DE2414840C3 - Molding compounds - Google Patents

Description

in which W, X, Y and Z are hydrogen atoms, nitrile groups, substituents containing nitrile groups, alkyl groups with 1 to 20 carbon atoms, alkylene groups with 1 to 20 carbon atoms, aryl groups having 1 to 20 carbon atoms and / or aralkyl groups having 1 to 20 carbon atoms mean, with the proviso that at least one of the groups W, X, Y and Z is a nitrile group and / or denotes a substituent containing a nitrile group, obtained polymers, b) 95 to 5 Parts by weight of homopolymers and / or copolymers of vinyl chloride and c) where appropriate usual additives in usual amounts.

2. Molding compositions consisting of a) 5 to 95 parts by weight by ring-opening polymerization of cyan-substituted norbornene derivatives of the general formula

in which W, X, Y and Z are hydrogen atoms, nitrile groups, substituents containing nitrile groups, alkyl groups with 1 to 20 carbon atoms, alkylene groups with 1 to 20 carbon atoms, aryl groups having 1 to 20 carbon atoms and / or aralkyl groups having 1 to 20 carbon atoms mean, with the proviso that at least one of the groups W, X, Y and Z is a nitrile group and / or denotes a substituent containing a nitrile group, obtained polymers, b) 95 to 5 Parts by weight of styrene homopolymers and / or vinyl copolymers containing at least 50

in which W, X, Y and Z hydrogen atoms, nitrile groups, Substituents containing nitrile groups, alkyl groups with 1 to 20 carbon atoms, alkylene groups with 1 to 20 carbon atoms, aryl groups having 1 to 20 carbon atoms and / or aralkyl groups having 1 to 20 carbon atoms means, with the proviso that at least one of the groups W, X, Y and Z is a nitrile group and / or denotes a substituent containing a nitrile group, obtained polymers, b) 95 to 5 Parts by weight by grafting on at least one vinyl compound from the group consisting of styrene and acrylonitrile and methyl methacrylate to at least one elastomer from the group consisting of butadiene rubber and acrylic ester rubber chlorinated polyethylene and ethylene-propylene rubber graft copolymers obtained and c) optionally customary additives in customary amounts.

4. Molding compositions according to claim 2, characterized in that the styrene homopolymers and / or vinyl copolymers at least one Elastomer from the group of butadiene rubber, acrylic ester rubber, chlorinated. Polyethylene and Contains ethylene propylene rubber.

5. Molding compositions according to claims 1 to 4, characterized in that they are used as by ring-opening polymerization The resulting polymers contain copolymers obtained by ring-opening polymerization the cyami-substituted norbornene derivatives containing other cyclo-olefinic compounds were obtained.

The invention relates to a molding compound or resin compound or resin composition containing a cyano-substituted by ring-opening polymerization Contains polymer obtained from norbornene derivatives and

possesses a number of excellent properties From a publication by R.E. Rinechart (Journal of Polymer Science 1969, Part C, No. 27, pp. 7 to 25) and published Japanese patent applications Nos. 22 705/67 and 7 552/68 shows that a new type of polymer can be produced by using Cycloolefins, such as cyclooctene, cyclopentene, cyclobutene, cyclooctadiene and norbornene, in an organic Solvents selected from aromatic hydrocarbons such as toluene, aliphatic hydrocarbons such as n-heptane, and low molecular weight Alcohols, such as methyl alcohol, using one of the halides of noble metals, such as ruthenium, Osmium and iridium or halides of transition metals such as titanium, molybdenum, tungsten and vanadium, prepared catalyst subjected to ring-opening polymerization

On the other hand, Francis W. Michelotti and William P. Keaveney (Journal of Polymer Science 1965, Part A, Vol. 3, pp. 895 to 905) that 5-chloromethyl-2-norbonen, a norbonen derivative, can actually be converted into a fiber polymer, if it is subjected to a ring-opening polymerization using ruthenium compounds as catalysts, while 5-cyano-2-norbonen, i.e. 5-cyano-bicyclo [2.2, l] hepten-2 no polymer obtained, even if this compound in the presence of ruthenium, osmium or iridium compounds as Subjected Catalysts to Ring-Opening Polymerization As can be seen from the above, can make some of the derivatives of cycloolefins, especially those of norbonen, by ring-opening polymerization using a certain Catalyst system are converted into polymers, while the other norbonene derivatives, even if if the same catalyst system is used, ring-opening polymerization is not accessible.

It has now been shown that one can obtain polymers by ring-opening polymerization of cyano-substituted norbonene derivatives if one Catalyst system used, which consists of compounds of tungsten and / or molybdenum and organic It has also been stated that the polymer is made using one of the compounds of titanium and / or vanadium and organic aluminum compounds existing catalyst system cannot be produced by ring-opening polymerization of cyano-substituted norbonen derivatives (cf. the Japanese Patent application No. 31 755/72 and 1 08 902/72). so

The above-mentioned polymers prepared by ring-opening polymerization of cyano-substituted norbonene derivatives can be used on an industrial scale are produced and not only have much better mechanical properties, such as impact strength and hardness, but also better transparency and moldability than commonly used synthetic resins such as polypropylene and polyvinyl chloride, so that these products can be used in various ways can apply, e.g. B. for the production of containers or foils, including z. B. common processing forms, such as injection molding or extrusion processes, applies.

On the other hand, enjoy vinyl chloride polymers that are z. B. through exceptional tensile strength, f> s Hardness and heat resistance distinguish themselves, growing in popularity. On top of that, recently significant improvements on the bad Impact strength or softening point (weak point) have been achieved by hard vinyl chloride resins, making this resin suitable for a wide variety of Applications is suitable if one tries, however, the impact resistance of vinyl chloride polymers to be improved by using a different polymer, e.g. B. chlorinated polyethylene, incorporated into the vinyl chloride polymer, there is the disadvantage that the Tensile strength, hardness, heat resistance and transparency of the vinyl chloride polymer are considerably deteriorated, although the incorporation a relatively small amount of the chlorinated polyethylene reduces the impact strength of the vinyl chloride polymers able to increase. Furthermore, by adding acrylonitrile-butadiene-styrene graft copolymers or methyl methacrylate-butadiene-styrene graft copolymers, the impact strength of the vinyl polymers can be increased without affecting the tensile strength, the hardness, the heat resistance and the Transparency of these products can be markedly deteriorated. However, this addition is always used by the unavoidable substantial deterioration in the physical properties characterizing the vinyl chloride polymers accompanies and results in poorer processability, chemical resistance and Weather resistance of these polymers.

As previously indicated, the heretofore stand out for overcoming the disadvantages of vinyl chloride resins Provided vinyl chloride polymer compositions actually consist of the fact that they are a Have improved impact strength, but have disadvantages on the other hand in that they have a have inferior tensile strength, hardness, heat resistance and transparency. As a result, the hitherto proposed vinyl chloride polymer compositions do not have all of the above-mentioned properties which are necessary for malleable resins, if these are to be used on an industrial scale. Accordingly, there is a strong need for the Development of new vinyl chloride polymer compositions which have all of the aforesaid properties own. It can therefore be assumed that the polymers produced from the above-mentioned cyano-substituted norbonen derivatives have a higher Impact resistance than vinyl chloride polymers can be used to improve the properties of the To improve vinyl chloride polymers.

Although the above-mentioned, by ring-opening polymerization of cyano-substituted norbonene derivatives produced polymers compared with other commonly used synthetic resins a Having a number of superior properties, they are not always characterized by satisfactory ones Processability and impact strength when they are used, for example, for mechanical workpieces, window frames, helmets and lampshades (e.g. for Street lights).

It has now been shown that the incorporation of rubber-like material into the polymers obtained by ring-opening polymerization of cyan-substituted norbonen derivatives improves their impact strength can significantly improve what is already proposed in Japanese Patent Application No. 97 233/73. However, the addition of such rubber material is still accompanied by the disadvantage that although the impact strength of the polymers from the cyano-substituted norbonene derivatives increases, itself their tensile strength deteriorates.

The common practice for improving the processability of common synthetic resins is either in lowering the molecular weight of the products or to incorporate a readily miscible plasticizer. However, these measures have the disadvantage that the tensile strength, the hardness and the softening point of the synthetic resins are deteriorated, although the processability of the polymers can be improved

It is accordingly an object of the invention to provide synthetic resin masks or resin compositions, which are free from the disadvantages mentioned and have excellent impact strengths, processability u. dgL exhibit a

The invention therefore relates to a resin composition which contains 5 to 95 parts by weight by ring-opening polymerization of cyano-substituted norbonen derivatives of the general formula

at least one nitrile group or one nitrile group containing substituents in the 5- and / or 6-position from Bicydo [2,2, l] hepten-2, as it is from the The following general formula shows the chemical structure of the monomer:

in which W, X, Y and Z hydrogen atoms, nitrile groups, substituents containing nitrile groups, alkyl groups with 1 to 20 carbon atoms, alkylene groups with 1 to 20 Carbon atoms, aryl groups with 1 to 20 carbon atoms and / or aralkyl groups with 1 to 20 Mean carbon atoms, where at least one of the groups W, X, Y or Z is a nitrile group and / or represents a substituent containing nitrile groups, obtained polymers and 95 to 5 parts by weight Contains homopolymers and / or copolymers of vinyl chloride.

The polyvinyl chloride resins incorporated in the resin composition of the present invention can be replaced through

1. a styrene or vinyl copolymer that at least 50% by weight of at least one vinyl compound such as styrene, acrylonitrile and / or methyl methacrylate, contains or

2. the styrene homopolymer or vinyl copolymer, in which at least one elastomer, such as a butadiene rubber, an acrylic ester rubber, chlorinated polyethylene and / or an ethylene-propylene rubber is incorporated or

3. a graft copolymer which is obtained by grafting on at least one of the vinyl compounds mentioned on the elastomer has received.

The resin compositions according to the invention not only have very good impact strength and processability, but also excellent heat resistance, tensile strength and hardness.

The van-substituted norbonen derivatives used as monomers according to the invention contain minin of W, X, Y and Z have the meanings mentioned above.

The substituents containing nitrile groups include the cyanomethyl group, the cyanoethyl group and the cyanopropyl group the cyano-n-butyl group, the cyano-isobutyl group and the ω-cyano-n-heptyl group. When Hydrocarbon groups can be methyl groups, ethyl groups, propyl groups, n-butyl groups, isobutyl groups, Octyl groups, phenyl groups, cyclohexyl groups and 2-octenyl groups may be present.

The monomers of the above general formula can be obtained by reacting cyclopentadiene with the Nitrile group-containing vinyl compounds obtained, in particular by a Diels-Alder reaction (see the Publication by H. L Holmes in “Organic Reaction ", Vol. 4, pp. 60-173, 1948, John Wiley and Sons, Inc.).

Typical monomers include

5-cyanobicyclo [2Äl] hepten-2,

5-cyano-5-methylbicyclo [2 ^, l] hepten-2,

5-cyano-5-n-octylbicyclo [2.2, l] bepten-2,

5,5-Dk.yanobicyclo [2,2, l] hepten-2,
5,6-dicyanobicyclo [2,2,1] hepten-2,
5-cyano-6-phenylbicyclo [2 ^, l] hepten-2
and a mixture of 5-w-cyano-n-heptyl-6-n-2-octenylbicyclo [2,2,1] hepten-2 and

5- <α-cyano-2-decenyl-6-n -pentylbicyclo- [2,2,1] hepten-2.

The polymers derived from the cyano-substituted norbornene derivatives can be obtained by ring-opening polymerization the various cyano-substituted ones obtained by the above-mentioned method Norbornene derivatives in the presence or absence of an inert organic solvent under Use of a catalyst system which consists of a mixture of organic aluminum compounds and compounds of tungsten and / or molybdenum or using a catalyst system produce, which consists of the mixture mentioned with at least one compound such as

h_s water, a peroxide, an epoxy, an organic Halide, an acetal compound, an orthocarbonic acid ester and / or an alcoholic compound has been moved.

The ring-opening polymerization proceeds according to the reaction scheme given below.

XY CH (Il

where W, X ₁ Y and Z have the meanings given above.

The polymers obtained show different properties, which depend on various factors, namely whether the double bond of the polymer is in the cis form or in the trans form is present or thereof, as the various substituents relate to each other and what their steric position is. The cyano-substituted norbonene derivatives can be used in in certain cases via their C = C double bond according to the following reaction scheme for a polymerization, d. H. vinyl polymerization

where W, X, Y and Z have the meanings given above.

However, this vinyl polymerization leads to polymers that differ in terms of their chemical structure differ from those used according to the invention.

The polymers formed by the ring-opening polymerization of the cyano-substituted norbonen derivatives not only include the homopolymers formed in the above-mentioned process cyano-substituted norbonen derivatives, but also copolymers produced by the ring-opening polymerization a mixture containing the cyano-substituted norbonene derivatives as main ingredients and others containing cycloolefinic compounds, the ring-opening polymerization in the same Way carried out as in the case of the preparation of the homopolymers of the cyano-substituted norbonene derivatives will.

Other cycloolefinic compounds used as comonomers for the preparation of the above-mentioned Copolymers are typically used, close

monocyclic olefins, such as cyclopentene,

Cycloheptene and cyclododecene;

non-conjugated cyclopolyenes such as

1, S-cyclooctadiene, 1 ^, g-cyclododecatriene, l-chloro-l.S-cyclooctadiene and norbornadiene;

Norbonene ester derivatives, such as

S-methoxycarbonyl-S-methyl-bicyclo-

[2,2, l] hepten-2,

5-acetoxybicydo [2Al] hepten-2, 5,6-dimethoxycarbonyl-bicyclo [2 ^, 1] hepten-2

andS-io-carbomethoxy-n-heptyl-B-n-octyl-

bicyclo [2.2, l] hepten-2;

Norbonene ether derivatives, such as 5-methoxy-bicyclo [2.2.1] hepten-2 _I 5-ethoxy-bicyclo [2.2, l] hepten-2, 5-cyclohexyloxybicyclo [2.2, l] hepten-2, 5 -Methoxy-methyl-bicyclo [2.2, l] hepten-2, S-methoxy-e-methoxymethyl-bicyclo- [2.2, l] hepten-2 and
5-phenoxybicyclo [2,2,1] hepten-2; Norbonenic anhydride derivatives, such as 3,6-methylene-1,2,3,6-tetrahydro-cisphthalic anhydride,
6- (5-carboxy-bicyclo [2,2,1] heptenyl) acetic anhydride,
4,7-methano-1-methyl-1,2,3,3a, 4,7,7 a, 8-naphthalene-1,2-dicarboxylic acid anhydride and 4- (bicyclo [2,2,1] 2-heptenyl) -phthalic anhydride;
Norbonenimidderivate, like N-Methyl-Se-methylen-l ^ Ae-tetrahydrocis-phthalimid,

N-methyl-3,6-methylene-1-methyl-1,23,6-tetrahydro-cis-phthalimide, bicyclo _(2/2, lihepta-2-en-5-spiro-3 '- (n-äthylsuccinimid) ,

2-methyl-2-aza-13-dioxo-5,8-methano-l Ä3,4,4a ^, 8,8a-octahydronäphthalin,
Ä

hydronaphthaJin-2ß-dicarboxyimide, N-methyl-4- (5-norborna-2-enyl) phthalimide, N- (5-norborna-2-enyl) methyl-maleic acid imide, N- {5-norborna-2-enyl) methyl-citraconic acid imide andN- (5-norborna-2-enyl) methylnaphthalene-23-dicarboxyimide;

aromatic norbonen derivatives, such as

ίο

., 4- dihydro-1,4-methano-naphthalene,

1,4-dihydro-1 ^ -methano-ö-methylnaphthalene,

M-dihydro-l ^ -methano-ö-methoxycarbonyl-

naphthalene,

6-chloro-1,4-dihydro-1,4-methanonaphthalene, s

S.e-diacetoxy-öJ-dichloro-M-dihydro-

1,4-methanonaphthalene,

5,8-diacetoxy-1,4-dihydro-1,4-methano-

6-methylnaphthalene,

5,8-diacetoxy-1 ^ -dihydro-ö.T-dimethoxy- ι η

1,4-methanonaphthalene,

M-dihydro-M-methanoanthracene,

9,10- diacetoxy-1,4-dihydro-1,4-methano-

anthracene and

M-dihydro-g.10-diphenyl- is

1,4-methanoanthracene;

norbonen derivatives containing polar groups,

ζ. B. norbonene halogen derivatives, such as

5-chloro-biscyclo [2.2, l] hepten-2

5.5-dichlorobicyclo ^ .ll] hepten-2 and ^ o 5,6-dichlorobicyclo [2.2, l] hepten-2und
Bicyclo [2,2, l] hepten-2 (norbonen)

one.

If the above-mentioned copolymers of the> _s cyano-substituted norbonen derivatives are used for the production of the resin compositions according to the invention, it is preferred to produce these copolymers by ring-opening polymerization of a mixture, the maximum 1 mole of the other cycloolefinic compounds per mole of the cyano-substituted norbonene derivatives contains. When the other cycloolefin compounds, e.g. B. the monocyclic olefins, such as Cyclopentene and cyclooctene, in an amount of more than 1 mole per mole of the cyano-substituted norbonen derivatives are used, the resin composition containing these copolymers shows a poorer surface hardness and a lower softening point.

If the homopolymer or the mixed polymer of the cyano-substituted norbonen derivatives (those in hereinafter referred to as "polymers of cyano-substituted norbonene derivatives") homogeneously with mixed with vinyl chloride resins, resin compositions can be obtained that not only have good tensile strength, The vinyl chloride resins have hardness and transparency, but they are also excellent Have impact strength and improved heat resistance.

The incorporation of the polymers of the cyano-substituted norbonene derivatives results in a very clear -so Effect, although the functional mechanism is still unknown, it is believed that this Polymers show good compatibility for the vinyl chloride resins and because of both components an unexpected synergistic effect give the desired effect.

The vinyl chloride resins into which the polymers of the cyano-substituted norbonen derivatives are incorporated can be by bulk polymerization, by solution polymerization, by emulsion polymerization or by suspension polymerization. According to the invention it is possible, not only Vinyl chloride homopolymers, but also copolymers to be used, the vinyl chloride as the main component and vinyl acetate, ethylene, propylene or vinyl ether. The use of vinyl chloride homopolymer, in particular the homopolymer with a high average degree of polymerization, results in the desired resin compositions with higher impact strength than those obtained by using the Above-mentioned copolymers is achieved. It should be noted that when vinyl chloride copolymers are used, the impact resistance of the resin composition obtained increases less, the greater the Is the proportion of composites copolymerized with vinyl chloride.

The proportions in which the above-mentioned resin compositions contain the constituents mentioned, depend on the quality of the objects to be manufactured for the practice as well as on economic ones Considerations. The resin compositions contain 95 to 5 parts by weight, preferably 90 to 20 parts by weight of the Vinyl chloride resins and 5 to 95 parts by weight, preferably 10 to 80 parts by weight of the polymers cyano-substituted norbonen derivatives. The reason for this is that smaller amounts of the polymers cyansubstituierten norbonenivate than 5 parts by weight are not sufficient to the impact resistance of the question Increasing vinyl chloride resins and amounts of derivatives which are higher than 95 parts by weight have the disadvantage possess that they make the resin compositions easily flammable.

The resin compositions mentioned not only show an improvement that is significant for the vinyl chloride resins low impact strength, but also possess high tensile strength, hardness, heat resistance, Transparency, solvent resistance, flame resistance and gas impermeability.

A mixture of the polymers of the cyano-substituted norbonen derivatives produced by the above process with styrene homopolymers or vinyl copolymers containing at least 50% by weight contain at least one vinyl compound such as styrene, acrylonitrile and / or methyl acrylate (with styrene homopolymers and vinyl copolymers are collectively referred to as "vinyl resins") leads to that the resin composition obtained has good processability.

The vinyl resins mixed with the polymers of the cyano-substituted norbonene derivatives for the preparation of the above-mentioned resin compositions with good processability are obtained by polymerizing at least one (monomeric) vinyl compound such as styrene, acrylonitrile and / or methyl methacrylate, with polymerisation in bulk, solution polymerisation, emulsion polymerisation or can carry out a suspension polymerization and a free radical initiator, e.g. B. can use an organic peroxide as a polymerization initiator. The vinyl resins include styrene homopolymers, acrylonitrile-styrene copolymers, methyl methacrylate-styrene copolymers, copolymers containing methyl methacrylate as the main component and other monomers, and acrylonitrile-styrene-methyl methacrylate polymerizate. The vinyl resins are produced by known technical processes and used in a variety of ways. The homopolymers and copolymers mentioned have a molecular weight which is generally between 100,000 and 500,000, a melt viscosity of ΙΟ ² to 10 ⁵ poise, determined with the Koka flow meter, the one Has nozzle with a diameter of 1 mm and a length of 10 mm and is operated with a load of 100 kg and at a temperature of 200 ° C.

The styrene homopolymer generally has a molecular weight of 200,000 to 500,000, a

Melt viscosity of 10 ² to 10 ⁵ poise, one with the Koka flow meter equipped with a nozzle 1 mm in diameter and 10 mm in length and operated under a load of 100 kg at a temperature of 200 ° C certain flow rate (Q) of 5 χ 10 ~ to 10 ~ ² and an intrinsic Viskositätszahi (intrinsic viscosity) of 0.7 to 0.9. The methyl methacrylate copolymers, which contain methyl methacrylate as the main component and other monomers, have a melt viscosity of 10 ³ to 10 ⁵ poise. The acrylonitrile-styrene copolymers contain at most 40% by weight of acrylonitrile and have a melt viscosity of 10 ³ to 10 ⁵ poise. The methyl methacrylate-styrene copolymers consist of 1 to 99% by weight of methyl methacrylate and 99 to 1% by weight of styrene and have a melt viscosity of 10 ² to 10 ⁵ . The acrylonitrile-styrene-methyl methacrylate terpolymers consist of 1 to 40% by weight of acrylonitrile and 99 to 60% by weight of a mixture of styrene and methyl methacrylate and have a melt viscosity of 10 ² to 10 ⁵ poise, the styrene content being the Mixture makes up 1 to 99% by weight.

The resin compositions according to the invention with good processability consist of 5 to 95 parts by weight of Polymers of cyano-substituted norbonen derivatives and 95 to 5 parts by weight of vinyl resins. Big shares the vinyl resins lead to a reduction in the softening point and the surface hardness of the resulting resin composition, although the processability of the resin composition is increased. So if it is it is desired to prepare a resin composition to be applied for purposes where a high one Softening point and high surface hardness are required, it is preferred that the resin composition from 60 to 95 parts by weight of the polymers of the cyano-substituted norbonen derivatives and 40 to 5 Parts by weight of the vinyl resins is formed. The vinyl resins, in particular styrene homopolymers and vinyl copolymers can be used individually or in combination can be used. Of course, it is possible to use a styrene homopolymer with one or more to mix different vinyl copolymers.

If necessary, the resin compositions in question with good processability with thermoplastic Resins, such as the homopolymers or copolymers of vinyl chloride and the terpolymers of acrylonitrile, butadiene and styrene and a rubber material such as a butadiene rubber, chlorinated Polyethylene and a polychloroprene rubber are mixed.

The vinyl resins into which the polymers of the cyano-substituted norbonen derivatives are incorporated can be replaced by a mixture of the vinyl resins and elastomers, as a result of which the resin composition obtained is particularly impact-resistant . The high impact strength or impact strength of the resin composition can also be achieved by using graft copolymers obtained by grafting vinyl compounds onto the elastomers mentioned in place of the mixture of the elastomer and the vinyl resins

Butadiene rubbers, acrylic ester rubbers, chlorinated polyethylene and ethylene-propylene rubbers can be used as elastomers. The elastomers can be used individually or in combination.

The butadiene rubbers consist of butadiene rubber

Tschuk (butadiene homopolymers) or styrene-butadiene rubber or acrylonitrile-butadiene rubber (copolymers containing butadiene as the main component and styrene or acrylonitrile). The copolymer can be formed by random copolymerization or by block copolymerization. The acrylic ester rubbers can comprise copolymers which have been produced from acrylic esters as the main constituent and minor amounts of, for example, acrylonitrile. These rubbers can be prepared by emulsion polymerization. The chlorinated polyethylene is obtained by chlorinating ethylene homopolymers with a high density, which extends from 0.93 to 0.97 g / cm ³ , or by chlorinating a copolymer of ethylene and an Λ-olefin. working in a solvent or in aqueous suspension. The chlorine content of the chlorinated polyethylene is generally 25 to 45% by weight. The ethylene-propylene rubbers are obtained by copolymerizing a mixture of ethylene and propylene or such a mixture which contains a small amount of a straight-chain or branched diolefin with two double bonds at the chain ends, 1,4-pentadiene, 1,5-hexadiene and 3 , 3-dimethyl-1,5-hexadiene, or a straight-chain or branched diolefin which has a single double bond at the chain ends, such as 1,4-hexadiene and 6-methyl-1,5-heptadiene, or a cyclic diene compound, such as Bicyclo [2.2, l] hepten-2. Of the ethylene-propylene rubbers, preferred are those in which the ratio of the ethylene units to the propylene units is 35:65 to 65:35. The above-mentioned rubbers or elastomers are obtained on an industrial scale by copolymerizing the components using a catalyst composed mainly of organic aluminum compounds and transition metal compounds, and they are used in a variety of ways.

The for the production of resin masses with particularly high impact strength by mixing with the Polymers of cyano-substituted norbonene derivatives used a mixture of vinyl resins and elastomers generally consists of 98 to 70 parts by weight of the vinyl resins and 2 to 30 parts by weight of the the elastomers mentioned above.

The above graft copolymers used according to the invention can be prepared by that at least one vinyl compound such as styrene, acrylonitrile and / or methyl methacrylate on the said Elastomer grafted on This grafting can be done by bulk polymerization, by solution polymerization, by emulsion polymerization, by suspension polymerization, or by a combination these polymerisation processes (e.g. by a combination of bulk polymerisation and suspension polymerization).

The graft copolymers formed by these processes typically include: high impact styrene resins obtained by grafting styrene onto butadiene rubber or styrene-butadiene rubber; Acrylonitrile-butadiene-styrene terpolymers (ABS resins) obtained by grafting styrene and acrylonitrile onto butadiene rubber, styrene-butadiene rubber or acrylonitrile-butadiene rubber (nitrile rubber); Methyl methacrylate-butadiene-styrene terpolymers obtained by grafting styrene and methyl methacrylate onto butariate rubber or styrene-butadiene rubber

obtained; Acrylonitrile-acrylic acid ester-styrene terpolymers (AAS resins) made by grafting styrene and acrylonitrile onto acrylic ester rubbers, in particular acrylic rubbers (copolymers of acrylic esters as the main component and a minor one Amount of, for example, acrylonitrile) are obtained; Graft copolymers (ACS resins) made by grafting obtained from acrylonitrile and styrene on chlorinated polyethylene (CPE); and graft copolymers (AES resins), which can be obtained by grafting acrylonitrile and styrene onto ethylene-propylene-rubber (Ethylene-propylene compound polymers; EPR or EPM) or on ethylene-propylene terpolymers (EPT or EPDM). All these graft copolymers are by known processes in technical Scale made.

The mixture of the styrene homopolymers and the elastomers or the vinyl copolymers and the elastomers and the graft copolymers can be used individually or in combination will. The mixture mentioned and the graft copolymers can also be used together.

The resin compositions according to the invention with high impact strength are selected in such a way that they are selected from 5 to 95, more preferably 35 to 95 parts by weight of the polymers from the cyano-substituted norbonen derivatives and 95 to 5, more preferably 70 to 5 parts by weight of that with the styrene homopolymer or the vinyl copolymers mixed elastomers or the graft copolymers exist.

The resin compositions according to the invention produced in this way not only have a very high one Impact resistance or impact strength, but also good tensile strength, high surface hardness, a high softening point and good heat resistance.

If necessary, the resin compositions mentioned with high impact strength can also be mixed with synthetic Resins, such as homopolymers or copolymers of vinyl chloride and methyl methacrylate resins (PMMA resins) or elastomers such as acrylonitrile butadiene rubbers (NBR) or butadiene rubbers, styrene-butadiene rubbers, chlorinated Polyethylene, chlorosulfonated polyethylene, ethylene-propylene rubbers, Ethylene-propylene terpolymers, chloroprene rubbers (CR) and acrylic rubber be mixed.

The constituents of the resin compositions or resin compositions of the present invention are generally in a dry mixer, such as a ribbon mixer, a rotating cone mixer, a rotary mixer or a Henschel mixer. However, a mixing device such as a rolling mill is included hot rollers, a Banbury mixer or a melt extrusion device suitable because with these devices the above ingredients in molten Condition can be mixed homogeneously relatively easily. Furthermore, the method in Depending on the nature of the constituents can be adjusted accordingly by adding a constituent to a solution in which the other component is dissolved, or to an aqueous or organic suspension, in that the other ingredient is suspended, admit and then the water or the organic solvent to achieve uniform mixing can distill off.

The resin compositions according to the invention, which are made from vinyl chloride resins and the polymers of the cyano-substituted norbonene derivatives can thereby can be made by simply mixing the two ingredients without the need for either to use a special procedure or to carry out the scuffing for a long period of time.

When the ingredients are mixed, a stabilizer is usually added to prevent decomposition or a degradation of the various polymer components (in particular the vinyl chloride resin)

ίο Avoid exposure to heat, oxygen, light (ultraviolet radiation) or ozone. As a stabilizer organic tin compounds are used, such as dibutyltin maleal and dibutyltin dilaurate, lead compounds, like basic lead phosphite, salts of organic

i_s acids, such as calcium stearate and cadmium stearate, Epoxy compounds and phenolic compounds. the However, the use of organic tin compounds is desirable in order to ensure the transparency of the resin compositions in question maintain.

It is also possible to use various additives that are commonly used in resins, such as flame retardants, plasticizers, lubricants, reinforcing agents, fillers, antistatic agents, Agents for improving electrical properties, ultraviolet light absorbing agents, foaming agents and coloring agents to be incorporated into the resin compositions of the present invention. This incorporation of further components is also the subject of the invention.

The resin compositions according to the invention can be produced by pressing, extrusion, injection molding. Blowing or pouring in in a similar way to the usual synthetic resins being molded into various products, such as Sheets, plates, rods, tubes, foils and processed products, e.g. B. Bags, packaging materials, Containers of various types, electrical parts including lighting equipment, various Daily used consumer goods, furniture, toys, agricultural equipment, machine parts, etc.

The following examples are intended to explain the invention further without, however, restricting it. In the examples and the comparative examples, the Vicat softening point was determined with a 3 mm thick test sample by determining the temperature (in ° C) at which a needle penetrates 1 mm into the test sample, whereby the ASTM regulation D-1525- 58T was used to determine the Vicat softening point. The Rockwell hardness is the value of the surface hardness (R) of the test sample was determined according to the ASTM specification D-785-51 at 2O ⁰ C. The Izod impact strength was determined using a 3 mm notched test sample after the ASTM test method D-256-56 in a thermostat at 2O ⁰ C. The tensile strength is the value (by the elongation of a dumbbell-shaped 1 mm thick test sample Japanese Industrial Standard JIS No. 3) was determined at a speed of 5 cm / min in a thermostat at 20 ^° C. The melt viscosity or the viscosity of the melt was determined that kg the resin at 200 ⁰ C under a load of 100 using a Koka-Fließmeßeinrichtung, the mm with a nozzle having a diameter of 1, and have a length of 10 mm is , examined.

B e i s ρ i e 1 e 1 to 4 and comparative examples 1 to 4

A 10-1 autoclave filled with dry nitrogen is charged with 4500 ml of 1,2-dichloroethane,

1500 ml (12 mol) of monomeric 5-cyano-bicycio [2.2, l] hepten-2 (cyannorbonen), 10 ml (0.12 mol) n-hexene-1 and 120 ml of a solution containing 0.2 Moles of tungsten hexachloride acialdehyde diethylacetal (which are present in a molar ratio of 1: 2, with 5 molar of tungsten hexachloride being present in an amount of 24 molar, which corresponds to 0.2 mol% based on the above-mentioned monomer) in 1,2-dichloroethane containing mixture is then heated to the reaction system at 70 ⁰ C. and 11.9 ml (96 millimoles) of diethylaluminum chloride to the reaction mixture. After the polymerization has been carried out for 5 hours with stirring, the reaction system is treated with 200 ml of ethanolamine and 10 g of the stabilizer bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane. The mass is then stirred for 30 minutes at this temperature. The product obtained (ie a solution containing the polymer formed) is diluted with 1,2-dichloroethane (the polymer having a concentration of about 10% by weight). 4000 ml of an aqueous solution which contains 1% by weight of the trisodium salt of nitrilotriacetic acid are then added and the mixture is stirred vigorously at 20 ° C. for 30 minutes. After standing, the mass separates into an aqueous phase and a 1,2-dichloroethane phase, whereupon the aqueous phase is separated off. The product is then washed three times with water. After the pH of the solution has reached 7, the polymer is precipitated by adding a large amount of methyl alcohol. The polymer purified in this way is dried overnight at 50 ° C. in a vacuum of less than 1 mm Hg each time, 1150 g of an essentially colorless, transparent polymer being obtained. The conversion is 80% of the monomer used. The polymer obtained as a product has an intrinsic viscosity of 0.64, an Izod impact strength of 6.3 kgcm per cm for a notched sample, a Vicat softening point of 26 ° C, a Rockwell hardness R of 127 and a melting point Viscosity of 8.6 10 ⁵ poises.

This in the above manner by ring-opening polymerization made from S-cyano-bicyclove ÄlJhepten ^ Polymer (polycyanonorbonen) is mixed with polyvinyl chloride in the proportions given in the table Both ingredients are added for about 5 minutes on a 2032 cm (8 inch) Mixing mill, which is operated at 175 ° C, kneaded At this point, the stabilizer used is 3 parts by weight of dibutyltin maleate, based on 100 parts by weight the total amount of resin, too. The kneaded resin is molded in a press at 190 ° C and immediately cooled in a water-cooled press and processed into test samples in this way. These test samples are then used to determine the Vicat softening point, the hardness, the Izod impact strength, the Tensile Strength and Transparency Used The results obtained are as follows Table compiled for comparison purposes the same studies on polyvinyl chloride resins obtained by blending this polyvinyl chloride with chlorinated polyethylene, which contains 30% chlorine, an acrylonitrile-butadiene-steel resin and carried out a polycyanonorbonen. The results obtained here are also as follows Table compiled

table

Mixing ratio (parts by weight)

PVC) PCN *) CPE ^J ) ABS ")

Vicat-Er Izod blow hardness Tensile strength Transpa softening tenacity at speed renz Point notched
sample ("C) (kg cm / cm) (R) (kg / cm?) 127 1.5 116 530 Well 122 2.3 119 540 Well 115 2.3 120 530 Well 96 2.3 121 540 Well 91 0.8 115 540 Well 133 2.3 122 510 Well 85 12.5 108 370 impenetrable sighted 86 11.0 101 460 Well

example
1
2
3
4th

Comparative example

Remarks:

80 60 40 20th

100

80

20th 40 60 80

100

20th

80 -

20th

Polyvinyl chloride.
Polycyanonorbonen.
Chlorinated polyethylene.
Acrylonitrile Butadiene Styrene Resin (ABS Resin).

Example 5

100 parts by weight of the polymer prepared by the process given in Example 1 from 5-cyano-bicydo [2.2, l] hepten-2 by ring-opening polymerization are kneaded with 20 parts by weight of polystyrene with a melt viscosity of 1.2 χ 10 ³ poise, an Izod impact strength for a notched specimen of 10 kg · cm / cm, a Vicat softening point of 78.9 ° C and a Rockwell hardness (R) of 118 and 0.5 wt. Parts of bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane as a stabilizer for 5 minutes on a mixing roll mill heated to 175 ° C. The mixture obtained in this way is heated for 3 minutes at

709 681/340

200 ° C and a pressure of 100 kg / cm ² and then pressed for 3 minutes at a pressure of 100 kg / cm ² in a water-cooled press to form a plate with a thickness of 3 mm kg · cm / cm and a Rockwell Här.e (R) of 120. The above mixture has a melt viscosity of 3.0 10 ⁵ poise and a Vicat softening point of 12 Γ C

Example 6

The same mixture as that described in Example 5 is prepared using the same procedures on a hot roller mixer, with the difference that polystyrene is added in an amount of 50 parts by weight. The mixture is then, as described in Example 5, in a hot press and a press cooled with water to form a sheet Melt viscosity of 1.6 10 ⁴ poise and a Vicat softening point of 114 ° C

Example 7

In the same way as described in Example 5, the mixture described there is prepared using a hot roller mixer, with the difference that polystyrene is used in an amount of 100 parts by weight. The mixture is then, as described in Example 5, with the aid a hot press and a press cooled with water to form a plate. The plate has an Izod impact strength for a notched specimen of 1.4 kg · cm / cm and a Rockwell hardness (R) of 122. The mixture described above shows a melt viscosity of 6.5 χ 10 ³ poise and a Vicat - Softening point of 99 ° C.

Example 8

In the same way as described in Example 5, the mixture of Example 5 is prepared using a hot roller mixer, with the difference that the 20 parts by weight of polystyrene used in Example 5 are replaced by 15 parts by weight of polystyrene with a melt viscosity 8.00 χ 10 ² poise, an Izod notched impact strength at sample of 1.0 kg · cm / cm, a Vicat softening point of 93.2 ° C and a Rockwell hardness (R) 120, replaces The mixture is then pressed in a hot press and a water-cooled press, as described in Example 5, to form a plate. The plate has an Izod impact strength with a notched specimen of 3.6 kg · cm / cm and a Rockwell hardness (R) of 122 The mixture mentioned has a melt viscosity of 2.8 10 ^s poise and a Vicat softening point of 123 ° C

Example 9

In the same way as described in Example 5, the mixture described in Example 5 is prepared using a hot roller mixer, with the difference that the 20 parts by weight of polystyrene used in Example 5 are replaced by 30 parts by weight of polystyrene with a melt viscosity of 3.2 χ 10 ² poise, an Izod notched impact strength at sample of 1.1 kg · cm / cm, a Vicat softening point of 99, O ⁰ C and a Rockwell hardness (R) 119 is replaced by the mixture is because with the help of a hot press and a water-cooled press, as described in Example 5, pressed to form a plate. The plate has an Izod impact strength for a notched specimen of 3.0 kg - cm / cm, a Rockwell hardness (R) of 123. The above-mentioned mixture shows a melt viscosity of 5.0 10 ⁴ poise and a Vicat - Softening point of 122 ° C

Example 10

ίο in the same way as described in example 5 using a hot roller mixer, the mixture given in Example 5, with the The difference is that the 20 parts by weight of polystyrene used there by 20 parts by weight of a Replaced methyl methacrylate resin, which has a melt viscosity of 2.75 χ 10 ⁴ poise, an Izod impact strength for a notched specimen of 1.1 kg - cm / cm, a Vicat softening point of 98 ° C and a Rockwell hardness (R) of 132 The mixture is then as described in Example 5, using a hot press and a water-cooled press to form a plate pressed The plate has an Izod impact strength with a notched specimen of 4.1 kg · cm / cm and one Rockwell hardness (R) of 127. The one described above Mixture has a melt viscosity of 33 × 10 ⁵ poise and a Vicat softening point of 121 ° C

Example U In the same way as described in Example 5 provides

using a hot roller mixer, the mixture described in Example 5, with the The difference is that the 20 parts by weight of polystyrene used there by 20 parts by weight of a Acrylonitrile-styrene copolymer replaces the 23

.15 wt .-% acrylonitrile and having a melt viscosity of 3.0 χ 10 ⁴ poise, an Izod notched impact strength at the sample of 13 kg · cm / cm, a Vicat softening point of 96.2 ⁰ C and a Rockwell - Has hardness (R) of 122 The mixture is then as in Example 5 described using a hot press and pressed in a water-cooled press to form a plate. The plate has an Izod impact strength notched sample of 33 kg · cm / cm and a Rockwell hardness (R) of 123. The mixture mentioned shows a melt viscosity of 3.6 10 ⁵ poise and a Vicat softening point of 124 ° C.

Example 12 A 500 ml stainless steel autoclave is charged

Steel, which is equipped with an electromagnetic stirrer, with 400 ml of water, 6 g of tricalcium phosphate and 0.03 g of the sodium salt of dodecylbenzenesulfonic acid and stirs the materials! well done. then one loads the autoclave with a separately prepared solution of a mixture of 92 g Methyl methacrylate, 108 g of monomeric styrene, 0.6 g tert-butyl peroxybenzoate and 2.0 g of tert-dodecyl mercaptan, whereupon the autoclave is filled with nitrogen gas washes

Then you polymerize the reactants Next for 3 hours at 120 ° C and then for 2 hours at 140 ° C. After cooling, the polymer beads are removed. The polymer beads are stirred with 1 1 of a washed aqueous hydrochloric acid solution containing 5 g of 25% hydrochloric acid After thorough washing with water, drying the Polymerisatkügelchen 24 hours at 6O ⁰ C in a vacuum dryer,

wherein one 185 g of the polymer obtained, the polymer consists of a Methylmethacryiat-styrene MischpoIymerisat containing 46 wt .-% of methyl methacrylate The copolymer has a melt viscosity of 431 χ 10 ³ poise, an Izod impact strength of notched sample of 1, 3 kg · cm / cm, a Vicat softening point of 903 "C and a Rockwell hardness (R) of 121.

The mixture given there is then prepared in the same way as described in Example 5, with the difference that the 20 parts by weight of polystyrene used in Example 5 are replaced by 30 parts by weight of the above methyl methacrylate-styrene copolymer. The mixture is then, as described in Example 5, pressed into a plate with the aid of a hot press and a water-cooled press. The plate has an Izod impact strength for a notched specimen of 2.9 kg-cm / cm and a Rockwell hardness (R) of 124. The mixture mentioned has a melt viscosity of 2.41 10 ⁵ poise and a Vicat softening point of 122 ° C

Example 13

The polymerization is effected in the same way as described in Example 12, with the difference that instead of the solution of the mixed constituents which was used to prepare the methyl methacrylate copolymer, a mixture of 110 g of styrene, 40 g of acrylonitrile, 50 g Methyl methacrylate 0.6 g of tert-butyl peroxybenzoate and 2 g of tert-butyl mercaptan used. After the end of the polymerization, the aftertreatment is carried out in the same way as described in Example 12, giving 165 g of polymer beads. The polymer consists of an acrylonitrile-styrene-methyl methacrylate terpolymer , - ¹⁵ wt .-% acrylonitrile, the 20, 55 wt .-% styrene and 25 wt .-% of methyl methacrylate the terpolymer has a melt viscosity of 3.03 χ 10 ³ poise, an Izod impact strength of notched sample of 1 , 2 kg · cm / cm, a Vicat softening point of 93 ° C and a Rockwell hardness (R) of 121.

The mixture is then prepared in the same way as described in Example 5, with the difference that the 20 parts by weight of polystyrene used there are replaced by 20 parts by weight of the acrylonitrile-styrene-methyl methacrylate terpolymer described above. The mixture is then, as described in Example 5, shaped into a plate with the aid of a hot press and a water-cooled press. The plate has an Izod impact strength for a notched specimen of 3.1 kg · cm / cm and a Rockwell hardness (R) of 122 The above mixture shows a melt viscosity of 3.5XiO ⁵ poise and a Vicat softening point of 123 ° C

Example 14

The ring-opening polymerization is carried out in the same way as indicated in Example 5, with the difference that the monomeric 5-cyano-bicyclo [2 l] hepten-2 used in Example 5 is replaced by the same number of moles (1332 g) of S -Cyano-S-methyl-bicyclo- [2.2, l] hepten-2 replaced. After the end of the ring-opening polymerization, the purification is carried out, giving 1100 g of the polymer material. This polymer product has an intrinsic viscosity of 0.77, a Izod impact strength for a notched specimen of 7.8 kg · cm / cm, a Vicat softening point of 148 ° C., a Rockwell hardness (R) of 127 and a melt viscosity of 1.6 ⁶ poise.

In the same way as described in Example 5, the mixture there is then using a with 190 ° C operated hot roller mixer produced, with the difference that instead of the in Example 5 used polymer prepared by ring-opening polymerization of 5-cyano-bicyclo [2Äl] hepten-2, carried out the above-described polymer in a similar manner Ring-opening polymerization from S-cyano-S-methyl-bicyclo [2.2, l] hepten-2 polymer used. The mixture obtained in this way is then as described in Example 5, using a hot press and a water-cooled press to form a plate processed The plate has an Izod impact strength with a notched specimen of 4.1 kg-cm / cm and a Rockwell hardness (R) of 325. The above mixture shows a melt viscosity of 3.6 × 10 ⁵ poise and a Vicat softening point of 142 ° C

Example 15

The same mixture is prepared in the same way as described in Example 14, with the difference that instead of the 20 parts by weight of polystyrene used in Example 14, 20 parts by weight of the methyl methacrylate resin used in Example 10 are used. processed into a plate with the aid of a hot press and a water-cooled press. The plate has an Izod impact strength with a notched specimen of 4.2 kg -cm / cm and a Rockwell hardness (R) of 124. The above mixture shows a melting point Viscosity of 7.0 x 10 ⁵ poise and a Vicat softening point of 142 ° C.

Example 16

As described in Example 14, the mixture there is prepared using a hot roller mixer, with the difference that the 20 parts by weight of polystyrene used in Example 14 are replaced by 20 parts by weight of the acrylonitrile-styrene copolymer used in Example 11. The mixture is then, as described in Example 14, shaped into a plate with the aid of a hot press and a water-cooled press. The plate has an Izod impact strength for a notched specimen of 3.9 kg cm / cm and a Rockwell hardness (R) of 125. The above mixture shows a melt viscosity of 7.1 10 ⁵ poise and a Vicat softening point of 144 ° C

Example 17

The mixture there is prepared in the same way as described in Example 14, with the difference that that the 20 parts by weight of polystyrene used in Example 14 by 20 parts by weight of the according to Example 12 used methyl methacrylate-styrene copolymer replaced. The mixture is then, as in Example 14 is described using a hot press and a water-cooled press to form a plate deformed The plate has an Izod impact strength

fi.s for a notched sample of 3.7 kg-cm / cm and a Rockwell hardness (R) of 124. The above mixture shows a melt viscosity of 7.9 × 10 ⁵ poise and a Vicat softening point of 143 ° C.

Example 18

The ring opening polymerization is carried out in the same way as described in Example 5, with the difference that instead of the 12 mol of 5-cyano-bicyclo [2Al] hepten-2 described in Example 5, 10 mol (1192 g) 5-cyano-bicyclic & [2ZlJiepten-2 and 2 mol (188 g) bicyclo [2 £ l] hepten-2 (norbonene) are used The mixed polymer obtained as product is essentially colorless and transparent and has an intrinsic viscosity of 0.67, an Izod impact strength for a notched sample of 6.88 kg · cm / cm, a Vicat softening point of 122 "C, a Rockwell hardness (R) of 120 and a melt viscosity of 5.7OxIO ⁵ POiSe.

The materials are then kneaded in the same manner as described in Example 5, with the difference that the polymer used in Example 5, prepared by ring-opening polymerization of 5-cyano-bicyclo [2 £, l] hepten-2, is produced by the above Replaced copolymer obtained by ring-opening polymerization of 5-cyano-bicyclo [2.2, l] hepten-2 and bicyclo [2.2, l] hepten-2. The kneaded mixture is then, as described in Example 5, shaped into a plate with the aid of a hot press and a water-cooled press. The plate has an Izod impact strength for a notched sample of 3.4 kg cm / cm and a Rockwell hardness (R. ) of 117. The above mixture has a melt viscosity of 1.05 χ 10 ⁵ poise and a Vicat softening point of 116 ° C.

Example 19

80 parts by weight of the polymer obtained from 5-cyano-bicyclo [2.2.1] hepten-2 by ring-opening polymerization according to the process described in Example 5 are kneaded with 20 parts by weight of an acrylonitrile-butadiene-styrene terpolymer having an Izod impact strength with a notched sample of 28.5 kg-cm / cm, a Rockwell hardness (R) of 105 and a Vicat softening point of 112 ° C and 0.5 part by weight of bis (2-hydroxy-3-tert-butyl-5- methylphenyl) methane as a stabilizer on a hot roller mixer, using the method given in Example 5. The kneaded mixture is then, as described in Example 5, pressed with the aid of a hot press and a water-cooled press to form a plate with a thickness of 3 mm The plate has an Izod impact strength for a notched specimen of 30.5 kg · cm / cm, a Rockwell hardness (R) of 121 and a Vicat softening point of 130 ^° C.

Example 20

The kneading is carried out on a hot roller mixer in the same way as in Example 19 described by, with the difference that 50 parts by weight of the acrylonitrile-butadiene-styrene terpolymer used in Example 19 and 50 parts by weight of the polymer prepared by ring-opening polymerization from 5-cyano-bicyclo [2.2.1] hepten-2 begins The kneaded mixture is as described in Example 19 in the heat and the cold to one Plate pressed. The plate has a notched specimen Izod impact strength of 283 kg-cm / cm, a Vicat softening point of 127 ° C and a Rockwell hardness (R) of 120.

Example 21

The kneading on the hot roller mixer is carried out in the same way as described in Example 19, with the difference that the acrylonitrile-butadiene-styrene terpolymer used in Example 19 in one Amount of 70 parts by weight and the polymer produced by ring-opening polymerization from S-cyano-bicyclo-zljhepten-2 in an amount of 30 Parts by weight are used. The kneaded mixture is as described in Example 19 in the Heat and cold pressed to form a plate The plate has an Izod impact strength with notched Sample of 30.3 kg cm / cm, a Vicat softening point of 122 ° C and a Rockwell hardness (R) of 115.

Example 22

The kneading on the hot roller mixer is carried out in the same way as described in Example 19, with the difference that instead of the in Example 19 used 20 parts by weight of the acrylonitrile butadiene Styrene terpolymer uses a terpolymer that by grafting styrene and acrylonitrile onto chlorinated polyethylene, an Izod impact strength for a notched specimen of 12.0kg-cm / cm, a Rockwell hardness (R) of 104 and has a Vicat softening point of 90 ° C. The kneaded mixture is, as described in Example 19, in the heat and in the cold to form a plate pressed The plate has an Izod impact strength with a notched specimen of 21.0 kg-cm / cm, a Vicat-Er softening point of 125 ° C and a Rockwell hardness (R) of 115.

Example 23

The kneading on the hot roller mixer is carried out in the same way as described in Example 19, with the difference that the acrylonitrile-butadiene-styrene terpolymer used in Example 19 is used replaced by a terpolymer which was obtained by grafting styrene and acrylonitrile onto an acrylic ester rubber and which was an Izod impact resistant ability with a notched sample of 10.0 kg-cm / cm, a Rockwell hardness (R) of 98 and a Vicat softening point of 102 ° C. The kneaded Mixture is, as described in Example 19, in the Heat and cold pressed to form a plate The plate has an Izod impact strength with notched Sample of 11.5 kg-cm / cm, a Vicat softening point of 126 ° C and a Rockwell hardness (R) of 119.

Example 24

The kneading is carried out in the same way as indicated in Example 19 on a hot roller mixer, with the difference that that in Example 19 Acrylonitrile-butadiene-styrene terpolymer used replaced by a terpolymer, which is replaced by Grafting of styrene and acrylonitrile on an ethylene-propylene rubber has received and the one Izod impact strength on a notched specimen of 93 kg cm / cm, a Rockwell hardness (R) of 110 and has a Vicat softening point of 104 ^° C. The kneaded mixture is, as described in Example 19, pressed in the heat and in the cold to form a sheet. The sheet has an Izod impact strength

for a notched sample of 15.4 kg-cm / cm, a Vicat softening point of 127 ^° C. and a Rockwell hardness (R) of 120.

Example 25

The kneading is carried out as described in Example 19, on a hot roller mixer, with the difference that the acrylonitrile-butadiene-styrene terpolymer used according to Example 19 is replaced by a terpolymer obtained by grafting styrene and methyl methacrylate onto butadiene rubber and which has a notched Izod impact strength of 15.2 kg-cm / cm, a Rockwell hardness (R) of 99 and a Vicat softening point of 106 ° C. The kneaded mixture is then formed into a plate while hot and cold, using the procedure given in Example 19. The plate has an Izod impact strength wedge with a notched specimen of 19.3 kg-cm / cm, a Vicat softening point of 126 ° C. and a Rockwell hardness (R) of 119.

Example 26

A 1-1 autoclave is charged with 125 ml distilled water, 125 ml of a 2% aqueous polyvinyl alcohol solution, 5 g of tricalcium phosphate and 0.025 g of the sodium salt of dodecylbenzenesulfonic acid. whereupon 40 g of chlorinated polyethylene with a Adds chlorine content of 40% by weight. The imported materials become good at room temperature mixed. Then the autoclave continues to be charged with a mixture of 104 g of methyl methacrylate and 56 g of styrene in which 0.32 g of tert-butyl peroxyacetate and 0.48 g of tert-dodecyl mercaptan have been dissolved. After one has filled the gas space of the autoclave with nitrogen, the interpolymerization is initially effected during 4 hours at 105 ° C and finally during 2 Hours at 145 ° C.

After the end of the copolymerization, the product is washed with an aqueous solution of Hydrochloric acid and then with water and dry it overnight in vacuo at 50 ° C. In this This results in a yield of the copolymer product of 99.5%. The product consists of relative rough particles. The graft copolymer has an Izod impact strength for a notched specimen of 32.3 kg · cm / cm, a Vicat softening point of 103 ° C and a Rockwell hardness (R) of 101.

The materials are then kneaded in the same way as described in Example 19, with the difference that, instead of the acrylonitrile-butadiene-styrene terpolymer used there, the graft copolymer (terpolymer) obtained by the above process is used. The kneaded mixture is as in Example 19 described, pressed in the heat and in the cold to form a plate. The plate has an Izod impact strength with a notched specimen of 293 kg- cm / cm, a Vicat softening point of 124 ° C. and a Rockwell hardness (R) of 121 .

Example 27

Kneading is carried out on a hot roller mixer in the same way as in Example 19 indicated, with the difference that the acrylonitrile-butadiene-styrene terpolymer used in Example 19 is replaced by a graft copolymer, that one 'obtained by grafting styrene onto a butadiene rubber and that an Izod impact strength in a notched specimen of

1 has 2.2 kg · cm / cm, a Rockwell hardness (R) of 119 and a Vicat softening point of 79.1 ° C. The kneaded mixture is, as indicated in Example 19, pressed in the heat and in the cold to form a plate. The plate has an Izod impact strength for a notched specimen of 21.3 kg-cm / cm, a Vicat softening point of 120 ^° C. and a Rockwell hardness (R) of 120.

_K) Example 28

As described in Example 19, 30 parts by weight of one are kneaded on a hot roller mixer impact-resistant mixture of 5 parts by weight of polybutadiene rubber and 25 parts by weight of an acrylonitrile

As a styrene copolymer (manufactured and sold from the Asahi Dow Chemical Company under the name "Tyril 767") with 70 parts by weight of the according to Example 19 by ring-opening polymerization of 5-cyano-bicyclo [2.2, l] hepten-2 produced Po-

: o lymerisais. The kneaded mixture becomes, in equal As indicated in Example 19, pressed in the heat and in the cold to form a plate. The plate owns an Izod impact strength on a notched specimen of 19.5 kg-cm / cm, a Vicat softening point of

2s 121 ° C and a Rockwell hardness (R) of 121.

Example 29

The kneading on a hot roller mixer is carried out in the same way as described in Example 28.

v> with the difference that you can do this in Example 28 used impact-resistant product replaced by an impact-resistant product, which consists of 5 parts by weight of a Butadiene-acrylonitrile copolymer and 25 parts by weight of polystyrene. The kneaded mixture is then, as described in Example 28, pressed in the heat and in the cold to form a plate. the Plate has an Izod impact strength on a notched specimen of 14.3 kg-cm / cm, a Vicat softening point of 122 ° C and a Rockwell hardness (R) of 120.

Example 30

Kneading is effected on the hot-roller mixer in the same way as described in Example 28, with the difference that instead of the impact-resistant product used in Example 2f, a different; impact-modified product is used, consisting of 5 Gewichtstei len chlorinated polyethylene containing 40% by weight Chloi, and 25 parts by weight of an acrylonitrile-styrene copolymer is The kneaded mixture is compressed in the heat and then in the cold to form a board to give the in Example 28 uses described ™ method The panel possesses an Izod impact strength with a notched specimen

19.3 kg-cm / cm, a Vicat softening point of 122 ° C and a Rockwell hardness (R) of 119.

Example 31

In the same manner as described in Example 28, kneading was carried out on a hot roll mixer werk, with the difference that you can do this in Example 2! The impact-resistant product used is replaced by another: the impact-resistant product made up of 7 parts by weight of the polybutadiene rubber used in Example 28 and 23 parts by weight of a methyl methacrylate lat-StyroI-copolymer consists, by weight of the 46 ⁰ / methyl methacrylate Kneaded Mischunj is then as described in Example 28, compressed in the Hitz <and in the cold into a sheet The Platti

has an Izod impact strength when the specimen is notched of 20.2 kg-cm / cm, a Vicat softening point of 121 ° C and a Rockwell hardness (R) of 121.

Example 32

In the same manner as in Example 28, a kneaded one is prepared using a hot roll mixer Mixture, with the difference that instead of the 30 parts by weight used in Example 28 of the impact-resistant product 50 parts by weight of an ι ο impact-resistant product used, which is made from 15 parts by weight of the polybutadiene used according to Example 28 and 35 parts by weight of the acrylonitrile-styrene copolymer used according to Example 28 and 50 parts by weight of the according to Example 19 by ι s ring-opening polymerization of 5-cyano-bicyclo [2.2, l] hepten-2 kneaded polymer produced. The kneaded mixture is then as in Example 28 described, pressed into a plate in the heat and in the cold. The plate has an Izod impact strength ^ o for a notched sample of 43.9 kg «m / cm, a Vicat softening point of 116 ° C. and a Rockwell hardness (R) of 115.

Example 33

The kneading on the hot roller mixer is carried out in the same way as described in Example 32, with the difference that the impact-resistant product used in Example 32 is replaced by another replaces heat-resistant product, which consists of 15 parts by weight of the acrylonitrile-butadiene-styrene terpolymer used in Example 19, 10 parts by weight of the chlorinated polyethylene from Example 30 and 25 parts by weight of the acrylonitrile-styrene copolymer of Example 30 The kneaded mixture is as described in Example 33 in the heat and in the cold pressed into a plate. The plate has an Izod impact strength on notched specimen of 73.5 kg · cm / cm, a Vicat softening point of 132 ° C and a Rockwell hardness (R) of 120.

Example 34

The kneading on the hot roller mixer is carried out in the same way as indicated in Example 28, with the difference that the impact-resistant product used in Example 28 is replaced by another Replaced impact-resistant product, which consists of 5 parts by weight of an acrylic ester rubber and 25 parts by weight of the Acrylonitrile-styrene copolymer used in Example 28. The kneaded mixture is, as described in Example 28, pressed in the heat and in the cold to form a plate. The plate has a Notched specimen Izod impact strength of 19.3 kg cm / cm, a Vicat softening point of 122 ° C and a Rockwell hardness (R) of 119.

Example 35

Effecting the kneading on a hot roll mill at 190 ⁰ C in the same manner as described in Example 19 with the difference that employed in Example 19, by ring-opening polymerization of 5-cyano-bicyclo [2 £ l] heptene-2 The polymer produced was replaced by the polymer produced according to Example 14 by ring-opening polymerisation from 5-cyano-5-methyl-bicyclo [2.2.1] hepten-2. The kneaded mixture is pressed into a plate in the heat and then in the cold, in the same manner as described in Example 19. The plate has an Izod impact strength on a notched specimen of 43.1 kg-cm / cm, a Vicat softening point of 140 ° C. and a Rockwell hardness (R) of 125.

Example 36

The kneading is carried out in the same way as described in Example 35 on a hot roller mixer, with the difference that instead of the acrylonitrile-butadiene-styrene terpolymer used in Example 35 the terpolymer used in Example 22 is used. The kneaded mixture is in pressed in the heat and then in the cold into a sheet using the procedure of Example 35. the Plate has an Izod impact strength on a notched specimen of 30.1 kg-cm / cm, a Vicat softening point of 137 ° C and a Rockwell hardness (R) of 123.

Example 37

A kneaded mixture is prepared using a hot roll mixer by the method of Example 35, with the difference that instead of the 20 parts by weight of the acrylonitrile-butadiene-styrene terpolymer used in Example 35, 30 parts by weight of an impact-resistant product composed of 7 parts by weight are used of the polybutadiene rubber of Example 28 and 23 parts by weight of the acrylonitrile-styrene copolymer of Example 28 and with the difference that 70 parts by weight of the according to Example 35 by ring-opening polymerization from S-cyano-S-methyl-bicyclo [2.2 , l] hepten-2 produced polymer are kneaded. The kneaded mixture is pressed in the heat and then in the cold, as described in Example 35, to form a plate. The plate has an Izod impact strength for a notched specimen of 24.1 kg-cm / cm, a Vicat softening point of 135 ^° C. and a Rockwell hardness (R) of 120.

Example 38

The kneading takes place on a hot roller mixer in the same way as described in Example 19, with the difference that the one used in Example 19, by ring-opening polymerization 5-Cyano-bicyclo [2.2, l] hepten-2 produced polymer by the according to Example 18 by ring-opening polymerization copolymer made from 5-cyano-bicyclo [2Al] hepten-2 and bicyclo [2Äl] hepten-2 replaced. The kneaded mixture becomes as in example 19 described, in the heat and in the cold to one Compressed plate The plate has an Izod impact strength for a notched specimen of 13.5 kg · cm / cm, a Vicat softening point of 116 ° C and a Rockwell hardness (R) of 122

Claims (3)

Patent claims: 1. Molding compounds, consisting of a) 5 to 95 Parts by weight by ring-opening polymerization of cyan-substituted norbornene derivatives of the general formula % By weight of at least one vinyl compound from the group consisting of styrene, acrylonitrile and methyl methacrylate and c) where appropriate, customary additives in customary amounts. 3. Molding compositions consisting of a) 5 to 95 parts by weight by ring-opening polymerization of cyan-substituted norbornene derivatives of the general formula