DE1900979A1 - Rigid, high-impact, thermoplastic molding compounds based on polyvinyl chloride and a graft polymer - Google Patents

Description

DR.ING. F. WUBSTHOFF β MUNICH ΘΟ DIFIuINCCPtTIJS 8CHWEIQERSTRASSEt DR.Ry.PKCHMA.NN TSumrOM S3 Ο «Sl DR. INC D. BKHRKNS "". »H.ad.» .., PATENTANWiLT * pbotbctpatsmt mCxc * »

1A-35

Description of the patent application

PECHINEI-SAIKT-GOBAIN

67, Boulevard du Ch & teau (92) Neuilly-sur-Seine

France

concerning

Rigid, high-impact, thermoplastic molding compounds based on polyvinyl chloride and a graft polymer

The present invention relates to rigid, impact-resistant thermoplastic molding compositions made from homo- and / - or copolymers of vinyl chloride and graft polymers based on butadiene, a nitrile of an acrylic derivative, a vinyl aromatic compound and an alkyl methacrylate exist.

It is known that the impact resistance of Horao- or copolymers of vinyl chloride can be improved by mixing with the following graft polymers:

Styrene and acrylonitrile on polybutadiene, a butadiene-aorylnitrileopolymer, a butadiene-styrene copolymer or a butadiene-styrene-acrylonitrile copolymer

Styrene and methyl methacrylate on polybutadiene or a Butadiene-styrene copolymers j.

Acrylonitrile, styrene and methyl methacrylate on a butadlene styrene polyraeren.

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These mixtures result in molding compounds with which moldings with improved impact resistance can be produced; However, the moldings are not transparent but opaque and, if they are thin, white spots that remain on the kinks or folds or under slight pressure are formed. These disadvantages severely limit the usefulness of these hates.

The present invention is based on the object to remedy these disadvantages. It brings molding compounds based on homo- and / or copolymers of vinyl chloride, which are easy to handle and process (kneading, extrusion, valnium deformation) and from which particularly transparent, can produce high-impact objects, which, if they are thin, leg or fold or do not form white spots even under strong pressure.

The molding compositions according to the invention should be 60-99% by weight, preferably 80-95% by weight. from homo- and / or copolymers of vinyl chloride and 40-1 wt .- #, preferably 20-5 wt .- # of a graft polymer whose trunk or chain is formed from butadiene, acrylonitrile, styrene and at least one crosslinking ionomer and the grafts or side chains are formed from at least one vinylc aromatic compound, at least one alkyl methacrylate, α ^ u least a nitrile of an acrylic derivative and optionally at least one crosslinking I-Ionooeren.

As Vinylohloridcopolymere all copolymers are referred to, at least 50 wt .- / »vinyl chloride units and vinyl ether and säureester as Coraonomeres -estereinheiten such as vinyl acetate, alkyl acrylates and alkyl methacrylates, fumarates, Ilalein-, Chlorfuraarsäureester, Chlormaleinsäureester, vinylidene chloride, vinyl pyridine, ethylene and / or Contain propylene.

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The copolymers and polymers of vinyl chloride can be prepared by emulsion polymerization, by polymerization in fine suspension (is carried out with the same catalysts as suspension polymerization, but carried out with emulsifiers such as emulsion polymerization) and preferably by polymerization produced in bulk or suspension polymerisation four den if maximum transparency is to be achieved.

The graft olynes consist of IC - 95 wt .- # of a main polymer or a main chain and 90 - 5 wt .- £ of grafts or side chains; the trunk is made of a copolymer *! formed, the *! O - 9 ^, 5 % by weight; 4 butadiene units, 2 - 30% by weight acrylonitrile units, 2 - * K>% by weight ;? Styrene units and 0.1-10% by weight, preferably C, 5-5% by weight units

of at least one crosslinking agent. The graft prices consist of 1 - 85 wt .-; S of at least one vinyl aromatic Compound, 1-85% by weight of at least one alkyl methacrylate, 0-3C wt .- # of at least one nitrile of an acrylic derivative and 0-5 wt .-) '* at least one crosslinking conomer.

For practical and economic reasons it was decided stipulates that the proportion of grafts in graft polymers should not be more than 90% by weight, & otherwise the reinforcing Capacity of the graft polymer is low. aside from that should preferably the proportion of grafts; i? .oht less than 5 wt .- / ^ if it is to be avoided that a Lump-forming polymer that is later difficult to mix is obtained will.

It was also found that the proportion of styrene units in the base polymer was not more than 10% by weight; be should, as the graft polymer would otherwise lose its reinforcing properties loses. The proportion of acrylonitrile should not be more than 30 wt .- ^, otherwise the heat resistance of the Fgraft polymer decreases.

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The aromatic vinyl compounds to be grafted on i. -Methylstyrene, chlorostyrenes and preferably styrene in question.

The alkyl methacrylate is chosen from the kethacrylates, whose alkyl group contains 1-5 carbon atoms.

The nitrile of an acrylic derivative is methacrylonitrile, chloroacrylonitrile and preferably acrylonitrile itself is used.

All vinyl- like and / or acrylic-like ionomers which have at least two ethylenic double bonds that polymerize radically with practically the same reactivity are referred to as crosslinking honeycomers. These conomers include, for example, divinylbenzenes, Dis.sth :. ^r Iacrylates and diacrylates of ilono and polyethylene glycol, di vinyl sulfur, divinyl ether, vinyl acrylate, trivinylbenzene and triraethylolpropane trimethacrylate.

The standard polymer is produced by emulsion polymerization in the presence of at least one initiator which forms free radicals and one or more emulsifiers at a temperature of 0-10O ⁰ C depending on the initiator used.

Hydrogen peroxide are used as radical-forming initiators, Persalts such as potassium and ammonium persulfate, organic perborates and peroxides e.g. tert-butylhyciraperoxide, cumene hydroperoxide., Diisopropylbenzene hydroperoxide, benzene peroxide, lauroyl peroxide, etc., optionally in conjunction with reducing agents such as ITatriujnformaldehyde sulfoxylate, sodium metabisulfite, aliphatic Amines or polyamines, mercaptans, misen (II) sulfate and Glucose in question.

Emulsifiers are especially alkali salts of fatty acids, modified resin acids (dresinates), alkylarylsulfonic acids, Alkyl sulfuric acids and alkyl sulfosuccinic acids.

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After the polymerization, a latex of the parent polymer becomes ■ meren obtained, the composition of which largely corresponds to the ratio of the monomers used.

The grafting onto the base polymer takes place in emulsion by adding the ilonomers to be grafted to the latex of the Parent polymers. The vinyl aromatic compound, alkyl methacrylate and optionally the crosslinking monomer are added individually or as a mixture with one another. Just that Acrylic derivative nitrile, if present, is preferably used with the vinyl aromatic compound and / or the alkyl methacrylate be admitted. The individual monomers or monomers present in a mixture are fed in either all at once or gradually; in the latter case, a Z-.:ischen polymerization can be used first carry out the added graft fraction, before the next serving is added; feeding can of course also take place continuously.

Simultaneously with the monomers to be grafted on can Polymerization regulators are added, e.g. mercaptans, in particular tert-dodecyl mercaptan, in a mixture from 0-2 wt .- #, based on the ilonomers to be grafted on.

In general, preferably no emulsifiers are added during the graft polymerization. But it can in some Cases can be very useful, especially to avoid the formation of crusts in larger slopes, before or during add additional emulsifier in aqueous solution to the plug, either all at once, or in portions or continuously. This emulsifier can be the same as that used in the manufacture, Position of the parent polymer is used or another and is selected from the list above.

The one used in making the parent polymer Initiator kaxm in to carry out the graft polymerization required minimum amount must be used. However, it is preferably used in excess and is in organic

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see solvents soluble or it will to the drain To support the graft reaction, a second initiator from the list given above.

The grafting reaction is at temperatures of 30 - 100 ⁰ C led to virtually complete conversion.

After completion of the grafting v / ground the latex 0.5-5 wt -.% _T based on the polymeric end product, a phenolic, phosphorus and / or sulfur-containing antioxidant is added, as is generally conventional in the manufacture of elastomers, in particular Dibutylparakresol, Trinonyl phenyl phosphite, dilauryl thiopropionate. The antioxidant does not necessarily have to be added, but the addition avoids the superficial oxidation of the graft polymer during the subsequent drying, which could adversely affect the properties.

The graft polymer is used either directly in the form of latex or isolated in manner known per se, for example by spray drying or by coagulation by adding calcium chloride, alum or mineral acid, and then centrifuging, straining and drying,

To produce the molding compositions according to the invention, the homopolymer or copolymer of vinyl chloride with the graft polymer mixed in the form of powders or latices. In the latter case, the mixture is then atomized or coagulated, washed and dried.

It has been shown) that

1. the composition of the parent polymer the properties of the mixtures of homo- or copolymers of vinyl chloride and graft polymers are strongly influenced. As a matter of fact each component affects the properties of the end product. So is "the impact resistance on

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Butadiene, the non-appearance of white or abundant ones Stains when folding or folding on acrylonitrile and the transparency, and increased heat resistance on styrene and that due to crosslinking monomers. In addition, it can be used to modify the refractive index of the parent polymer Styrene this refractive index approximates the refractive index of the polymer to be reinforced and in this way the Transparency of the elastomeric component and thus also of the Improve the end product.

2. The components of the PfroOfreiser are also essential; the vinyl aromatic compound changes the refractive index of the graft polymer, so that depending on the used Amount of refractive index of the graft polymer modified in this way can be that it practically coincides with the refractive index of the polymer to be reinforced. on In this way, the transparency and the heat resistance of the molding compositions can be improved. Alkyl methacrylate gives that Graft polymer its compatibility with the reinforcement. Polymers without affecting its heat resistance. The citrile of an acrylic derivative improves the compatibility.

The invention also relates to that from the molding compositions received products, e.g. plates, bottles, packaging films, especially for the food industry, bottles in which water, wine, Cl, dairy products, etc.are more stored v / earth.

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At BOiel 1

Production of the parent polymer

In a stainless steel autoclave, capacity 22 liters, provided with a stirrer

11,000 g demineralized water, 100 g potassium stearate,
15 g potassium persulfate,
3 g tert-dodecyl mercaptan, 2 100 g butadiene,
600 g acrylonitrile,
600 g styrene and

• 150 g of commercially available divinylbenzene were introduced. The Geniisch was ervrärmt under Hühren 15 h at 60 ⁰ C. Thereupon the degree of Umwandlurgs was 95, o. The unreacted butadiene was degassed and cooled, the latex formed on 5O ⁰ C. The latex particles had a composition corresponding to the monomers fed.

Production of the graft polymer.

The latex obtained above was stirred at 50 ⁰ C and h in the course of 5 with a mixture of 1 g 5 CO Hethylmethacrylat and 2 500 g of styrene containing dissolved the 10 g of cumene hydroperoxide was added. In addition, 3 g of sodium formaldehyde sulfoxylate were added. '

Wax completion of the addition of the reward, the mixture was kept 3 h at 5O ⁰ C. The grafting reaction was then ended. The latex was cooled and a solution of 50 g of dibutyl paracresol in 200 g of dichloroethane was added.

The latex was then coagulated by adding a calcium chloride solution in three times the theoretical range , calculated on the emulsifier present in the latex. The particles were spun off, washed and dried. The composition; the obtained graft polymer corresponded to the

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used monomers.

Production of the molding composition according to the invention.

90 parts by weight of polyvinyl chloride obtained by suspension polymerization and having a viscosity number of 110 were mixed with 10 parts by weight of the above graft polymer and 1 part by weight of organic tin compound as a stabilizer. The mixture was kneaded at 160 ° C. and the film obtained was pressed into sheets; punched from these plates vrurden samples with which the impact strength to the American standard ASTM D 256-56 vjurde determined in accordance with.

The measurements showed a notched impact strength of 20 kgcm / om, while the notched impact strength of the polyvinyl chloride without the addition of graft polymers, only one notch

Had an impact strength of 5 kgcra / cm.

The samples had excellent transparency, comparable to that of crystal glass.

The thin film obtained by calendering showed at Folding or temporarily deforming no permanent white discoloration.

Example 2

Beisgiel χ was repeated, but the graft reaction was carried out at 60 ⁰ C with the following monomers

X 300 g yeast methyl methacrylate, 2 QOO g styrene,

500 g of acrylonitrile.

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The notched impact strength of the molding compound produced therewith was 25 kgcn / cra.

The thin film produced by calendering was completely transparent and did not show any when it was folded permanent white stain formation.

Example 3

A comparative experiment was carried out and the procedure was as in Example 2, with the difference that the parent polymer is a butadiene-styrene copolymer and not was a butadiene-styrene-acrylonitrile copolymer.

Production of the Stamrapol7 / meren.

In a stainless steel autoclave, capacity 22 liters, provided with a stirrer

11 000 g demineralized water, 100 g potassium stearate,
15 g potassium persulfate,
3 g of tert-dodecyl mercaptan, 2,400 g of butadiene and

600 grams of styrene

given. The mixture was polymerized for 28 hours at 60 ° C; thereupon the pressure still present was 1 bar. The unreacted butadiene was vented, and the latex formed at 5O ⁰ C cooled.

Division of the graft polymer.

The latex obtained was ^{kept at 50 °} C. with stirring and with a device made of 1,500 g of methylraethacrylate | Z 000 g of styrene and 500 g of acrylonitrile, containing 10 g of dissolved cumene hydroperoxide, are added. In addition, J g of sodium formaldehyde sulfoxylate was added.

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The grafting reaction was over after 5 hours. The latex was then cooled and a solution of 50 g of dibutylpacresol in 200 g of dichloroethane was added.

The latex obtained was coagulated and the polymer spun off, washed and dried.

Production of the molding compound.

90 parts by weight of polyvinyl chloride obtained by suspension polymerization and having a viscosity number of 110 were mixed with 10 parts by weight of the above graft polymer and 1 part by weight of organic tin compound. The mixture was kneaded at 160 ° C. and made into a film. The film was pressed to form sheets. These plates were colored light yellow and, in contrast to the completely transparent plates according to Example 2, opalescent.

The thin film obtained by calendering showed, after folding or a temporary deformation, a clear, white and persistent discoloration.

The impact strength was 20 kgcm / cm. Example h

Production of the parent polymer.

The base polymer was according to Example 1, however, with 75 g Diethylene glycol dimethacrylate instead of 150 g divinylbenzene manufactured.

Production of the graft polymer.

1,500 g of styrene containing 9 g of cumene hydroperoxide and 5 g were added to the latex, which was kept at 60 ° C., with stirring Given sodium formaldehyde sulfoxylate.

It was polymerized for 5 hours and then 1,500 g of methyl methacrylate containing 9 g of e

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Cumene hydroperoxide was added to 5 g of sodium formaldehyde sulfoxylate. A further 3 λ were polymerized and the latex was then treated with a solution of % g of dibutyl paracresol in 2CO g of dichloroethane. According to Example 1, the latex vrurde then coagulated and centrifuged the polymer gev, ash ^T and dried.

Hers tell IUTg of? Orramasse.

100 Gevr. - parts by suspensions ^ olynerication obtained polyvinyl chloride with viscosity number 110 were with different amounts of the above graft polymers and 1 part by weight of organic tin compound mixed and the mixture kneaded and pressed. The panels obtained were completely see-through. The proportion of graft polymers as well as the corresponding values for the notched impact strength are compiled in the following table.

Tabel

Graft polymer impact strength Gevj. -Parts kgcm / cm

0 5

5 8-10

10 25

15 30

20 30

30 25

40 15

Example 5

100 parts by weight of a vinyl chloride-vinyl acetate copolymer with about Ik f »vinyl acetate were mixed with 15 parts by weight of graft polymer according to Example k and 1 part by weight of organic tin compound.

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After kneading and compression molding, transparent plates were obtained, the impact strength of which was over 30 kgcm / cm 'while the copolymer was without the addition of graft polymer had a notched impact strength of only 3 kgcm / cm.

Example 6

Production of the parent polymer.

In a stainless steel autoclave, capacity 22 liters, provided with a stirrer

11 000 g demineralized hater, 100 g Katriundiodylsulfosucciriat, 2 700 g butadiene, 250 g acrylonitrile, 150 g styrene, 100 g commercial divinylbene sol,

3 g cumene hydroperoxide, 0.01 g iron (II) sulfate, Submitted 30 g of sodium pyrophosphate and 30 g of glucose.

^{The mixture was heated to 30 °} C. for 20 h with stirring. The butadiene not reacted was degassed. The latex particles have a composition corresponding to the ionomers used.

Production of the graft polymer.

The above latex was heated to 60 ⁰ C and with stirring with 3 g Hatriumformaldelr'c'sulfoxylat and then in the course of ^ with a Gemicch rus 1 500 grams and 100 g Hethylmethacrylat Ilonoäthylenglykol dimethacrylate containing added 3 g of cumene hydroperoxide.

There was 2 hours polymerized thereon g of styrene containing 3 g of cumene hydroperoxide was added over h h 1 500th

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It was polymerized for a further 2 h and then a solution of 50 g of dibutylparacresol .in -OO g of dichloroethane was added. In Example 1, the latex was coagulated and the polymer was washed and dried.

Production of the molding compound.

100 parts obtained by suspension polymerization Polyvinyl chloride with viscosity number 120 was produced with 10 parts by weight of the above graft polymer and 1 part by weight mixed organic sense connection. ! laugh at the kneading and Presses gave clear plates. The notched impact strength was so high that the samples under the 7-search conditions did not break () '30 kgcrc / cm \

Example 7

The base polymer was produced according to Example 1.

Production of the graft polymer.

The latex vjurde to 8O ⁰ G heated and stirring during the whole graft reaction !! maintained at this temperature. There were 2 g iiatriumfornaldehydsulfoxylat and then a mixture of 1 500 g butyl methacrylate and 1 000 grams styrene containing h g cumene hydroperoxide was added.

It was polymerized for 6 hours, then 1500 g of styrene containing 2 g of cumene hydroperoxide were added.

It was polymerized for a further 3 hours and then, as in Example 1, the latex was coagulated and the polymer was spun off, washed and dried.

Manufacture of the mold mass.

100 parts by weight obtained by cash register polymerization Polyvinyl chloride with a viscosity of 80 with 20 parts by weight of the above graft polymer, 1 part by weight

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organic tin compound and 2 parts by weight of glycerol monostearate mixed up. :: after the lines and presses were completely transparent plates obtained, their notched impact strength Was 23 kgcn / cm.

A film made by injection molding with aluminum showed at Fold or, in the case of temporary deformation, no permanent white discoloration.

Example 3

The Staircnpolyneren was prepared according to Example 6.
Manufacture of the graft polymer.

The latex was hardened to 6 ° C. and kept at this temperature during the entire grafting reaction with stirring. 3 G of sodium formaldehyde sulfoxylate were added and then, in the course of 3 hours, a mixture of 1,500 g of methyl methacrylate and y * g of acrylonitrile, containing 3 g of cumene hydroperoxide, was added. It was polymerized for 2 hours Uncl then in the course of 3 hours with a mixture of 1 5C ¹ O g of styrene and acrylonitrile 30C g containing added 3 g of cumene hydroperoxide.

It was another 2 h polymerized, to a solution of X> g Dibutylparakresol in 20ü g dichloroethane was added ^1. Coagulation, washing and drying were carried out according to Example 1.

Production of the molding compound.

There were 100 parts by weight by suspension polymerization obtained polyvinyl chloride with viscosity number 12G with 10 parts by weight of the above graft polymer and 1 part by weight organic tin compound mixed and the mixture kneaded and pressed. The plates obtained were transparent and very slightly yellow in color, their notched impact strength was over 30 kgcn / cm.

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Example 9

Production of the parent polymer.

In a stainless steel autoclave equipped with a stirrer Steel, capacity 22 liters

10,000 g demineralized water, 100 g sodium alkyl sulfate,
3 g potassium persulfate and
1 g of tert-dodec3 ^r lmercaptan and then a mixture of
Jj- 000 g butadiene,
1,000 g acrylonitrile,
1,000 g of styrene and

200 g of commercial divinylbenzene

admitted. The reaction mixture was heated to 85 ^° C. for k h with stirring; then the pressure was <1 bar. The unreacted butadiene was degassed and cooled, the latex formed on 6O ⁰ C.

Production of the graft polymer.

An amount of latex corresponding to 5,000 g of stock polymer was left in the autoclave and this was diluted with water to a volume of about 1k liter. This latex was kept at 60 ° C. with stirring, and 0.6 g of Hatriuraformaldehyde sulfoxylate and then 200 g of methyl methacrylate were added. It was polymerized for 2 hours, then 250 g of styrene were added and polymerized for a further 2 hours. The latex was then cooled and 50 g of dibutyl paracresol dissolved in 200 g of dichloroethane were added.

The latex was coagulated, then the particles were spun, washed and dried.

Production of the molding compound.

100 parts by weight of polyvinyl chloride obtained by bulk polymerization and having a viscosity of 80 were used 10 parts by weight of the above graft polymer, 1 part by weight of organic

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Tin compound and 2 parts by weight of glycerol stearate mixed.

After kneading and pressing, transparent plates became that looked like glass. The notched

speed was over 30 kgcm / cn. One obtained by blow molding after folding, the thin film did not show any permanent white stains.

Claims

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Claims (7)

Claims Rigid, highly impact-resistant, thermoplastic molding compounds based on polyvinyl chloride and a graft polymer, characterized in that they are 6ΰ - 99 wt .- ^, preferably 3C - 95 Gev: .-; j Hono- and / or copolymers of vinyl chloride and ^ iO - 1 Gevr .-; ~ 3, preferably 20-5 wt. -: 'o contain graft polymer whose trunk is formed from butadiene, acrylonitrile, styrene and at least one crosslinking monomer and whose grafts are made from at least one vinylaromatic compound, at least one alkyl methacrylate, at least one nitrile of an acrylic derivative and optionally at least one crosslinking agent are formed. 2. Form masses according to claim 1, characterized in that the graft polymer consists of 10-95 wt .- ^ of a stem polymer and 90-5 wt .- ^ of grafts, the stannic polymer being a copolymer which l \ Q - 9 ^, 5 wt .- # butadiene, 2 - 30 wt .- ^ acrylonitrile, 2-HQ wt .- / i styrene and C l - 10, preferably 0.5-5 wt -.% contains Vernetzungsraitteleinheiten and the grafts are formed from 1-35% by weight vinyl aromatic compound, 1-85% by weight alkyl methacrylate, G-30% by weight optionally substituted nitrile of an acrylic derivative and 0-5% by weight crosslinking agent. 3. Molding compositions according to claim 1 or 2, characterized in that g e k e η η draws that the grafts of ^ -ethylstyrene, a chlorostyrene and / or preferably contain units derived from styrene. 909848/1260 BA £> QRiGiNAt -SJ- lA-35 ^ 4. Molding compositions according to claim 1 to 3, characterized in that the grafts of alkyl methacrylates, whose x alkyl group contains 1-5 carbon atoms Units included. 5. Molding compositions according to claim 1 to 4, characterized in that the grafts of methacrylonitrile, Chloroacrylonitrile and preferred values derived from acrylonitrile Units included. 6. Molding compositions according to claim 1 to 5ι, characterized in that they are used as crosslinking agent divinylbenzenes, Whore ti :? acrylates and diacrylates of mono- and polyethylene glycol, Di vinyls chvref el, divinyl ether, vinyl acrylate, trivinyl benzene and / or trimethylolpropane trine ethacrylate. 7. Use of the molding compositions according to claim 1 to 6 for the production of plates, bottles, packaging films, in particular for the food industry, bottles for storing ■ Uasser, vfein, oil, dairy products, etc. BATH ORIGINAL 909848/1260