacrylic acid.

This polymer is an essential component of the polyester molding compositions according to the invention for their satisfactory processing into finished moldings with the desired surface smoothness and dimensional stability. However, in order to ensure satisfactory behavior in these compositions, the polymer itself must also have certain properties. For example, Qs should start with. of the vinyl monomer component do not react or dissolve in it to such an extent that the viscosity of the polyester batch increases too quickly to completely wet and envelop the reinforcing material. On the other hand, however, it should react to a sufficient extent with the vinyl monomer to form a relatively stable, uniform phase with this component and in this way not to exude on the surface of the polyester compositions during storage.

If the polyester formulation contains a chemical thickener, the carboxyl groups are very likely to react with it in a similar manner as with the carboxyl groups of the polyester. It is also believed that the polymer additive, albeit it because of the lack of carbon-carbon double bonds, it is not actively involved in the crosslinking reaction via the carbon-carbon double bonds participates, but very likely to a small extent through a chain transmission mechanism is grafted onto the thermosetting resin. These

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The reaction contributes to a closer bond between the thermoplastic polymer molecules in the polyester base and prevents exudation on the surface.

The thermoplastic polymer component used meets the requirements mentioned above. She affects that Viscosity behavior of the polyester batch is not decisive, does not sweat during storage even after prolonged aging on the surface of the mixed polyester molding compounds and is, like an electron microscopic examination of Shows cracks in the surface of the hardened resin molding compounds, apparently to a compatible integral part with the resin portion of these compositions.

Surprisingly, it has been found that the polymer addition has a unique, beneficial and unexpected effect on the Exerts viscosity behavior of the polyester approach. Shortly after its production, the approach knows how to guarantee it a satisfactory wetting and coating of the reinforcing materials and fillers on the desired low viscosity. Shortly thereafter, the viscosity of the mixed batches increases at such a rate that it is necessary to achieve a Satisfactory aging viscosity of the approach required storage time is significantly shortened.

For example, an inventive, reinforced, thermosetting After its production, molding compound usually has a higher viscosity than water. Within 10 to 30 minutes

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utes after production can vary depending on the viscosity of the approach after the one added along with a chemical thickener Amount of thermoplastic polymer to a value of more than 1 million cP. By adding appropriate amounts of these Components it is therefore possible to control the increase in viscosity of the batch as desired. Non-flowable and easy to be handled for the dough pressing process and the procedure Molding compounds suitable for the production of GRP panels can easily be used in this way within 60 minutes of production of the approach. In this way the Use of the thermosetting molding compositions according to the invention which can be processed considerably faster after their production than comparable conventional molding compounds, for the manufacturer noticeable savings in overall production costs. It can also be seen without further ado that the molding compositions according to the invention are particularly suitable for the dough pressing process and the process for producing To carry out GRP panels continuously.

To produce the thermoplastic component of the invention Molding compounds is a monomer mixture of vinyl chloride, Vinyl acetate and the olefinically unsaturated monomeric acid in a suitable suspending or dispersing agent polymerized containing aqueous medium. The polymerization temperature generally varies from about 50 to 130 and in particular 75 to 110 ° C. The reaction pressures used can be equal to the vapor pressure of the monomer device be at reaction temperature or they can be

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ses vapor pressure, which by pumping in a sufficient Amount of water in the reactor "until it is reached and maintained the desired pressure is achieved. The polymerization reaction is carried out with the help of a free radical forming compound carried out as initiator, either at the beginning of the reaction or continuously at a prescribed rate is added.

Depending on the polymerization conditions and the particular initiator used, the polymeric products obtained have possibly viscosity numbers (see viscosity number in example 8) from about 0.20 to 0.70. Despite being made in the absence of a chain transmitter, these Polymers the desired low molecular weight and those to achieve their satisfactory behavior in the invention Molding compounds required solubility properties.

The thermoplastic polymer component generally contains 40 to 70% by weight of vinyl chloride, 25 to 55% by weight of vinyl acetate and 0.2 to 6% by weight of unsaturated carboxylic acid, such as, for. B. Crotonic Acid The thermoplastic polymer preferably used contains 50 to 65% by weight of vinyl chloride, 30 to 49% by weight of vinyl acetate and 0.5 to 30% by weight of acid. As described above, the polyester molding compositions containing the polymers are generally in-amounts of 2 to 25 and in particular of t-is "20 <3öv. * Bessogert · share. On the total resin system of the approach. The resin system used here is composed of einef combination of unsaturated

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Polyester, unsaturated monomer and thermoplo.tisch.em monomer em.

The mixture of polyester, monomer and polymer can alone cured by the action of heat or preferably by adding a suitable curing initiator. Suitable Curing initiators are benzoyl peroxide, tert-butyl peroctoate, Di-t-butyl peroctoate, t-butyl perbenzoate, cyclohexanone peroxide, Di-t-butyl peroxide, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, t-butylazobisisobutyronitrile, di-t-butyl ~ diperphthalate, 2,5-dimethyl-2,5-bis- (2-ethylhexanoylperoxy) -hexane, 1, i-di-t-butylperoxy-JiJ ^ -trimethylcyclohexane, 2- (t-butylazo) -isobutyronitrile, Lauroyl peroxide, isopropylbenzyl hydroperoxide, t-butylbenzyl hydroperoxide, methyl ethyl ketone peroxide, I-hydroxycyclohexyl hydroperoxide-I, similar compounds or combinations of these initiators.

The suitable initiators are expediently used in an amount of about 0.1 to 3.0% by weight, based on the weight of the entire resin system consisting of three components. The molding compound is cured under pressure and temperature conditions which, when using closed “preferably nit ν; ^ given pressure a:? bsi tender compression forms are common. Lac * jtiär "cungsg * 3sohwindigkei" c dex ¹ molding compound can be

Inhibitors, mSj> Hydroquinone, tert.-Butyl-Bencalaali ^ a ozl® .: uiitraciilorchinon or from ge "wt - ii Bescüinunigerii, like certain amines, ζ. B. Dimethylaniii.1., I) iä"" njlanil: Lii _: Di-n-iirop ^ lani-lin * Diiaethyl-p-toluidine,

2 υ 9 δ w S / 's \ 13

p-Diethylaminoazobenzene imd.Dimethyl-m-aminophenol or of Control metal bars such as cobalt or manganese naphthenate.

The molding compositions according to the invention which are preferably used contain to reduce the resin content and / or to improve the physical properties of the molded parts fillers. Suitable mineral fillers are e.g. B. clay, ground limestone or gypsum white, talc, calcium carbonate and cellulose in any form. To improve flame resistance Aluminum hydroxide, sodium borate or antimony oxide can be used will. Other fillers that also serve as reinforcement material are staple glass fibers, glass mats, sisal, Asbestos or synthetic polyamide, polyester or acrylic fibers and high temperature-resistant fibers, in particular. Carbon and boron fibers.

In addition, the molding compounds generally also contain additives, such as softening ?, mold lubricants and coloring materials such as B. pigments or dyes. The used in detail The quantities of a certain additive are usually determined by its particular function in the molding compound.

Molding compounds suitable for the compression molding process are produced in such a way that that 50 to 70% by weight of an unsaturated polyester usually with 50 to 50% by weight of an unsaturated monomer to an easily manageable liquid and the remaining monomer with the normally solid thermoplastic polymer can be premixed to a syrup. The two monomer

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solutions are either presented separately or as a homogeneous, not ' demixing one-component resin brought onto the market.

The molding compositions according to the invention are, depending on the shape of the molded body to be produced, t, q \) ± _s 50 seconds at temperatures of about 120 to 165.degree. C. and pressures of about 3-5

formed up to 140.6 kg / cm. Compression molding, compression molding or Injection molding processes are equally important for processing of the thermosetting resins.

The examples illustrate the invention.

(Unless otherwise stated, all parts are parts by weight)

example 1

An unsaturated one for the production of the molding compositions according to the invention suitable polyester is by esterification of 1.05 mol Propylene glycol with 0.33 moles of isophthalic acid and 0.67 moles of fumaric acid produced to an acid number of less than 30.

The polyester obtained is dissolved in styrene, so that an unsaturated polyester resin with about 62% by weight solids content is obtained receives.

Examples 2-4

According to Example 1, unsaturated polyesters and unsaturated polyester resins are produced from the starting compounds listed in Table I. The results are in

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Table I compiled.

Table I.

Unsaturated polyester resins "Example Mr.: 1 ·

Per peel glycol 1.05 1.05 1.10 i, io Isophthalic acid 0.33 0.33 0.33 0.50 Draw in the acid anhydride - - 0.67 0.50 JFumar's acid 0.67 0.67 - - Acid number below 30th 45 20th 20th Solid content in styrene, Weight percent 62 67 68

*) Bie numbers mean mole counting, unless otherwise stated ο

Examples 5-7

In this example, e & emiseli-bonded bromine is produced as an unsaturated polyester containing ammhemaendes Hittel from the amounts of glycols listed in Table II with the corresponding amounts of tetrahydrophthalic anhydride and sharkic anhydride up to an acidity of less than 35. In each case, the bromine (0.5 mol) is added to the letrahydrophthalic acid residue in accordance with the procedure according to ÜSA Batentschrift 3,536-82, the maleic acid double bond according to the invention not being involved.

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ligt remains. After the bromination, the respective polyester product becomes dissolved in styrene, so that you get an unsaturated polyester resin with the solids content given in the table receives.

Table II **) 6th *
7th Example Έτ * : 5 - - Ethylene glycol 1.10 1.10 - Diethylene glycol - - 1.10 Neopentyl glycol - Tetrahydrophthalic 0.55 0.45 acid anhydride 0.50 0.45 0.55 Maleic anhydride 0.50 35 35 Acid number below 35 Solid content in styrene '77 68 Weight percent 70 about high bromine content, 30th 25th Weight percent. 20th

**) The figures mean numbers of moles, unless otherwise stated *

Example 8

A polymer is made from vinyl chloride, vinyl acetate and crotonic acid as follows:

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A 379 liter pressure reactor is equipped with a stirrer, a thermocouple, a pressure regulator, a temperature control device with appropriate heating and cooling equipment, Baffles, a baffle plate and external pumps for feeding in the initiator solution and water.

The reactor is fed as follows:

121 g polyvinylpyrrolidone as a dispersant

(PVP-K90 from GAF Corp., Ν.Ϊ., - Ν.Υ., V.St.A.)

1348 g crotonic acid
318 kg of water.

The reactor is sealed and evacuated from 660 torr to 76 torr using a vacuum pump. \Afterward the reactor is filled with vinyl chloride to atmospheric pressure. This evacuation and filling with vinyl chloride is repeated, the reactor was then evacuated again and 60.36 kg of vinyl acetate and 61.2 kg of vinyl chloride were added.

The reaction mixture is then heated to 90 ° C. The reaction pressure at this temperature is 10.9 atm. Tert-butyl peroxypivalate (75% in mineral spirits) is diluted with methanol and a solution containing 15% by weight of active initiator was prepared. This initiator solution is continuously with a medium Feed rate of 8.5 ml / minute approximately 270 minutes long pumped into the reactor. The reactor contents are then for another 30 minutes to ensure complete

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Decomposition of the initiator kept at a temperature of 90.degree. The reactor pressure is 1.83 atm. The reactor is then cooled to 60 ° C., the contents of the reactor are drawn off and the polymer is separated off from the other constituents by centrifugation and then dried. The yield is 105 ₅ 36 kg of white, granular polymer product, that is, based on the Ilonomerzuspeisung, 86%.

The chlorine analysis shows a vinyl chloride content of the polymer of 57 »5% by weight.

The molecular weight of the polymer is determined by viscosity measurements. The viscosity number is measured with a capillary viscometer determined at 30 ° C on solutions containing 1 g of the polymer in 100 ml of cyclohexanone. The viscosity number is defined as follows:

Viscosity - ^L ^ the solution viscosity number fzeit - _Duration of the solvent

The viscosity number of the polymer is 0.4-3 and its Acid number 4.3

Examples 9-13

In these examples, following the procedure of Example 3 other polymers made from vinyl chloride, vinyl acetate and crotonic acid, but with the composition as in the following Table III described is changed. As indicated

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ben, some polymerization attempts are made in a small one Reactor carried out.

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Example no .:

Reactor size, liter ¹ charge of vinyl chloride, kg of vinyl acetate, kg of crotonic acid, g of crotonic acid in the monomer charge, percent by weight of suspending agent, g of water, kg of reactionate eraper ature,. ⁰ C

Reaction pressure, atÜ to reaction rose inn at the end of the reaction

Response time, hours

Tabel 8th III 10 11 12th - 26 f
β ** N>
N>
CD
cn 379 9 3.79 3.79 379 13th I. 61.2 3.79 0.5 0.5 60.8 3.79 60.36 0.5 0.5 0.5 61.2 0.5 1348 0.5 11 17th 2020 0.5 1.0 2.8 1.0 1.5 1.5 33 ₁₂₁ a) 0.25 3.0 ^b) 2.0 ^b) ₁₂₁ a) 3.0 318 3.0 * 1.99 1.99 318.45 1.5 ° ^} 90 1.99 80 80 80 1.99 10.9 80 · 28.1 21.1 9.21 95 1.83 21.1 .22.5 21.1 1.62 21.1 4.5 21.1 2.25 2.75 21.1 1.75 1.0
*

Table III (continued)

O CD CD 00

Example STr. :

Initiator feed rate, ml / min

Yield, based on the total Monozierenbe delivery,

Vinyl chloride, percent by weight *)

10

11

Acid number viscosity number

8.5

57.5 4.3 0.43

0.1 "5

0.22

82 1 79 , 6 64 7th 57, 9 62 , 2 58 4th ■ 1, 48 3 , 46 7, 45 O, 0 0,

10.0

82

57.5
7.3
0.51

»45

69

59.0 11.9 0.34

a) = PVP-K90

b) = polyvinyl alcohol (Elvanol 50-4 ² , EI du Pont de Nemours)

c) = To maintain the liquid level in the reactor

water pumped into the reactor

.rO

*) = as described above. £ ?.

cn

CD

Example 14

In order to show that reinforced polyester molding compounds made from conventional, not containing thermoplastic polymer components produced moldings generally have a rough surface and throw themselves on cooling, becomes a Resin molding composition containing polyester product from Example 2 for producing a panel using the preforming process applied:

In a high shear mixer, combine the following components and hold for 1 to 2 minutes mixed:

Amount xn Components Parts by weight Polyester-styrene solution from example 2 86 t-butyl peroctoate (initiator) 1 Zelec UN *) mold release agent 0.5 Styrene 14th

100 parts of the calcium carbonate filler are added to this mixture added in the course of 1-2 minutes and then the obtained Mixture stirred at high shear for 4-5 minutes.

The mass produced in this way is placed on 2 layers of glass

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fiber mat (670 g / m ² , OCF M 8600, manuf. Owens Corning Fiberglass) poured and covered with 0.25 mm thick glass fiber fleece · The impregnated mat is in a form (JO, 5 x 30.5 x 2.5 cm) heated to 135 ° C for 2 minutes at 35> 2 atmospheric pressure, then removed from the mold and cooled to room temperature. The molded part is badly warped and has a fairly rough surface.

In order to obtain numerical comparative figures for the relative surface smoothness, the surface smoothness of the mold plate is measured with a Bendlx microcorders (manufactured by Bendix Corp., Industrial Metrology Division) according to the one specified in the manufacturer's instructions Er »JO 440 Procedure determined. The microcorder values are through Kessen determined in four statistically selected zones. Each value represents the mean of four 1.27 cm segments along a 5 * 08 cm long track. The mean of the 4 tracks represents the desired mean value for the entire plate.

The mean surface smoothness of the panel produced is 10.16 yes, measured with the Bendix microcorder * Here mean lower values smoother surfaces.

Example 15-17

Following the general application procedure of Example 14 are the thermoplastic polymers of various examples above containing resin molding compositions produced. In all cases the amounts of components used in the preparation correspond to the amounts used in Example 14, but

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the amounts of polyester, styrene monomer and (thermoplastics acc Table IV below can be changed. The one with the molding compound containing no thermoplastic polymer Values obtained from Example 14 are included in Table IV for purposes of comparison. Impregnation of the preforms and compression molding are carried out as described in the previous example. The following results are obtained:

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Tabel IV 15th 16 17th Example ITr » 14th 2 1 2 Polyester-styrene solution
from example no <> 2 56 62 62 Parts by weight 86

Styrene, parts by weight

Polymer of Example No. <> parts by weight

Calcium carbotate,
Parts by weight

Fiberglass mat,
Parts by weight

Zelec UN *)

Parts by weight ■

t-butyl peroctoate initiator,

Parts by weight

100

78

0.5

1.0

30.5 24.5 24.5

13 12 8 13.5 13.5 13.5

100

78

0.5

-> 1.0

MCR

400 ^b 133 ° 170 ° 125 ^C

*) As described in example 14

ä) MCR = measured with the Bendix microcorder Surface smoothness values

b) Plate badly warped

c) Plate not warped.

209885/1159

The above MCE values show that thermoplastic Molded bodies produced containing polymers in comparison with those produced from a conventional reinforced unsaturated one Polyester mass obtained moldings ^ a considerably have better surface smoothness. In addition, they are with Moldings produced by the improved molding compositions according to the invention are hardly warped.

Examples 18-23

The following effects, namely the effect of the thermoplastic polymer on the rate of viscosity increase, the lack of phase separation and the non-sticky consistency of the thermosetting molding compound after aging are determined as follows:

400 g of a mixture of a polyester, styrene and a thermoplastic polymer are placed in a 995 g beaker weighed and then the resin mixture while stirring 400 g calcium carbonate were slowly added with high shear force. Stirring is continued until the mixture has reached a temperature of 37 »8 ° C. (with a Premier Mill Corp. Temple EA stirrer in the generally after 2 to 5 minutes). The viscosity of the mixture is measured with a Brookfield viscometer (model RVT with spindle No. 6 or model HBT with spindle No. 3 at 2.5 Rpm).

Then the desired amount of a chemical thick-

209885/1159

means in the mixture, stirred and then with the storage of the Molding compound started. The entire molding compound is poured into a wide-shark glass bottle which is kept at 37-8 ° C Water bath stands. The Brookfield viscosity of the mass being stored is measured every 10 minutes for at least 60 minutes.

The bottle is then closed, stored in a constant temperature oven for a few days and during this time the hardness of the mass is measured at certain intervals using a penetrometer (Precision Scientific Company) fitted with a Humboldt needle Mr * .H-1310 and a 100 g weight. The needle is placed on the surface of the sample, the instrument is unlocked for 5 seconds and the penetrometer reading is noted (a lower value indicates a harder sample). The mean of at least 3 values is noted. · Any separation into solid and liquid phases is determined by visual observation. Various polyester batches are produced and their viscosity behavior is determined using the method described above. The polyester-styrene solution from Example 1 is used in the amounts given in Table V in each batch. Unless otherwise stated, the thickener is CaleiumhydroxLd.Pie results are summarized in the following table: ■ -.-

209885/1159

le Y

Example no .:

Polyester, parts by weight

thermoplastic polymer of Example Ur. Weight steep

Calcium carbonate, parts by weight thickener, parts by weight

19th

400

20th

280

'21

224

22nd

149

23

224

cn styrene, _{parts by weight}

- - 11 11 10 10 0 0 120 ^a 120 ^a 80 ^a 120 ^a AC) C) (^ 4th 12th 4th 12th 2.5 12 * 0 0 0 56 37 56

a = 45 percent by weight solids solution in styrene; "b = modifier (Marco Chemical Co.)

Brookfield viscosity '

10 ³ cP min. 0 TO 20 30 40

(M = χ 103, e.g. 1.5 M - 1,500.00 cP). .S

*) = HBT model viscometer, spindle. No. 5 "at 2.5 rpm Ms to full scale deflection. ^

1 and 0.5 rpm for higher values, - - *

3.2. 3.8 22 4th 22nd * ° M. 48, 0 M. 6.4 4.8 480 86 4th 1 , 2 M. - M. 54.4 8.0 1.5 M. 182 1 , 3 * M 1, 3 128 16.0 256 1 , 6 1, 6th 520 22.4 - 440 - - 1.0 M.

! Table V (port setting)

Example Ur. :

Penetrometer values Hunt (at 52.2 ⁰ C) 1 "2
3
4th 209885, 5 ^ » 6th
7th cn

19th

20th

21

22nd

25th

P. 285 440 277 335 15C P. 198 285 222 270 - P. 172 - 200- 250 - P. - - - - - 115 P. - 265 - - 113 P. 165 240 182 205 100 P. _ 218 191 80

P = liquid, penetrometer value above 500

All of the mixtures listed above exhibit throughout Aging time on a non-sticky surface. During this time there will be no phase breakdown in the mixtures observed.

The above results show that by adding a thermoplastic polymer, the viscosities of polyester batches can be increased to the desired values after a very short aging time, although considerably smaller amounts are conventional chemical thickeners can be used.

Examples 24-26

Following the general procedure of Example 8, polymers are made in a 3 »79 liter reactor made from monomer mixtures of vinyl chloride, vinyl acetate and olefinically unsaturated acids as shown in the table below. the The concentration of the initiator (in methanol) corresponds in each case to that of Example 8. The initiator is given with the specified, fed into the polymerization mixture at the prescribed rate. In addition, each is used to maintain of the liquid level, water is pumped into the reactor. The results are summarized in the table below:

209885/1159

Example no.

feed

»G

Vinyl acetate »g methacrylic acid» g

Itaconic acid, g

te

G-

,, a til

Table YI

ml / min

Yield, "be ^ og ^ rt suf clie @ © saatmoTioitteretiauspe i sinag,

Vi s "fc o s it it sz.ah.1 Acid number '

a) =

*) α like 495-495 IO

1 _t C

5.8

495

1 * 0

26th

492 492

13th

2 . 2 t 2 t 95 95 η 80 25th 21 * 4 · ; "'2i, 20th
. · Ο 1 * 25 1* . "η . ·. * ■ 0 * - β € 8

0.3-8

9.4

All polymer products are dissolved in styrene and a prescribed Amount of calcium hydroxide, Ca (OH ^ i added to the resulting solution as a thickener. The solutions are then 60 minutes and 18 hours after the start of storage and observed whether they are still flowable. There will be the following Get results;

Flowability of the

Polymer

Product in styrene, %

ThH storage storage

Example 24 35 2 * 3 about a no

Example 25 35 2 * 3 'something-, no

Example 26 45 3 * 0 yes no

*} Parts by weight per 100 parts by weight

The results obtained show that, in particular, the unsaturated acid monomers used to produce these polyester products, together with a chemical thickener, produce a solution of the polymer in styrene which, after aging, is no longer flowable from that used in individual MoBQKeren from.

To explain this further », polymers are made according to the method of the present invention from various percentages by weight

209885/1159

Crotonic acid-containing monomer mixtures prepared. the obtained products are dissolved in styrene and treated with Ca (OlOo, as described above. The results are shown below:

Flowability of the

solution

Acid concentration polymer concentration

tion *) tration. Ca (OH) ₂ 60 minutes 18 hours

in styrene, ^ _ ,, "storage storage

0.00 0.25 0.50 1.00 1.50 3.00

45 45 45 35 45 35

3 2.3

3 2.3

Yes

yes something

something no no

*) Parts by weight fed into the polymerization vessel

Yes

Yes

no no no

209885/1159

The above results indicate that one out of polymerization a mixture containing only vinyl chloride and vinyl acetate and no unsaturated acid monomers Polymer together with the chemical thickener described does not result in mixtures that are no longer flowable and therefore easy to handle after storage. Veiter show polyester approaches, the such non-acidic polymers together with chemical thickeners such as inorganic oxides and hydroxides, usually a phase separation after aging Polyester mixtures containing thermoplastic polymers together with chemical thickeners do not phase separate after aging on.

Examples 27-37

As shown in these examples, the viscosity behavior of the polyester compositions with aging can be determined by using different Thickeners or different concentrations of thickeners, through the use of different types of polyester and the thermoplastic polymers contained therein in detail are modified. According to the in Examples 18 to 23 The batches prepared and the results obtained are listed below:

209885/1159

ΙΌ
O

CD
OO
CO

cn

Ul

«Ο

3example

No .: 27

? clyester-St yr olio solution of Example 2 «<

Part by weight 400

thermo "Blasti sciiee

Polymer

vcn example no

Part by weight ^a 0

C al G line ar— "bonat,

Parts by weight 400 <■

Dickmixtel Oa (OH) ₂

Parts by weight

Styrene,
Weight xeile

Brookfield-Yi sic ο six ät *) 1C ^ c? There. '

10
20th
30th
40
50
60

12th

11 11 11 11 11 11 11

28

213

24 120

30th

Table VII
31

32

33

34

35

36

140/140

12th

12th

12th

-> 400

400 400 ■ 400

- $ ► Ca (OH) ₉ calcium

^ oxide Oa (OH) ₂ Ca (OH) ₂ MgO Hg (OH) ₂ Ca (OH) ₂ ,

^ r

.8th

12th

a) = 45 fo concentration in styrene solution

26 30 124 700 1.7H> 2, OH

26th

53
784
1.4M

M = cP χ 10 '

• 7.

26th
32

53
150
227

19 21

131 26

31

36

48

- ■ 728 67

87
determined as described above

35

80

195

310

48 46 42 4.0 40 48 76

Ni CD CT!

example

27 28

Penetrieter - Werxe

(at 32.2 ⁰ C)

29

Table VII (continued)

32

33

34

36

1 240 2 O CO 4th 151 CO
CO 5 145 cn
^^ 6th - ^^ 7th 114 cn «Ο

330 345 252 . - - 212 194 204 154 200 • mm 182

252 365 520 225 - P. - - - 162 - 420 172 285 - - 220 310 159 205 305 - 184 260 260 "

170

F = flowable, penetrometer values> 500

All approaches prove. Aging non-sticky Surfaces on.

*) = The penetrometer value of this approach is after 3 days of aging 188, which indicates a relatively viscous material.

For comparison, polyester sets according to Example 29 are under Use of the thermoplastic component, a polymer produced in accordance with the process in Example 8 I) CScIrTi eb en, However, only a mixture of vinyl chloride and vinyl acetate without unsaturated acid monomers is used. An approach with this thermoplastic component in combination with a chemical thickener shows the secretion a sticky liquid layer.

Examples 38 "through 4-1

Following the general procedure of Examples 18 to 23 flame retardant polyester-containing approaches with and made without chemical thickeners. These approaches and their viscosity values after aging are summarized below :

209885/1 159

*) Table ι Ca (OH) ₂ / III 39 26th 40 41 Example no. a) 38 6th 432 7th 7th Polyester styrene
solution of
Example no. Brookfield viscosity 6th 242 - 400 221 Parts by weight 10 cP minutes 400 8th - no 8th thermoplastic
Polymer of
Example no. O no" 120 - 0 120 a)
Parts by weight 10 0 - Calcium carbonate, 20th A_nr \ Γ * ο \ kf * i r> Vi Ι "ο 4 ~ c * · ΐ * 1 ο 30th Δ ΠΓ \ m T-WW vrtiWJ-L / Xlbo belle
Thickener * ', 40 HKJU ^ 1 2 Π-ΡΛλΜ P Vl "t ~ Q ~ f ~ P" 1 * 1 P 50 12 ^ I C— VJvW JL-Xl UO Ki Kj X-J_C
Styrene, 60 38 0 59 Parts by weight 0 = as described above 8th 13th 42 32 24 580 72 56 800 80 108 820 84 160 870 88 330 1.1 M. 90 450 1.2 M.

20988b / 1 1 b 9

22295S1

In the batches of Example 39 and 4-1, no air vent and no sticky liquid layer can be seen after aging »

Examples 42 to

3föimplatten are made by different molding processes under? Er * production of the following resin preparations:

209885/1159

Table IX

Example Mr. :

Polyester-Styro! Solution
from example Kr.

Parts by weight

thermoplastic. Polymer ■ of example no.

Parts by weight
Styrene, parts by weight
Calcium carbonate, ■ parts by weight of clay, parts by weight
Mold release agents,

G ewi ent st e il e
chemical thickener ',

Parts by weight

Antimony trioxide, parts by weight Type of glass fibers,

Parts by weight

'Art. of the initiator

Parts by weight

Type of approach d «molding compound

42

43

44

2 61.5

■ 13.5 25 100 O

. ZeIec ΉΈ 0.5

0 0

O.G.F. M8600

mat

86

tBPO 1.0

for hand-operated ferries with preform

4 56

'• 3.5 50.5 128 0

ZeIec WE 1.0

0 0

O.C.F. 832 0.64 cm fiber

57

tBPB 1.0

for dough pressing processes

2/5;
23.5 / 32.2 ^a)

13.5
30.8

100

Calcium stearate
3.0

2.0
5.0

O.G.F. 832

0.4 cm fiber

52

- 46 45

2 56

12th

13.5 30.5 150 0

a) * contains 1.0! Beile Iriäthylphosphat

b) = Modification process (M, Marco Chemical) *) = E.I. du Pont de Semours

tBPO tBPB

tBPB tBPB

. 1.0 1.0

• • for Peigpress- for procedure Process for the production with formerly of GRP panels Thickener

t -Buirylpe ro et ο at
■ t-butyl perbenzoate

Calciurast earat <jD 3.0. S.

3.0 0

O.C.F. 2.54 cm fiber

103

Each of the foregoing approaches comes in a form for manufacture of plates with the dimensions 3> Ο, 5 χ 30.5 x 2.5 cm shaped. '

The approach to the hand molding process using a preform is made by adding the polyester-styrene solution, the thermoplastic polymer, the initiator and the Mold release agent mixed with high shear for 1 to 2 minutes and then · the mineral fillers slowly added with gentle stirring. The resulting mixture is then further stirred with high shear for 4 to 5 minutes. The finished batch is poured onto a glass fiber mat and covered with a 0.2 μm thick glass fiber fleece. The impregnated Mat is placed in the mold and at 155 C and 35j2 atü molded for 2 minutes. The shaped body is then removed and cooled to room temperature.

The batch for the dough pressing process is prepared by mixing the polyester-styrene solution, the thermoplastic polymer, the initiator and the mold release agent and then adding the mineral fillers as described above. The glass fibers are then added and the mixture is thoroughly stirred. The batch is removed from the mixer and ^{shaped at 149 °} C. and 70.3 atmospheres for 1.5 minutes. The molding is then removed from the mold and cooled to room temperature.

The approach to the dough pressing process with a chemical thickener is made like the approach for the dough pressing process; · ",

20988b / 11 & 9

however, the approach before the addition of the glass fibers is a chemical one Thickeners in one given in the table above Amount is added. After aging, the batch is molded at 149 ° C. and 70.3 atmospheres for 3 minutes. The molded body is then removed from the mold and cooled to room temperature.

The approach to the process of making GPK sheets is including the addition of the chemical thickener like the approach for the dough pressing process

manufactured. The finished batch is then made using a machine for the production of molding compounds for GRP panels applied to glass fibers. After aging, the film cover is removed and a non-sticky molding compound for the process for producing GRP panels is obtained. This is molded at 1 ^ 9 ° C and 70.3 atm for 2 minutes. The plate is then removed from the mold and cooled to room temperature.

None of the moldings produced was warped.

The surface smoothness and physical properties the moldings obtained are shown in Table X below.

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Claims (10)

Claims \ ί Improved thermosetting molding compounds, characterized by a content of (a) 20 to about 60 parts by weight of a polymerizable unsaturated polyester, (b) about 20 to 65 parts by weight of a polymerizable vinyl monomer, (C) approximately 2 to 25 parts by weight of a saturated thermoplastic polymer obtained by suspension polymerization of a monomer mixture of vinyl chloride, vinyl acetate and / 1 to 2 an olefinically unsaturated acyclic monomer with 7 Carboxyl groups of the general formulas I or II ' _λ r1_C-R ² R ^ HC = C-CQOH _R 3_c__c00H. H ₂ C - COOH wherein R is a hydrogen atom or a methyl, carboxyl p
or phenyl group, R is a hydrogen atom or a 12 - Represents carboxyl group, but R and R are not equilateral Are carboxyl groups, R ^ is a hydrogen atom or a methylol group and R is a hydrogen atom or a hydroxyl group means, in an aqueous medium at temperatures from 50 to 1 ^ ofc was prepared in the presence of a polymerisation initiator, and optionally (d) usual filling and auxiliary equipments, reinforcement materials, Mold release tablets, printing media, pigments, initiator or accelerators. ORiGlNAL INSPECTED 2. Molding compositions according to claim 1, characterized in that the polyester (a) is from a polyol, in particular a Cp .. "- Polymethylene glycol, propylene glycol, butylene glycol, a C ^ _ _2Q polyethylene glycol, dipropylene glycol or its higher homologues, Neopentyl glycole bsw. a mixture of these polyols, as well as a polycarboxylic acid, especially fumaric acid; Maleic, itaconic, citraconic, mesaconic or chloromaleic acid or their anhydrides or a mixture of these acids and anhydrides or a mixture of these acids and anhydrides with at least one saturated dicarboxylic acid. J>. Molding compositions according to claim 1, characterized in that the polyester (a) was produced from 0.8 to 1.2 mol of polyol per 1 mol of polycarboxylic acids). 4. Molding compositions according to claim 1, characterized in that the polyester (a) of fumaric acid, isophthalic acid and an alkylene glycol was produced. 5 · Molding compositions according to claim 1, characterized in that the polyester (a) is made from maleic anhydride, isophthalic acid and an alkylene glycol. 6. Molding compositions according to claim 1, characterized in that the polyester (a) (1) a 0 £ ß-unsaturated olefinic carboxylic acid with up to to about 20 G-atoms or their anhydride, (2) bucket of skin-substituted dicarboxylic acid with * ""., "' up to about 20 carbon atoms or their anhydride, the unsaturated Carbon level fh ^ hl enstoffbundeneri at most in Pern: :: i \ mr ^ tlv.c contains binding states, and a polyol with 2 to 24 carbon atoms was prepared, the polyester being about 15 to 6 ¹ mol percent of component (1), an amount of component (2) sufficient for a halogen content of 10 to 50 percent by weight and 100 to 125 percent of the stoichiometrically required in relation to the carboxylic acids used Amount of component O) contains. 7. Molding compositions according to claim 1, characterized in that the Vinyl monomers (b) is styrene, chlorostyrene or tert-butylstyrene. 8. Molding compositions according to claim 1, characterized in that the thermoplastic polymer (c) 40 to 70 percent by weight vinyl chloride, 25 to 55 percent by weight of vinyl acetate and 0.2 to 6.0 percent by weight of the olefinically unsaturated acyclic Contains monomers. 9. Molding compositions according to claim 1, characterized in that the thermoplastic polymers (c) containing crotonic acid, fumaric acid, itaconic acid or methacrylic acid as acyclic monomers. 10. Use of the molding compositions according to claims 1 to 9 for Production of reinforced moldings. ORIGINAL $ 209,885 / $ 115