DE2414840A1 - RESIN COMPOUND - Google Patents

Description

The invention relates to a resin mass or resin composition, the one substituted by the ring-opening polymerization of cyano Contains polymer obtained from norbonene derivatives and has a number of excellent properties. From a publication by R.E. Rinechart (Journal of Polymer Science 1969, Part C, No 27, Pages 7 to 25) and published Japanese patent applications No. 227O5 / 67 and 7552/68 shows that a new type of polymer can be produced by using cycloolefins, such as cyclooctene, cyclopentene, cyclobutene, cyclooctadiene and norbonene, in an organic solvent 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

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Noble metals such as ruthen, osmium and iridium or halides of transition metals such as titanium, molybdenum, tungsten and vanadium, ring-opening polymerization catalyst produced undergoes.

On the other hand, Francis W. Michelotti and William P. Keaveney give (Journal of Polymer Science 1965, Part A, Vol.3, pages 895 to 905) that 5-chloromethyl-2-norbonen, a norbonen derivative, can actually be converted into a fiber polymer if it is a ring-opening polymerization using Subjects ruthenium compounds as catalysts, while 5-cyano-2-norbonen, that is, 5-cyano-bicyclo / 2.2.1 ^ hepten-2 no polymer is obtained, even if this compound is used in the presence of ruthenium, osmium or iridium compounds Subjected catalysts to ring-opening polymerization. As can be seen from the above, some of the Derivatives of cycloolefins, especially those of norbonen, by ring-opening polymerization using a certain Catalyst system can be converted into polymers, while the other norbonene derivatives, even if one uses the same catalyst system used, a ring-opening polymerization are not accessible.

It has now been shown that ring-opening polymerization of cyano-substituted norbonene derivatives polymers can be obtained if a catalyst system is used which consists of compounds of tungsten and / or molybdenum and organic aluminum compounds. It has also been stated that the Polymer using one of the compounds of titanium and / or vanadium and organic aluminum compounds existing catalyst system not through ring-opening polymerization cyano-substituted norbonene derivatives are produced (see Japanese Patent Application Nos. 31755/72 and 108902/72).

Those mentioned, by ring-opening polymerization of cyano-substituted Polymers produced from norbonene derivatives can be produced and possess on an industrial scale

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not only much better mechanical properties, such as impact strength and hardness, but also better transparency and Deformability than commonly used synthetic resins such as polypropylene and polyvinyl chloride, making these products can be used in a variety of ways, for example for the production of containers or foils, for which one, for example, usual Processing forms, such as injection molding or extrusion molding, applies.

On the other hand, enjoy vinyl chloride polymers that are used for Example characterized by exceptional tensile strength, hardness and heat resistance, growing in popularity. Come in addition, that recently significant improvements in terms of poor impact strength or the softening point (weak point) have been achieved by hard vinyl chloride resins so this Resin is suitable for a wide variety of uses. However, if you try to improve the impact strength of vinyl chloride polymers to be improved by adding another polymer, for example chlorinated polyethylene, to the vinyl chloride polymer incorporated, there is a disadvantage that the tensile strength, the hardness, the heat resistance and the transparency the vinyl chloride polymers are considerably worsened, although the incorporation of 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 1- "graft copolymers or methyl methacrylate-butadiene-styrene graft copolymers the impact strength of the vinyl polymers can be increased without the Tensile strength, hardness, heat resistance and transparency of these products are markedly deteriorated. However, this addition is always accompanied by the inevitable substantial deterioration which accompanies the physical properties distinguishing vinyl chloride polymers and results in poorer processability, chemical resistance and weather resistance of these polymers.

As already indicated, the vinyl chloride resins provided so far to eliminate the disadvantages of vinyl chloride resins stand out.

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Polymer compositions actually consist of, as a whole, that they have improved impact strength, however, have disadvantages on the other hand in that they have a have inferior tensile strength, hardness, heat resistance and transparency. As a result, have the proposed so far Vinyl chloride polymer compositions do not have all of the above mentioned properties necessary for malleable resins, if these are to be used on an industrial scale There is a strong need for the development of new vinyl chloride polymer compositions containing all of the foregoing Possess properties. Therefore, it can be presumed that those selected from the above-mentioned cyano-substituted norbonen derivatives Polymers produced which have a higher impact strength than vinyl chloride polymers can be used for this purpose, to improve the properties of the vinyl chloride polymers.

Although the above-mentioned, by ring opening polymerization of Cyan-substituted norbonen derivatives compared with other commonly used synthetic polymers Resins possess a number of superior properties, they are not always characterized by satisfactory processability and impact resistance, for example when used on mechanical workpieces, window frames, helmets and lampshades (e.g. for street lamps).

It has now been shown that the incorporation of rubber-like material into the cyan-substituted by ring-opening polymerization Norbonene derivatives obtained polymers whose impact strength can significantly improve, which is already in the Japanese Patent Application No. 97233/73 is proposed. However, the addition of such rubber material is still limited by the The disadvantage is that, although the impact strength of the polymers made from the cyano-substituted norbonene derivatives increases their tensile strength deteriorates.

Common practice for improving the processability of common synthetic resins is either by molecular weight of the products or a readily miscible plasticizer

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to incorporate. 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 is increased the polymers can be improved.

It is accordingly an object of the invention to provide synthetic resin compositions or resin compositions free from the foregoing Disadvantages are and are excellent in impact resistance, processability and the like.

The invention therefore provides a resin composition which is 5 to parts by weight by ring-opening polymerization of cyan-substituted Norbonen derivatives of the general formula

in which W, X, Y and Z hydrogen atoms, nitrile groups, nitrile

Gruopen-containing substituents, alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 1 to 20 carbon atoms, aryl groups with 1 to 20 carbon atoms and / or aralkyl groups having 1 to 20 carbon atoms, at least one of the groups W, X, Y or Z is a nitrile group and / or a nitrile group Represents substituents,

polymers obtained and 95 to 5 parts by weight of homopolymers and / or contains copolymers of vinyl chloride.

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

1. a styrene or vinyl copolymer containing 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

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at least one elastomer, such as. a butadiene rubber, an acrylic ester rubber, chlorinated polyethylene and / or a Ethylene-propylene rubber is incorporated or 3. a graft copolymer, which can be at least received one of the vinyl compounds mentioned on the elastomer.

The resin compositions according to the invention not only have a very good one Impact resistance and processability, but also excellent Heat resistance, tensile strength and hardness.

The cyano-substituted norbonen derivatives used as monomers according to the invention contain at least one nitrile group or one a nitrile group-containing substituent in the 5- and / or 6-position of bicyclo / 2.2.i7hepten-2, as is evident from the following general formula that reflects the chemical structure of the monomer:

in which W, X, Y and Z have the meanings mentioned above.

The substituents containing nitrile groups include the cyanomethyl group, the cyanoethyl group ,. the cyanopropyl group, the cyano-n-butyl group, the cyanisobutyl group and the CO-cyano-n-heptyl group a. As hydrocarbon groups, methyl groups, Ethyl groups, propyl groups, n-butyl groups, isobutyl groups, octyl groups, phenyl groups, cyclohexyl groups and 2- octenyl groups to be available.

The monomers of the above general formula can be reacted obtained from cyclopentadiene with the nitrile group-containing vinyl compounds, in particular by a Diels-Alder reaction (See the publication by H.L. Holmes in "Organic Reaction "Vol.4, pages 60-173, 1948, John Wiley and Sons, Inc.)

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Some of the monomers can also be obtained by reacting Dicyclor > entadiene with the vinyl compounds containing nitrile groups produce. The nitrile group-containing vinyl compounds that can be used for this reaction include acrylonitrile, Methacrylonitrile, ot-n-octy! Acrylonitrile, vinylidenecyanide, Fumaric acid dinitrile (fumaronitrile), maleic acid dinitrile (Maleonitrile), allyl cyanide, cinnamonitrile and linoleic acid nitrile a. Starting from these vinyl compounds containing the nitrile group, the above-mentioned Diels-Alder reaction is obtained S-Cyanobicyclo / S.2.1 / hepten-2, S-Cyano-S-methylbicyclo / ^. 2.1 / hepten-2, S-Cyano-S-n-octylbicyclo / iZ ^ .I. / hepten ^, 5,5-Dicyanobicyclo / 2.2.1_7hepten-2 , 5, o-dicyanobicyclo / S. 2.17hepten-2, 5-cyano-6-phenylbicyclo / 2.2.1j ^ hepten-2 and a mixture of 5-ω-cyano-n-heptyl-6-n-2-octenylbicyclo / 2.2. 1./hepten-2 and 5-W-cyano-2-decenyl-6-n-pentylbicyclo / 2.2.1_7hepten-2. Of the Substituent can be in the endo or exo position. Although the cyano-substituted norhone derivatives from two groups of If there are isomers that result from the endo and exo positions occupied by the substituent groups, the different isomeric groups can be effectively separated from each other by precision distillation. The endoisomer of For example, 5-cyanobicyclo / 2.2.1_ / hepten-2 remains at room temperature solid and has a boiling point of 88 ° C at 12 mm Hg. The exoisomer is in the form of a colorless one at room temperature Liquid before which at 12 mm Hg has a boiling point of 80.5 ° C, at 20 C a density of 1.0065 g / cm and at 20 C has a refractive index of 1.4862 with respect to the sodium D line. These isomers can be used separately or together in the Ring opening polymerization can be used. It is possible to have a single one or two or more different ones of the above mentioned to use cyano-substituted norbonene derivatives.

Those derived from the cyano-substituted norbonene derivatives Polymers can be obtained by ring-opening polymerization of the various types of cyano-substituted ones obtained by the above-mentioned process Norbonen derivatives in the presence or absence of an inert organic solvent using a Catalyst system that consists of a mixture of organic

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Aluminum compounds and compounds of tungsten and / or molybdenum consists or using a catalyst system produce, which consists of the mixture mentioned, with at least one compound such as water, a peroxide, a Epoxide, an organic halide, an acetal compound, an orthocarbonic acid ester and / or an alcoholic compound are added has been.

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

W,

-CH = CH

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

The polymers obtained show different properties, which depend on various factors, namely on whether the double bond of the polymer is in the cis form or in the trans form is present or how the various substituents relate to one another and what their steric position is.

The cyano-substituted norbonen derivatives can in certain cases via their C = C double bond according to the following reaction scheme undergo polymerization, that is, vinyl polymerization

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

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However, this vinyl polymerization leads to polymers which are differ with regard to their chemical structure from those used according to the invention.

The organic aluminum compounds forming part of the catalytic system used in the ring-opening polymerization correspond to the following general formulas AlR ₃ or AIR X _3- (in which R is an alkyl or aryl group , X is a halogen atom, a hydrogen atom or an alkoxy group, and η 1, 1.5 or 2) or the general formula AlR ₃ ^ H ₃ O (in which R has the meanings given above and an H ₂ O / AlR ₃ molar ratio of <1.5 is maintained).

The compounds covered by the above formula AlR ₃ are trialkyl aluminum compounds such as trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trihexyl aluminum and trioctyl aluminum, and tri-aluminum aluminum compounds such as triphenyl aluminum.

Include the compounds encompassed by the above formula AlR ^ X a: dialkyl aluminum monohalides, such as diethyl aluminum monochloride, Di-n-propyl aluminum monochloride, diisobutyl aluminum monochloride, Di-n-butyl aluminum monochloride, diethyl aluminum monobroinide and diethyl aluminum monoiodide; Dialkyl aluminum monohydrides, such as diethyl aluminum monohydride, di-npropyl aluminum monohydride and diisobutyl aluminum monohydride; Diaryl aluminum monohalides, such as dibenzyl aluminum monochloride, Diphenyl aluminum monochloride, dibenzyl aluminum monobromide and ditolyl aluminum monochloride; and dialkyl aluminum monoalkylates, such as diethyl aluminum monoethylate and diisobutyl aluminum monobutylate.

The general formula AlR ₁ -X ₁ ^ includes ethylaluminum sesquichloride, ethylaluminum sesguibromide and diisobutylaluminum sesquichloride.

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The general formula AlRX »includes alkyl aluminum dihalides / such as ethyl aluminum dichloride, ethyl aluminum dibromide, propyl aluminum dichloride, Isobutyl aluminum dichloride, ethyl aluminum dibromide and ethyl aluminum iodide; Aryl aluminum dihalides, such as benzyl aluminum dichloride, benzyl aluminum dibromide, To IyI aluminum dichloride and phenyl aluminum dichloride; and alkyl aluminum dialkylates, such as ethyl aluminum diethylate.

The mixtures denoted by the formula AlR ₃ -H ₃ O are mixtures of trialkylaluminum compounds and water in which the trialkylaluminum compound is present in an amount of at least 2 moles, based on 3 moles of V7asser. These mixtures include, for example, a mixture of triethyl aluminum and water in which triethyl aluminum and water should be contained in an amount of 1: 0.5.

The most preferred of the organic aluminum compounds given above are triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diethyl aluminum monochloride, di-n-butyl aluminum monochloride, Ethyl aluminum sesquichloride, diethyl aluminum monobutylate and a mixture of triethyl aluminum and water in which triethyl aluminum and water are in a molar ratio of 1: 0.5 are included.

The compounds of tungsten and molybdenum, which partially form the catalyst system erfinduncrsgemäß used include halides of tungsten and molybdenum, such as tungsten hexachloride, tungsten pentachloride, tungsten hexafluoride, tungsten pentafluoride, molybdenum pentachloride, Molybdänhexachlorid, molybdenum pentafluoride, molybdenum hexafluoride, Molybdänpentabromchlorid and Molybdänpentabromid; Oxyhalides of tungsten and molybdenum such as tungsten oxitetrachloride, tungsten oxitetrabromide, tungsten oxyichloride, molybdenum oxy trichloride and molybdenum oxy tetrachloride; and additionally molybdenum _{dioxide acetylacetonate / MoO 2} (CH ₃ COCH = C (CH ₃ ) O-) ₂ , which will be abbreviated as MoO ₂ (AcAc) ₂ in the following, tungsten hexaalkoxide, tungsten hexaphenolate, tetrachlorotungsten diphenolate, tetrachloro tungsten triamide and dichloro-tungsten dialcoholate

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Tungsten halides, such as the compound of

Formula Al.W ₀ Cl ₄₀ , which can be obtained by reducing tungsten halides 4 j Io

obtained with aluminum powder. The most preferred of the compounds of tungsten and molybdenum mentioned are molybdenum pentachloride, Tungsten hexachloride and tungsten oxitetrachloride (WOCl.). That The molar ratio of the organic aluminum compound to the compounds of tungsten or molybdenum is generally greater than 0.1, preferably greater than 0.5. The use of less than 0.1 moles of the organic aluminum compounds, based on 1 mole of the compounds of tungsten or molybdenum does not give practical polymerization activity. A Catalyst system containing 10 moles of organic aluminum compounds based on -1 mole of compounds of tungsten or Containing molybdenum gives a particularly high level of polymerization activity.

Although the above-mentioned binary, made of organic aluminum compounds and compounds of tungsten or molybdenum catalyst system consisting of ring-opening polymerization Cyan-substituted norbonene derivatives can be achieved by adding a third component to the said binary Catalyst system, which converts it into a ternary system is, the polymerization activity is significantly increased and the properties of the using the binary catalyst system obtained polymers can be varied further.

As a third component, at least one of the following group of compounds can be used, which are water, peroxides, Epoxides, organic halides, acetal compounds, alcoholic compounds, phenolic compounds, orthoformic acid esters and orthocarbonic acid esters. The peroxides include alkyl peroxides such as tertiary butyl peroxide; Aryl peroxides such as benzoyl peroxide; Alkyl or aralkyl hydroperoxides, such as tert-butyl hydroperoxide and cumene hydroperoxide; Hydrogen peroxide; Peracids such as peracetic acid; and esters derived from these peracids, Ketones and aldehydes. Ethylene oxide, pronylene oxide, Butylene oxide, epichlorohydrin, allyl glycidyl ether and butadiene oxide can be used. As organic halides can

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ter-butyl hypohalite compounds; Allyl halides such as allyl chloride; tert-alkyl halides, such as tert-butyl chloride; halogenated Ketones such as ol-chloroacetone; and halogenated alcohols such as 2-chloroethanol can be used. As acetal compounds are Acetaldehyde diethylacetal, diethoxymethane, acetone dimethy acetal and dichloroacetaldehyde dimethyl acetal are suitable. The alcoholic compounds include methyl alcohol, ethyl alcohol, n-propyl alcohol, n-butyl alcohol and isobutyl alcohol.

Phenol, p-methylphenol, ρ, ρ'-isonropylenediphenol, 2,6-dimethylphenol, p-chlorophenol, 1,3-benzenediol and 1,3,5-benzenetriol can be used. The orthoformic acid esters include methyl orthoformate and ethyl orthoformate. The orthocarbonic acid ester can be Ethyl orthoacetate, n-propyl orthopropionate and Use butyl orthophenylacetate. The preferred orthocarboxylic acid esters are alkyl orthoformates and in particular Methyl orthoformate and ethyl orthoformate. Water is also an effective third ingredient for the said catalyst system. Although the amount of the added third component depends on its type, it is generally 0.1 to 6 moles, more preferably 0.3 moles, based on 1 mole of the compounds of tungsten or Molybdenum.

Although the amount in which the catalyst system in question to the monomers consisting of the cyano-substituted norbonene derivatives is added, depending on the nature of the monomer, etc., the compounds of tungsten or molybdenum should generally be in Amounts of 0.001 to 20 moles, or more preferably 0.1 to 5 moles, per 100 moles of the monomer can be added. The addition of more than 20 moles of the compounds of tungsten or molybdenum per 100 moles of the monomer not only results in high cost, but also yields no further increase in the catalytic effect, so that this excess addition in particular reduces the polymerization activity does not increase further. On the other hand, if excessively large amounts of the compounds of tungsten or molybdenum are used,

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contains the reaction system after the ring-opening polymerization is completed There are still considerable amounts of residual tungsten or molybdenum compounds that are difficult to remove. The presence this catalyst component in the polymer obtained leads to an undesired discoloration of the latter. This discoloration deepens the color of a resin composition containing such a colored polymer during the subsequent deformation svor gang and leads to a thermal deterioration of the product obtained.

As already mentioned, the ring-opening polymerization can cyano-substituted norbonene derivatives using the catalyst system described above, optionally in the presence of a inert organic solvent can be carried out. Inert organic solvents which form the catalyst system are preferred for this purpose not affect. Typical solvents of this type are aliphatic hydrocarbons, such as pentane, heptane, Hexane, petroleum ether and decane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as Cyclohexane, decalin and cyclooctane; halogenated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, 1,2-dichloropropane, Chloroform, chlorobenzene and carbon tetrachloride; and ether how Diethyl ether and tetrahydrofuran. The said inert organic Solvents can be used singly or in combinations.

The catalytic constituents, the monomer (the cyan-substituted Norbonene derivatives) and the (optionally used) inert organic solvent can be used in different order be admitted. The typical process sequence consists in first adding the inert organic solvent, then the monomer, then the compounds of tungsten or molybdenum, then the third component (if used) and finally add the organic aluminum compounds. It is also possible to use the desired compounds of the catalytic components, to mix the monomer and the solvent and to heat them separately before proceeding in the ring-opening polymerization can be used.

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-, -14 -

The goal of ring-opening polymerization can be as described above can be fully achieved by doing the ring opening polymerization the cyano-substituted norbonene derivatives carries out in the presence of a catalyst system, the compounds of Tungsten and / or molybdenum and organic aluminum compounds or a mixture of both types of compounds and the aforementioned third component contains. On the other hand, the molecular weight the polymer obtained can be controlled by adding it to the polymerization system -olefins, such as ethylene, propylene, Butene-1 and hexene-1; internal olefins such as butene-2 and hexene-2; conjugated diolefins such as butadiene and isoprene; or non-conjugated Diolefins such as 1,4-hexadiene adds. In this case it is it is generally advisable to use 0.01 to 10 parts by weight of the molecular weight controlling agent per 100 parts by weight of the to use cyano-substituted norbonen derivatives used as monomers.

As already mentioned, the polymer can be produced by ring-opening polymerization of the monomer in question in the presence of an inert organic solvent or in the absence of the solvent (Polymerization in the mass). If you use an inert organic solvent, you put this in generally in an amount of 1 to 10 parts by volume per 1 part by volume of the monomer.

The ring-opening polymerization is generally conducted at a temperature from -100 ⁰ C to +200 ⁰ C, carried out preferably from -40 ⁰ C to +100 C. At a temperature below -100 ⁰ C temperature, the reaction system does not display the desired polymerization, resulting in a very slow polymerization process result. In this case the polymerization proceeds very slowly and in certain cases leads to the mixture of the inert organic solvent and the monomer solidifying. On the other hand is obtained at a temperature of more than 200 ⁰ C by the ring-opening polymerization, no polymer with good quality, so that these Temneraturen are undesirable for practical use.

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The ring-opening polymerization is preferably carried out in one inert atmosphere, for example in the presence of argon or nitrogen. When oxygen and moisture in the reaction system are present, the catalytic components, that is, the organic aluminum compounds and the compounds of tungsten or molybdenum are changed, whereby the Reproducibility of the polymerization is prevented.

The removal of the catalyst residue and the recovery of the polymer formed after the end of the ring-opening polymerization can be carried out by procedures commonly used in the solution polymerization of isonrene and butadiene will. In particular if a solution is obtained in the ring-opening polymerization that is the one obtained in the polymerization Contains polymer, the unreacted portion of the monomer and the catalyst residue in a low molecular weight Alcohol, for example methyl alcohol or ethyl alcohol, the one gerinae menae containing hydrochloric acid, poured, causing at the same time the catalyst residue is removed and the polymer formed is precipitated out. The elimination of the catalyst residue and the recovery of the polymer can furthermore be achieved by first treating the ring-opening polymerization solution obtained evenly with a water-immiscible solvent, for example methylene chloride, and then dilute the solution with water that contains a chelating agent such as nitrilotriacetic acid or ethylenediaminetetraacetic acid contains, treated, whereby the catalyst residue is removed, whereupon the polymer and the organic solvent with the help of a Danrof stripping process (steam stripping) wins.

The cyan-substituted ones through the ring-opening polymerization Polymers formed by norbonene derivatives not only include the homopolymers of the formed in the above-mentioned process cyane-substituted norbonen derivatives, but also copolymers, which are produced by the ring opening polymerization of a mixture which the cyano-substituted norbonen derivatives as main components and other cycloolofinic compounds have been formed,

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the ring opening polymerization in the same way as in Case of the preparation of the cyan-substituted homopolymers Norbonene derivatives is carried out.

Further cycloolefinic compounds which are typically used as comonomers for the preparation of the abovementioned copolymers include monocyclic olefins such as cyclopentene, cycloheptene and cyclododecene; non-conjugated cyclopolyenes such as 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 1-chloro-1,5-cyclooctadiene and norbornadiene; Norbonene ester derivatives, such as S-methoxycarbonyl-S-methyl-bicyclo / Ä. 2.1 / hepten-2, 5-acetoxybicyclo / 2.2.1Jhepten-2, 5, e-dimethoxycarbonyl-bicyclo / S.2.1 / hepten-2 and 5-W-carbomethoxy-n-heptyl-Sn-octyl-bicyclo / ä ^ .1,7 hepten-2; Norbonene ether derivatives, such as S-methoxy-bicyclo / S ^. Λ] hepten-2, S-ethoxy-bicyclo / ^. 2.1_7hepten-2, 5-Cyciohexyloxybicyclo / 2.2. i7hepten-2, S-methoxy-methyl-bicyclo / iZ. 2.17hepten-2, S-methoxy-G-methoxymethyl-bicyclo / iZ. 2. t / heDten-2 and 5-phenoxybicyclo / 2.2.1_7hepten-2; Norbonic anhydride derivatives, such as 3,6-methylene-1,2,3, o-tetrahydro-cis-dhthalic anhydride, 6- (B-carboxy-bicyclo / ^. 2.1 / heptenyl) acetic anhydride, 4,7-methano-1-methyl- 1,2,3,3a, 4,7,7a, 8-naphthalene-1,2-dicarboxylic anhydride and 4- (bicyclo / 2.2.1 / 2-heptenyl) phthalic anhydride; Norbonenimide derivatives, such as N-methyl-3,6-methylene-1,2,3,6-tetrahydro-cisphthalimide, N-methyl-S ^ -methylene-i-methyl-i, 2,3,6-tetrahydro-cisphthalimide, Bicyclo / "2. 2. Vhepta-2-en-5-spiro-3 '- (n-ethyl succinimal), 2-methyl-2-aza-1,3-dioxo-5,8-methano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, N-ethyl-5,8-methano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene-2,3-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 and N- (5-norborna -2-enyl) methyl-naphthalene-2,3-dicarboxyimide; aromatic norbonen derivatives, such as 1,4-dihydro-1,4-methano-naphthalene, 1,4-dihydro-1,4-methano-6-methylnanhthalene, 1 , 4-Dihvdro-1,4, -methano-6-laethoxycarbonylnaphthalin, 6-chloro-1,4-dihydro-1,4-methanonephthalin, 5,8-diacetoxy-6,7-dichloro-1,4-dihydro- 1,4-methanonaphthalene, 5,8-diacetoxy-1,4-dihydro-1,4-methano-6-methylnanhthalene, 5,8-diacetoxy-1,4-dihydro-6,7-dimethoxy-1,4- methanonanhthalin, 1,4-dihydro-1,4-methanoanthracene, 9,10-diacetoxy-

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1,4-dihydro-1,4-methanoanthracene and 1,4-dihydro-9,10-diphenyl-1,4-methanoanthracene; Norbonen derivatives containing polar groups, for example norbonenhalogen derivatives, such as 5-chlorobicyclo / i2.2. * \ J heoten-2, 5, S-dichloro-bicyclo / ^^. 1 / hepten-2 and 5,6-dichlorobicyclo / 2.2. iyhepten-2; and bicyclo / 2.2. iyhepten-2 (norbonen) a.

When the above-mentioned copolymers of the cyano-substituted norbonene derivatives for the production of the resin compositions according to the invention are used, it is preferred to prepare these copolymers by ring-opening polymerization of a mixture which contains at most 1 mole of the other cycloolefinic compounds per mole of the cyano-substituted norbonen derivatives. If the other cycloolefin compounds, for example the monocyclic olefins such as cyclopentene and cyclooctene, in an amount greater than this used as 1 mole per mole of the cyano-substituted norbonen derivatives the resin composition containing these copolymers shows a poorer surface hardness and a lower surface hardness Softening point.

If the homopolymer or the copolymer of the cyan-substituted Norbonen derivatives (hereinafter referred to as "polymers of cyano-substituted norbonen derivatives") can be mixed homogeneously with the vinyl chloride resins Resin masses obtained that not only have the good tensile strength, hardness and transparency of vinyl chloride resins, but also that also have excellent impact resistance and improved heat resistance.

The incorporation of the polymers of the cyano-substituted norbonene derivatives gives a very clear effect, although the functional mechanism is still unknown. It is believed, that these polymers show good compatibility with the vinyl chloride resins and both components because of an unexpected synergistic effect produce the desired effect.

The vinyl chloride resins in which the polymers of the cyano-substituted Norbonen derivatives can be incorporated by

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Polymerization in bulk by solution polymerization Emulsion polymerization or by suspension polymerization. According to the invention it is possible to use not only vinyl chloride homopolymers, but also to use mixed polymers that contain vinyl chloride as the main component and vinyl acetate, Contains ethylene, propylene or vinyl ether. The usage of Vinyl chloride homopolymer, in particular the homopolymer with a high average degree of polymerization, results Desired resin compositions with higher impact strength than achieved by using the above-mentioned copolymers will. It should be noted that when vinyl chloride copolymers are used, the impact strength of the resin composition obtained rises less, the greater the proportion of the compounds copolymerized with vinyl chloride.

The proportions in which the above-mentioned resin compositions the mentioned Containing ingredients 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 of the cyano-substituted norbonen derivatives. The reason for this is that the amounts of the polymers of the cyano-substituted norbonen derivatives than 5 parts by weight are not sufficient to increase the impact strength of the vinyl chloride resins in question and amounts of derivatives higher than 95 parts by weight have the disadvantage that they make the resin compositions easily flammable.

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

A mixture of the polymers produced by the above process of the cyano-substituted norbonen derivatives with styrene homopolymers or vinyl copolymers containing at least 50

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% by weight of at least one vinyl compound such as styrene, acrylonitrile and / or contain methyl acrylate {v / where styrene homopolymers and vinyl copolymers are referred to collectively as "vinyl resins" are) leads to the fact that the resin composition obtained has good processability having.

Those for the production of the above-mentioned resin compositions with good processability with the polymers of cyano-substituted norbonene derivatives mixed vinyl resins are obtained by polymerizing at least one (monomeric) vinyl compound such as styrene, Acrylonitrile and / or methyl methacrylate, with a polymerization in bulk, solution polymerization, emulsion polymerization or suspension polymerization may and may use a free radical initiator, for example, an organic peroxide, as the polymerization initiator can. The vinyl resins include styrene homopolymers, acrylonitrile-styrene copolymers, Methyl methacrylate-styrene copolymers, copolymers containing methyl methacrylate as Main component and other monomers contain and acrylonitrile-styrene-methyl methacrylate polymers a. The vinyl resins are produced by known technical processes and are diverse used. The homopolymers and copolymers mentioned have a molecular weight that is generally between

2 ζ

100,000 and 500,000, a melt viscosity of 10 to 10

Poise, determined with the coca flowmeter, which has a nozzle has a diameter of 1 mm and a length of 10 mm and with a load of 100 kg and at a temperature of 200 ° C is operated.

The styrene homopolymer generally has a molecular

2 weight from 200,000 to 500,000, a melt viscosity of 10 to 10 poise, one with the coca flow meter fitted with a nozzle with a diameter of 1 mm and a length of 10 mm and is operated with a load of 100 kg at a temperature of 200 C, certain flow velocities

- 1 - 2

speed (0) from 5 χ 10 to 10 and an intrinsic viscosity of 0.7 to 0.9. The methyl methacrylate copolymers, the methyl methacrylate as a main component and

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contain other monomers, have a melt viscosity of 10 to 10 poise. The acrylonitrile-styrene copolymers contain at most 40% by weight of acrylonitrile and have a melt viscosity of 10 to 10 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

2 5
Melt viscosity of 10 to 10 poise. 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

2 5

sity from 10 to 10 poise, the styrene content of the mixture

1 to 99% by weight.

The resin compositions according to the invention exist with good processability from 5 to 95 parts by weight of the polymers of the eye-substituted Norbonen derivatives and 95 to 5 parts by weight of the vinyl resins. Large proportions of vinyl resins lead to a reduction the softening point and the surface hardness of the resulting Resin compound, although the processability of the resin compound is increased. Therefore, if it is desired to make a Harz breed, to be used for purposes requiring a high softening point and high surface hardness, It is preferred that the resin composition consists of 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. The vinyl resins, in particular styrene homopolymers and vinyl copolymers can be used individually or in combination. Of course, it is possible to use a styrene homopolymer with an or to mix several different vinyl copolymers.

If necessary, the resin compositions in question can have good processability with thermoplastic resins, such as the homopolymers or copolymers of vinyl chloride and the tertiary polymers of acrylonitrile, butadiene and styrene and a rubber material such as butadiene rubber, chlorinated polyethylene and a polychloroprene rubber are mixed.

The vinyl resins in which the polymers of the cyano-substituted

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Norbonen derivatives can be incorporated by mixing be replaced from the vinyl resins and elastomers, whereby the resin composition obtained is particularly impact-resistant. The high impact resistance or impact strength of the resin composition can also be achieved by using instead of the mixture of the elastomer and the vinyl resins used graft copolymers, which are obtained by grafting vinyl compounds onto the elastomers mentioned receives.

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

The butadiene rubbers consist of butadiene rubber (butadiene homopolymers) or styrene-butadiene rubber or acrylonitrile-butadiene rubber (copolymers containing butadiene as Main component and contain styrene or acrylonitrile). The copolymer can be obtained by random copolymerization or form by block copolymerization. The acrylic ester rubbers may include copolymers made from acrylic esters as the main component and minor amounts of, for example Acrylonitrile have been produced. These rubbers can be prepared by emulsion polymerization. The chlorinated Polyethylene is obtained by chlorinating ethylene homopolymers with a high density ranging from 0.93 to 0.97 g / cm or by chlorination of a copolymer of ethylene and a t * -olefin, being in a solvent or in aqueous suspension works. 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 Mixture that has a small amount of a straight or branched chain Diolefins 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 one

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Diene compound such as bicyclo / 2.2. i / heOten-2. Of the Ethylene-propylene rubbers are preferred in which the The ratio of the ethylene units to the propylene units is 35:65 to 65:35. The rubbers or elastomers mentioned above obtained on an industrial scale by interpolymerization of the constituents using a catalyst that predominantly consists of organic aluminum compounds and transition metal compounds, and are used in a variety of ways.

For the production of resin masses with particularly high impact strength by mixing with the polymers of the cyano-substituted norbonene derivatives used mixture of vinyl resins and Elastomers generally consist of 98 to 70 parts by weight of the vinyl resins and 2 to 30 parts by weight of those mentioned above Elastomers.

The above graft copolymers used according to the invention can be prepared by adding at least one vinyl compound, such as styrene, acrylonitrile and / or methyl methacrylate grafted onto said elastomer. This graft can by bulk polymerization, by solution polymerization, by emulsion polymerisation, by suspension polymerisation or by a combination of these polymerisation processes (for Example by a combination of a polymerization in the Mass and suspension polymerization) can be achieved.

The graft copolymers formed by these processes typically include: Highly impact resistant styrenic resins which Grafting of styrene onto butadiene rubber or styrene-butadiene rubber can be obtained; Acrylonitrile-butadiene-styrene terpolymers (ABS resins) made by grafting styrene and acrylonitrile on butadiene rubber, styrene-butadiene rubber or acrylonitrile-butadiene rubber (nitrile rubber); Methyl methacrylate-butadiene-styrene terpolymers, which by Grafting of styrene and methyl methacrylate onto butadiene rubber or styrene-butadiene rubber are obtained; Acrylonitrile-acrylic acid ester-styrene terpolymarisate (AAS resins), which by grafting styrene and acrylonitrile onto acrylic ester rubbers,

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special acrylic rubbers (copolymers of acrylic esters as the main ingredient and a small amount of, for example, acrylonitrile); Graft copolymers (ACS resins), obtained by grafting acrylonitrile and styrene onto chlorinated polyethylene (CPE); and graft copolymers (ÄES resins), which can be obtained by grafting on acrylonitrile and styrene on ethylene-propylene rubber (ethylene-propylene copolymers; EPR or EPM) or on ethylene-propylene terpolymers (EPT or EPDM). All these graft copolymers are known Process produced on an industrial scale.

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

The high impact resin compositions of the present invention 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 the one with the styrene homopolymer or the vinyl copolymers mixed elastomers or the graft copolymers exist.

The resin compositions according to the invention prepared in this way not only have very high impact strength 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 rubbers polyethylene, chloro-sulfonated Polyä Thylen, ethylene-propylene Xautschuken, A ^- Thylen-propylene

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Ternopolymers, chloroprene rubbers (CR) and acrylic rubber be mixed.

The constituents of the resin compositions or resin compositions according to the invention are generally mixed in a dry mixer such as a ribbon mixer, a mixer with a rotating cone, a rotary mixer or a Henschel mixer. However , a mixing device such as a mixing roll mill with hot rollers, a Banbury mixer or a melt extrusion device is suitable, since the above-mentioned constituents in the molten state can be mixed relatively easily homogeneously with these devices. Furthermore, depending on the nature of the constituents, the method can be adapted accordingly by adding one constituent to a solution in which the other constituent is dissolved or to an aqueous or organic suspension in which the other constituent is suspended, and then adding to the Achieving uniform mixing, the water or the organic solvent can distill off.

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

When the ingredients are mixed, a stabilizer is usually added to prevent the decomposition or breakdown of the various polymer components (especially vinyl chloride resin), by exposure to heat, oxygen, light (ultraviolet radiation) or ozone. As a stabilizer organotin compounds are used, such as dibutyltin maleate and dibutyltin dilaurate, lead compounds such as basic lead phosphite, Organic acid salts such as calcium stearate and cadmium stearate, enoxy compounds and phonol compounds. the However, use of organic tin compounds is desirable in order to maintain the transparency of the resin compositions in question.

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Furthermore, it is * possible to use various additives, which are usually in "Harzon use, such as flame retardants, plasticizers, Lubricants, reinforcing agents, fillers, antistatic Agents, agents for improving electrical properties, ultraviolet light absorbing agents, foaming agents and colorants to be incorporated into the resin compositions of the present invention. This incorporation of further components is also the subject the invention.

The resin compositions according to the invention can by pressing, extrusion, Injecting, blowing or pouring molded into various products in a similar way to the usual synthetic resins such as sheets, plates, rods, tubes, foils and further processed products, e.g. bags, packaging materials, Containers of various types, electrical parts including lighting equipment, various daily consumables, 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 ram thick test sample by determining the temperature (in C) at which a needle penetrates 1 mm into the test sample, according to ASTM regulation D-1525- 58T was used to determine the Vicat softening point. The Rockwell hardness stands for the value of the surface hardness (R) of the test sample, which was determined according to ASTM regulation D-785-51 at 20 ° C. The Izod impact strength was determined using a 3 mm thick notched test specimen according to ASTM test specification D-255-56 in a thermostat at 20 ° C. The tensile strength stands for the value determined by stretching a dumbbell-shaped 1 mm thick test specimen (Japanese Industrial Standard JIS No. 3) at a speed of 5 cm / min in a thermostat at 20 ° C. The melt viscosity or the viscosity of the melt was determined by "the resin is at 200 ⁰ C .for a load of 100 kg using a Koka-Fließmeßeinrichtung that with a nozzle having a diameter

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- 26 is equipped with 1 mm and a length of 10 mm.

Examples 1 to 4 and Comparative Examples 1 to 4

A 10! Autoclave filled with dry nitrogen is charged with 4500 ml 1,2-dichloroethane, 1500 ml (12 mol) monomeric * S-Cyano-bicyclo / ä ^. 1 / hepten-2 (cyanorbonen), 10 ml (0.12 mol) n-hexene-1 and 120 ml of a solution containing 0.2 mol of tungsten hexachloride acetaldehyde diethyl acetal (which are present in a 1: 2 molar ratio, with tungsten hexachloride in an amount of 24 millimoles is present, which is 0.2 mole percent based on the above mentioned monomers corresponds) in 1,2-dichloroethane. The reaction system is then heated to 70 ° C. and 11.9 ml (96 millimoles) of diethylaluminum chloride are added to the reaction mixture. After the polymerization has been carried out with stirring for 5 hours, the reaction system is treated with 200 ml Ethanolamine and 10 g of the stabilizer bis (2-hydroxy-3-tert-butyl-5-methylOhenyl) methane (available under the designation "Yoshinox 2246" from Yoshitomi Chemicals Mfg.Co.). Then stir the mass for 30 minutes at this temperature. The product obtained (that is, one containing the polymer formed Solution) diluted with 1,2-dichloroethane (where the Polymer has a concentration of about 10% by weight). Then 4000 ml of an aqueous solution is added which contains 1% by weight of the trisodium salt of nitrilotriacetic acid and stirs vigorously for 30 minutes at 20 ° C. After standing the mass is separated 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 left at 50 ° C. overnight dried in a vacuum of less than 1 mm Hg, giving 1150 g of an essentially colorless, transparent polymer receives. The conversion is 80% of the monomer used. The polymer obtained as a product has a base molar mass Viscosity number of 0.64, an Izod impact strength of 6.3 kg cm per cm for a notched sample, a Vicat hearing

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point of 26 ° C, a Rockwell hardness R of 127 and a melt viscosity of 8.6 χ 10 poises.

The in the above manner by ring-opening polymerization from S-Cyano-bicyclo / S ^. 1 ._7hepten-2 produced polymer (polycyanone orbonen) is added in the proportions given in Table I with polyvinyl chloride (produced by Kureha Chemical Industry Co., Ltd. and available under the name "Kureha S901"). Both ingredients are kneaded for about 5 minutes on an 8 inch mixer mill operating at 175 ° C. At this point, 3 parts by weight of dibutyltin maleate, based on 100 parts by weight of the total amount of resin, are added as a stabilizer. The kneaded resin is shaped in a press at 190 ° C. and immediately cooled in a water-cooled press and processed in this way into test samples. These test specimens are then used to determine the Vicat softening point, hardness, Izod impact strength, tensile strength and transparency. The results obtained are summarized in Table I below. For comparison purposes, the same tests on polyvinyl chloride (commercially available under the name "Kureha S901 ^M" ), resins obtained by mixing this polyvinyl chloride with chlorinated polyethylene (available from Showa Denko KK under the trade name "Elaslen"), the 30 % Chlorine, an acrylonitrile-butadiene-styrene resin (manufactured and sold under the name "Kaneace" by Kanegafuchi Kagaku KK) and a polycyanonorbonene. The results obtained here are also summarized in Table I below.

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Table I.

Mix ratio (weight
tetlo)., _____ PCM < ² > CPE ^ί3) - Vicat extension
point of interest toughness HMrte Zucf firm
ability - transparency I.
M. example 1 PVC * ¹ 20th - (° 0) at notch
ter sample
(kg * cm / cm) (kg / W) Well CO
I. 2 80 40 - 127 1/5 116 530 Well 3 60 60 122 2.3 119 540 Well 4th 40 80 - 115 2.3 120 530 Well yGrglexcns-
VJ * - ■ - - ^ L £ ^ β U, H. C ^ -, η-.
1 20th « - 96 2.3 121 540 Well O 2 100 loo 20th 91 0.8 115 540 Well 3 _ - 20th 133 2.3 122 510 impenetrable
sighted 4th 80 85 '12.5 108 370 Well
—Τ! 80 86 11, 0 101 460

(1) polyvinyl chloride

(2) polycyanonorbonene

(3) Chlorinated polyethylene

(4) Aerylrtitiril Butadlene Styrene Resin (ABS Resin)

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Eelsole1 5 100 parts by weight of the in Example are kneaded

1 specified process from 5-cyano-Μσγσ1ο / "2.2. | / Heoten-2 polymer produced by ring-opening polymerisation with 20 parts by weight of polystyrene (produced and sold by Japan Polystyrene Mfg.Co. under the name" Esbrite ") with a melt -Viscosity of 1.2 χ 10 poise, an Izodh impact strength for a notched specimen of 10 kgcm / cm, a Vieat softening point of 78.9 ⁰ C and a Rockwell hardness (R) of 118 and 0.5 parts by weight bis ( 2-hydroxy-3-tert-butyl-5-methylphenyl) methane as a stabilizer for 5 minutes on a mixing roller mill heated to 175 ° C. The mixture obtained in this way is heated for 3 minutes at 200 ° C. and a pressure of

100 kg / cm and then for 3 minutes at a pressure of

100 kg / cm pressed in a water-cooled press to form a plate with a thickness of 3 mm. This plate has an impact strength with a notched * »robe of 3.3 kg · cm / cm and a rock: well hardness (R) of 12Ο. The above mixture has a melt viscosity of 3.0 10 poise and a Vicat softening point of 't 21 ⁹ C-.

Example 6

The same mixture as that described in Example 5 is prepared using the same procedures on a hot roll mixer with the difference that polystyrene is added in a menu of 50 parts by weight. The mixture is then as described in Example 5, pressed in a hot press and a press cooled with water to form a plate. The as a product Accruing plate has an iζodine impact strength with notched Sample of 2 "4 kg ° cm / cm and a Rockwell hardness (R) of 12O" -Die

4 The above mixture shows a melt viscosity of 1.6 10 poise

and a Vicat softening point of 114 ° C. Example 7

In the same way as described in Example 5, one puts under Use of an Ilcißwalzenmischwerk the mixture described there

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-3O-

with the difference that polystyrene is used in an amount of 100 parts by weight. The mixture is then as described in Example 5 _r, a heat press and a, water-cooled press to pressed by means of a plate. The plastic has an Izod impact strength in a notched specimen of - ,,. 1.4 kg - cm / cm and a Rockwell hardness (R) of 122. The mixture described above shows a Sehmelz viscosity of 6.5 χ 10 poise and a Vicat softening point of 99 ° C. ^. .. "

Example 8 -, -.-, · -. - ^ v

In the same way as described in Example 5, the mixture of Example 5 is prepared using a hot roller mixer. here, with the difference that one used in Example 5, 20 parts by weight of polystyrene by 15 parts by weight of polystyrene. (manufactured and sold by Japan Polystyrene Mfg.Co.

under the name "Esbrite * 4") with a Sehmelz viscosity

from 3.00 10 poise, an Izod impact strength with notched _; Sample of 1.6 kg ^e cm / cm, a Vicat softening point of 93.2 C and a Rockwell hardness (R) of 120, replaced. The mixture is then pressed into a plate in a hot press and a water-cooled press, as described in Example 5. The plate has an 'Izod notched specimen impact strength of 3.6 kg-cm / cm and a Rockwell hardness (R) of 122. The aforesaid

5 '"■ mixture has a melt viscosity of 2.8 χ 10 poise and

a "Vicat softening point of 123 C.

Example 9

In the same way as described in Example 5, does Raan produce the mixture described in Example 5 using a hot roller mixer _{? e} with the difference that the 20 parts by weight used in. Example 5 polystyrene produced by 30 parts by weight of polystyrene (and sold by.

Japan Polystyrene Mfg "Co". under the name "Esbrite * 8" $ with

a Sehmelz viscosity of 3.2 10 poise, an Izod impact strength with a notched sample of 1.1 kg ° cm / cm, a Vicat

Softening point of 99 ^ O ° C and a Rockwell hardness (R) of 119 replaced. The mixture is then made using a hot press

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and a water-cooled press, as described in Example 5, 2TU pressed on a plate. The plate has an Izod impact strength for a notched sample of 3.0 kg * cm / cm, a "Rockwell hardness" (R) of 123. The above mixture shows a melt viscosity of 5.0 10 poise and a Vicat softening point of 122 ° C.

Ice cream 1O

In the same way as described in Example 5, using a hot roller mixer, the mixture given in Example 5 is prepared, with the difference that the 20 parts by weight of polystyrene used there are replaced by 20 parts by weight of a methyl methacrylate resin {manufactured by Mitsubishi Rayon Mfσ «Co. under the name "Acrypet M * 001 ⁿ ) , which has a Sctrnelz viscosity of 2.75 10 poise, an Izod impact strength for a notched sample of 1.1 kg-cm / cm, a Vicat softening point of 9 8 ° C and a Rockwell hardness (R) of 132. The mixture is then pressed with the aid of a hot press and a water-cooled press to form a plate, as described in Example 5. The plate has a zod impact strength with a notched specimen of 4.1 kg ° cm / cm and a Rockwell hardness (R) of

127. The mixture described above has a melt viscose-

■ "■■■ - 5
tat of 3.5 χ 10 poise and a Vicat adult point of

Example 11

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 there are produced by 20 parts by weight of an acrylonitrile-styrene mixed polymer! And sold by the company Asahi Dow chemistries! Coninany under the name "Tyril 767 '°), which contains 23% by weight of acrylonitrile and a melt viscosity of 3.0 10 poise, an Izod impact strength for a notched sample of Ij ₇ S kg" cm / cm Vicat softening point of 96 ^ 2 ⁰ C and a Rockwell hardness (R) of 122 »The mixture is then _f . as described in example 5,

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-Sl-

with the help of a hot press and a water-cooled press pressed into a plate. The plate has an Izod impact strength with a notched sample of 3.5 kg · cm / cm and a Rockwell hardness (R) of 123. The mixture mentioned shows a melt viscosity of 3.6 10 poise and a Vicat softening point of 124 ° C.

Example 12

A 500 ml stainless steel autoclave is charged, the equipped with an electromagnetic stirrer, with 400 ml of water, 6 g of Tricalciunrahosphat and 0.03 g of the sodium salt of Dodecylbenzenesulfonic acid and stir the materials well. The autoclave is then charged with a separately prepared one Solution of a mixture of 92 α methyl methacrylate, 108 g monomeric styrene, 0.6 g tert.-3utylr> eroxybenzoate and 2.0 g tert.-dodecyl mercantan, whereupon the autoclave with nitrogen gas

SOÜlt.

The reactants are then initially polymerized during 3 hours at 120 ° C and then for 2 hours at 140 ° C. After cooling, the polymer beads are removed. the Polymerizatkürielchen are stirred with 1 1 of a aqueous hydrochloric acid solution, the 5 g Contains 25% hydrochloric acid. After washing well with The polymer beads are dried in water for 24 hours at 60 ° C. in a vacuum dryer, 185 g of the polymer being obtained, The polymer consists of a methyl methacrylate-styrene copolymer, containing 46% by weight methyl methacrylate. The copolymer has a melt viscosity of 4.81 χ 10 poise, an Izod impact strength on a notched specimen of 1.3 kg * cm / cm, a Vicat softening point of 90.3 C and a Rockwell hardness (R) of 121.

It is then prepared in the same manner as described in Example 5 the mixture given there, with the difference that the 20 parts by weight of polystyrene used according to Example 5 by 30 parts by weight of the above methyl methacrylate styrene

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Copolymer replaced. The mixture is then, as in example 5, pressed with the aid of a hot press and a water-cooled press to form a plate. The plate owns an Izod impact strength on 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 poise and a Vicat softening point of 122 ° C.

Example 13

The polymerization is effected in the same way as described in Bei-SOiel 12, with the difference that instead of the solution of the mixed constituents that was used to prepare the methyl methacrylate copolymer, a mixture of 110 g of styrene, 40 g of acrylonitrile, 50 g of methyl methacrylate, 0.6 g of tert-butyl peroxybenzoate and 2.5 g of tert-butyl mercaptan are used. After the end of the polymerization, the aftertreatment is carried out in the same way as described in Example 12, with nan receiving 165 g of polymer beads. The polymer consists of an acrylonitrile-styrene-methyl methacrylate polymer which contains 20% by weight of acrylonitrile, 55% by weight of styrene and 25% by weight of methyl methacrylate. The terpolymer has a melt viscosity of 3.03 χ 10 poise, an Izod impact strength for a notched specimen of 1.2 kg · cm / cm, a Vic,
121

Vicat softening point of 93 ° C and a Rockwell hardness (R) of

The mixture is then prepared in the same way as described in Example 5, with the difference that the there used 20 parts by weight of polystyrene by 20 parts by weight of the above. Acrylonitrile-styrene - methyl methacrylate teroolymerizate replaced. The mixture is then, as described in Example 5, using a hot press and a water-cooled press Press formed into a plate. The plate has an Izod impact strength on a notched specimen of 3.1 kg · cm / cm and a Rockwell hardness (R) of 122. The above mixture shows a melt viscosity of 3.5 10 poise and a Vicat softening point from 123 C.

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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-Cvano-bicYclo / "2.2.1 / heoten-2 used in Example 5 is replaced by the same number of moles (1332 g ) S-cyano-S-methyl-bicyclo- £ 2. 2.1 / hepten-2. After the end of the ring-opening polymerization, the purification is carried out, which gives 1100 g of the polymer material. This polymerizer product has an intrinsic viscosity of 0. 77, an 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 10 poise .

In the same way as described in Example 5, the mixture there is then operated using one operated at 190.degree Hot roller mixer produced, with the difference that one instead of that used in Example 5, by ring-opening polymerization of 5-cyano-bicyclo / 2.2.1.7henten-2 produced polymer, that described above, similarly by ring-opening polymerization from S-cyano-S-methyl-bicyclo / S. 2.1Jhepten-2 produced polymer used. The mixture obtained in this way is then, as described in Example 5, with the aid processed into a plate using a hot press and a water-cooled press. The plate has an Izod impact strength with a notched specimen of 4.1 kq-cm / cm and a Rockwell hardness (R) of 125. The above mixture shows a melt viscosity of 3.6 10 poise and a Vicat softening instinct of 142 ° C.

Example 15

In the same way as described in example 14, the same mixture is produced, with the difference that instead of the in Example 14, 20 parts by weight of polystyrene used 20 parts by weight of the methyl methacrylate resin used in Example 10 begins. The mixture is then, as described in Example 14, using a hot press and a water-cooled press Press processed into a plate. The plate has a 2 Izod impact strength with a notched sample of 4.2 kg * cm / cn and one

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Rockwell hardness (R) of 124. The above mixture shows an enamel Viscosity of 7.0 χ 10 poise and a Vicat softening point of 142 ° C.

Example 16

As described in Example 14, using a HeiQwalzenmischwerk produces the mixture there, with the difference that the 20 parts by weight of polystyrene used in Example 14 by 20 parts by weight of that used in Example 11 Acrylonitrile-styrene copolymer replaced. The mixture is then, as described in Example 14, using a hot press and formed into a plate using a water-cooled press. The plate has an Izod impact strength on a notched specimen of 3.9 kg * cr> / cm and a Rockwell hardness (R) of 125. The above Mixture shows a melt viscosity of 7.1 χ 10 poise and a Vicat softening point of 144 C. ..-

Example 17

In the same way as described in example 14, the Mixture there, with the difference that the example is close 14 used 20 parts by weight of polystyrene by 20 parts by weight of the methyl methacrylate-Stvrol-Mischnolyaerisats used according to Example 12 replaced. The mixture is then, as described in Example 14, with the aid of a hot press and a deformed into a plate using a water-cooled press. The plate owns an Izod impact strength on a notched specimen of 3.7 kci-cm./cm and a lockwell hardness (R) of 124. The above mixture shows a melt viscosity of 7.9 χ 10 poise and a Vicat softening point of 143 ° C.

Example 18

performs the ring-opening polymerization in the same way as in Example 5 described by, with the difference that instead of the 12 mol of 5-cyano-bicyclo described in Example 5 /2.2.l/hepten-2 10 Hol (1192 g) B-cyano-bicyclo / ^. 2. i7hepten-2 and 2 mol (188 g) bicyclo / 2.2.i7hepten-2 (norbonen) are used. After loading

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At the end of the ring-opening polymerization, cleaning takes place in the same way as in Example 5, where nan 1164 g of the copolymer is obtained. The copolymer obtained as a 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 5.70 χ 10 poise.

Then knead the materials in the same way as in example 5 described, with the difference that that used in Example 5, by channel opening polymerization of S-Cyano-bicyclo / ä ^. 1./hepten-2 produced polymer by the Replaces the above copolymer, which is produced by ring-opening polymerization from S-Cyano-bicyclö / Ä. 2.1./her>ten-2 and Bicylco /2.2.i7henten-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 on notched specimen of 3.4 kg * cm / cm and a Rockwell hardness (R) of 117. The above The mixture has a melt viscosity of 1.05 χ 10 poise and a Vicat softening point of 116 C.

Example 19

Min kneads 80 parts by weight of the ring-opening polymerization according to the process described in Example 5 from 5-cyanobicyclo / 2.2.1_7henten-2 obtained polymer with 20 parts by weight of an acrylonitrile-butadiene-styrene terpolymer (available and sold by Toray Industries, Inc. under the designation "Toyolac 100") having an Izod impact strength for a notched sample of 28.5 kg-cm / cm, a Rockwell hardness (R) of 105 and an aa Vicat softening point of 112 ° C, and 0.5 part by weight Bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane as a stabilizer on a hot roller mixer, using the procedure given in Example 5. The kneaded Mixture is then, as described in Example 5, using a hot press and a water-cooled press to form one

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Pressed plate with a thickness of 3 mm. The plate has an Izod notched impact strength at ^ü robe of 30, 5 kg cra / 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 described in Example 19, 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 S-cyano- bicyclo / ^^. Ij henten-2 produced polymer is used. The kneaded mixture is pressed as described in Example 19 in the heat and cold to form a plate. The plate has an Izod impact strength on a notched specimen of 28.5 kg · cm / cm, a

Vica

Vicat softening point of 127c and a Rockwell hardness (R) of

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 a mente of 70 parts by weight and the by .Rn Rinaöf tion polymer is ation from S-cyano-bicyclo / ^. 2.1.7hepten-2 produced polymer can be used in an amount of 30 parts by weight. As described in the example, the kneaded mixture is crushed in the heat and in the cold to form a plate. The plate has an Izod impact strength for a notched specimen 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 takes place in the same way as described in Example 19, with the difference that, instead of that used in Example 19, 20 parts by weight of Acrylonitrile-butadiene-styrene ternpolymer is a ternpolymer

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is used, which has been obtained by grafting Stvrol and acrylonitrile onto chlorinated polyethylene (manufactured and sold by Showa Denko KK under the name "NF-920"), which has an Izod impact strength for a notched sample of 12.0 kg · cm / cm, a Rockwell hardness (R) of 104 and a Vicat softening point of 90 ^° C. to v / eist. The kneaded mixture is, as described in Example 19, pressed in the heat and in the cold to form a plate. The plate has an Izod

Vicat softening point of 125 ° C and a Rockwell hardness (R)

Notched specimen impact strength of 21.0 kg "cm / cm", one

Vicat-En

from 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 polymer used in Example 19 is used replaced by a terpolymer made by grafting styrene and acrylonitrile onto an acrylic ester rubber (manufactured and sold by Hitachi Chemical Co, under the designation "Vitax-V-6101") and that is, an Izod impact strength on a notched specimen 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 in the cold pressed on a plate. The plate has an Izod impact strength for a 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 the acrylonitrile-butadiene-styrene terpolymer used in Example 19 is used replaced by a terpolymer, which is replaced by Grafting of styrene and acrylonitrile onto an ethylene-propylene rubber (manufactured and sold by Toray Industries, Inc. under the designation "WH-1000") and that is, an Izod impact strength on a notched specimen of

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9.3 kg · cm / cm, having a Rockwell hardness (R) of 110 and a Vicat Erveichungsnunkt of 104 ⁰ C. As described in Example 19, the kneaded hybrid is crushed in the heat and in the cold to form a sheet. The plate has an Izod impact strength on a notched specimen of 15.4 kg · cm / cm, a Vicat softening point of 127 ° C. and a Rockwell hardness (R) of 120.

Example 25

The kneading takes place, as described in Example 19, on a hot roller mixer, with the difference that according to the example 19 used acrylonitrile-3utadiene-styrene terpolymer is replaced by Gin Temolymerisat, which is grafted on of styrene and methyl methacrylate on butadiene rubber (manufactured and sold by Toray Industries, Inc. under the name "Toyolac 900") and an Izod impact strength for a notched sample of 15.2 ka · cm / cm, a Rockwell hardness (R) of 99 and a Vicat Softening Point of 106C. The kneaded mixture is then deformed into a plate in the hot and in the cold, the same as that given in Example 19 Procedure applies. The sheet has an Izod impact strength for a notched sample of 19.3 kg * cm / cm, a Vicat softening point of 126 ° C and a Rockwe11 hardness (R) of 119.

Example 26

A 1 liter autoclave is charged with 125 ml of distilled water, 125 ml of a 2% strength aqueous polyvinyl alcohol solution, 5 g of tricalcium phosphate and 0.025 g of the sodium salt of dodccylbenzenesulfonic acid, after which 40 g of chlorinated polyethylene with a chlorine content of 40% by weight are added. The imported materials are mixed at the cut room temperature. Then the autoclave is still charged with a mixture of 104 g of methylnothacrylite and 5 g of styrene in which 0.32 g of tert-butyl peroxyacetate and 0.48 g of tert-dodecyl mercaptan have been dissolved. After having filled nan the gas space of the autoclave with nitrogen, it causes the first copolymerization for 4 hours at 105 ⁰ C and finally for 2 hours at 145 ° C.

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After the mixed polymerization has ended, Tnan washes the product with an aqueous solution of hydrochloric acid and then with water and dry it overnight in vacuo at 50 C. In this case results in a yield of the copolymer product of 99.5%. The product consists of relatively coarse particles. The graft copolymer has an Izod impact strength for a notched sample of 32.3 kg "cra / cm, a Vicat softening point of 103 ° C and a Rockwell hardness (R) of 101.

Then knead the materials in the same way as in the example 19 described, with the difference that instead of the acrylonitrile-butadiene-styrene polymer used there the graft copolymer obtained by the above process (Ternalyrnerisat) is used. The kneaded mixture will be like described in Example 19, pressed in the heat and in the cold to form a plate. The plate has an Izod impact strength Shark notched sample of 29.3 kg'cra / cm, a Vicat softening grade > okt of 124 ° C and a Rockwell hardness (P) of 121.

Example 27

M = in causes kneading on a hot roller mixer in the same way as indicated in example 19, with the difference that the acrylonitrile-butadiene-styrene-olefin used in example 19 is replaced by a graft copolymer which nan obtained by applying styrene to a butadiene rubber (manufactured and sold by Japan Polystyrene Mfg.Co. under the name "Esbrite 500A") and having an Izod impact strength on a notched specimen of 12.2 kg · cm / cm, has an "ockwell (R) hardness (R)" of 119 and a Vicat softening point of 79.1 ° C. The kneaded mixture is, as indicated in the example, 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-an / cn, a Vicat softening point of 120 ^° C. and a Rockwell hardness (R) of 120.

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Example 23

It is kneaded, as described in Example 19, on a hot roller mixer 30 parts by weight of an impact-resistant mixture of 5 parts by weight of polybutadiene rubber (manufactured and sold from Janan, Synthetic Rubber Mfg.Co. under the name "BR-01") and 25 parts by weight of an acrylonitrile-styrene copolymer (manufactured and sold by Asahi Dow Chemical Company under the designation "Tyril 767") at 70 parts by weight that according to Example 19 by ring-opening polymerization from S-Cyano-bicyclo / ä ^. 1_ / hepten-2 produced polymer. The kneaded mixture is, in the same way as indicated in Example 19, in the heat and in the cold to one Plate pressed. The plate has an Izod impact strength at notched sample of 19.5 kg * cm / cm, a Vicat softening element of 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 Way as described in Example 28, with the difference that the impact-resistant product used in Example 28 through a Replaced impact-resistant product made from 5 parts by weight of a butadiene-acrylonitrile copolymer (manufactured and sold from Japan Geon Co. under the designation "Hycar 1042") and 25 parts by weight of polystyrene (manufactured and sold by of Japan Polystyrene Mfg.Co. under the name "Esbrite * 2") consists. 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 for 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

The kneading is carried out on the hot roller mixer in the same way Orphan as described in Example 28, with the difference that Tan instead of the impact-resistant product used in Example 28 another high impact product used, that of 5 parts by weight

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chlorinated polyethylene / containing 40% by weight of chlorine (manufactured and distributed by Showa Denko K.K. under the Designation "Elaslen 401A") and 25 parts by weight of an acrylonitrile-gtyrene mixed polymer (manufactured and sold by Asahi Dow Chemical Company under the designation "Tyril 767") consists. The kneaded mixture is pressed in the heat and then in the cold to form a plate, the example applies the procedure described. The plate has an Izod impact strength for a notched specimen of 19/3 kg * cm / cm, 'one

Vicat-Er ^ of 119.

Vicat softening point of 122 C and a Rockwell hardness (R)

Example 31

In the same way as described in Example 28, kneading takes place on a hot roller mixer, with the difference that the impact-resistant product used in Example 28 is replaced by another impact-resistant product which is composed of 7 parts by weight of the polybutadiene rubber used in 3eisniel 28 and 23 parts by weight of a methyl methacrylate-Stvrol mixed polymer consists, which contains 46% by weight of methyl methacrylate. The kneaded mixture is then, as described in Example 28, squeezed into a plate in the heat and in the cold. The plate has an Izod impact strength with a notched specimen of 20.2 kg · cm / cn, a Vicat softening point of 121 C and a Rockwell hardness (R) of 121.

Example 32

In the same way as in Example 28, a kneaded mixture is prepared using a hot roller mixer, with the The difference is that instead of the 30 'parts by weight of the impact-resistant product used in Example 28, 50 parts by weight of a impact resistant product used, which consists of 15 parts by weight of the according to Example 23 used polybutadiene and 35 parts by weight of the acrylonitrile-styrene copolymer used according to Example 28 and 5O parts by weight of the according to Example by ring-opening polymerization of 5-cyano-bicyclo / '2.2.1 / hepten-2 prepared polymer kneaded. The kneaded

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Mixture is then, as described in Example 28, wassed in the heat and in the cold to form a plate. The plate has an Izod impact strength for a notched specimen of 43.9 kg · cm / cm, a Vicat softening point of 116 ° C. and a Rockwell hardness (R) of 115.

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 mixed polymer of Example 30 consists. The kneaded mixture is, as described in Example 33, in the heat and in the Cold wears away to a plate. The plate has an Izod

Vicat soft point of 132 ° C and a Rockwell hardness (R)

Notched specimen impact strength of 73.5 kg-cm / cm, one

Vicat-F.r *

from 120.

Example 34

The knotting 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 impact-resistant product made from 5 parts by weight of an acrylic ester rubber (manufactured and sold by Janan Zeon Company under the designation "Hycar 4021") and 25 parts by weight of the acrylonitrile-styrene mixture used in Example 28. The kneaded mixture is, as described in Example 28, in the heat and in the cold to form a ^p .latto vcrr> re "t Vicat calibration point of 122 C and sine 'Rockwell hardness (R) of 119.

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- 44-BeiSOiel 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 only. 2.1.7hepten-2 produced polymer by the according to Example 14 by ring opening polymerization from S-cyano-S-nethyl-bicyclo / ^^. 1_7hePten-2 produced polymer replaced. The kneaded mixture is pressed in the heat and then in the cold, in the same manner as described in Example 19, su a plate. The plate has an Izod impact strength for 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 the terpolymer used in Example 22 is used instead of the acrylonitrile-butadiene-styrene polymer used in Example 35. The kneaded mixture is pressed into a plate while hot and then cold, 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

Using a hot roller mixer according to the A kneaded mixture was prepared using the procedure of Example 35, except that the one used in Example 35 was used instead 20 parts by weight of the acrylonitrile-butadiene-styrene terpolymer 30 parts by weight of an impact-resistant product used that consists of 7 parts by weight 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 the according to Example 35 by ring-opening polymerization

. 2. i / her> ten-2 produced polymer

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be kneaded. The kneaded mixture becomes one in the heat and then in the cold as described in Example 35 Plate pressed. The plate has an Izod impact strength for a notched sample of 24.1 kg · cm / cm, a Vicat softening point of 135 ° C and - a Rockwell hardness (R) of 120.

ι -

Example 38

The kneading takes place on a hot roller machine i-n the same Way as described in Example 19, with the difference that the one used in Example 19, by ring-opening polymerization from S-Cyano-bicyclo / Ä. 2. i7het> ten-2 produced polymer by the according to Example 18 by ring-opening polymerization from 5-cyano-bicyclo / 2. 2.1_ / henten-2 and bicyclo / 2.2.1 / hepten-2 produced copolymer replaced. The kneaded mixture is, as described in Example 19, pressed in the heat and in the cold to form a plate. The plate has an Izod impact strength with a notched sample of 13.5 kgcm / cm, a Vicat softening skin of 116 ° C and a Rockwell hardness (R) from 122.

5 0 9 8 1 7/1 U 3

Claims (1)

1. Resin composition containing 5 to 95 parts by weight by ring-opening polymerization of cyano-substituted norbonen derivatives of the general formula in the V1, 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, aralkyl groups with 1 to 20 carbon atoms and / or aralkyl groups with 1 to 20 carbon atoms mean, with the proviso that at least one of the groups W, X, Y and Z means a nitrile group and / or a substituent containing a nitrile group, polymers obtained and 95 to 5 parts by weight of homopolymers and / or copolymers of vinyl chloride. 2. Resin composition / containing 5 to 95 parts by weight by ring-opening polymerization of cyan-substituted morbon derivatives of the general formula 509817/1143 24U840 in the W, X, Y and Z hydrogen atoms, nitrile groups, nitrile equipoene containing substituents, alkyl groups with 1 to 20 carbon atoms, Alkyl groups with 1 to 20 carbon atoms, aryl groups with 1 to 20 carbon atoms and / or aralkyl groups with 1 to 20 carbon atoms, with the proviso that at least one of the groups W, X, Y and Z is a Nitrilgrutjpe and / or one containing a nitrile greenpe Substituents means polymers obtained and 9-5 to 5 parts by weight of styrene homopolymers and / or vinyl mixed polymers, the at least 50% by weight of at least one vinyl compound such as styrene, acrylonitrile and / or methyl methacrylate. 3. Resin composition containing 5 to 95 parts by weight by ring opening polymerization of cvan-substituted norbonen derivatives of the general formula , T in the W, X, Y and Z hydrogen atoms, nitrile green, nitrile green containing substituents, alkyl green with 1 to 20 carbon atoms, alkenyl green with 1 to 20 carbon atoms, aryl green with 1 to 20 carbon atoms and / or aralkyl group with 1 to 20 carbon atoms, with Provided that at least one of the greens ^{v <} 7, X, Y and Z denotes a nitrile green and / or a substituent containing a nitrile green, obtained "olymerisate and 95 to 5 parts by weight by Aufnfronfen at least one vinyl compound such as styrene, acrylonitrile and / or methyl methacrylate on at least one elastomer, such as a butadiene rubber, an acrylic ester rubber, a chlorinated polyethylene and / or a Sthvlen-Pronvlen rubber, ffroof copolymers obtained. 509817/1143 24H840 4i resin composition according to claim 2, characterized in that the styrene homopolymers and / or Vinyl mixed polymers at least one elastomer, such as a butadiene rubber, an acrylic ester rubber contain chlorinated polyethylene and / or an ethylene-propylene rubber. 5. resin composition according to claim 2, characterized in that that they consist of 60 to 95 parts by weight of the ring-opening polymerization of cyano-substituted norbonene derivatives obtained polymers and 40 to 5 parts by weight of styrene homopolymers and / or vinyl copolymers consists. 6. resin composition according to claims 1 to 4, characterized in that that it contains copolymers as polymers obtained by ring-opening polymerization, that by ring-opening polymerization, the other is cycloolefinic Compounds containing cyano-substituted norbonen derivatives were obtained. 7. Resin composition according to claim 6, characterized in that irtonocyclische than other cycloolefinic compounds olefins, non-konjucrierte cyclopolyenes "riorbonenesterder ivate, Morbonenätherderivate ·, Norbonens Sureanhydridderivate, florbonenimidderivate _r aromatic norbornene derivatives _T · iJorbonenhalogenderivate and / or bicyclo / 2.2. iJ ^ hepten-2 are included. δο resin composition according to claim!, characterized in that that as vinyl chloride copolymers vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, Contain vinyl chloride-propylene copolymers and / or vinyl chloride-vinyl ether copolymers are. 9. resin composition according to claim 2, characterized gekenrt- indicates that as vinyl copolymers acrylonitrile-Stvrol copolymers, Methyl methacrylate-styrene mixed poly- 5098 17/1143 24U840 _ 49 - merisate, methyl methacrylate copolymers, the predominantly consist of methyl methacrylate, and / or acrylonitrile-styrene-methyl methacrylate terpolymers are included. TO. Resin composition according to claim 3, characterized in that that as elastomers butadiene rubbers, Styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, Acrylic ester-acrylonitrile copolymers, chlorinated ethylene co-polymers, chlorinated ethylene-o (-olefin copolymers, Ethylene-propylene rubbers and / or ethylene-propylene terpolymers are included. 11. Resin composition according to claim 4, characterized in that butadiene rubbers as elastomers, Styrene-butadiene rubbers, acrylonitrile-butadiene rubbers, Acrylic ester-acrylonitrile copolymers, chlorinated ethylene homo-polymers, chlorinated ethylene ot-olefin copolymers, Ethylene-propylene rubbers and / or ethylene-propylene terpolymers are included. 509817/1 143