METHOD OF PRODUCTION OF POLYMERS AND COPOLYMERS OF CYCLOALKENE OF NORBORNENE TYPE

Abstract: Method of metathetical polymerization and copolymerization of cycloalkenes of norbornene type in the presence of catalytic system which is comprised of a) a catalytic precursor prepared by reaction of a tungsten compound containing at least one atom of chlorine, bromine and/or iodine with sterically hindered amines, whereby concentration of the tungsten is 0.01 to 50 milimols per mol of monomer and molar ratio of tungsten/amine is 0.01 to 1:5, b) cocatalyst selected from the group of organic compounds of aluminium, tin, lead, silicon, lithium, magnesium, boron, zinc or germanium, whereby molar ratio tungsten/cocatalyst is 1:1 to 1:20 and possibly, c) moderator of the polymerization reaction selected from the group of ethers, esters, ketons or nitriles in mole ratio cocatalyst/moderator 1:1 to 1:10.

Description: METHOD OF PRODUCTION OF POLYMERS AND COPOLYMERS op CYCLOALKENE OF NORBORNENE TYPE FIEIJ) OF THE ABI The invention relates to metathetical polymerisation f cyclσalkenes σl nσrbσrnene type by catalysts based on tungsten compounds during injection moulding by RIM (Reaction Injection Moulding) method. STftTE OF THE ART Patent speci ications US 4,400.340 and US 4,426.502 disclose metathetical polymerization of cyclσalkenes by ring opening by the action of catalytic system containing transition metal. By mixing two streams, of which the firs contains catalyst and the Beσσnd the σσcatalyst, cross-linked polymer is obtained containing double bonds in the chain. As catalytic components of the metathet ically polymerizing system compounds based on halogenides and oxyhalogenides of tungsten, molybdenum, tantalum or rhenium and tetraalkyl- ammσnium salts of tungsten and molybdenum a.re uped. Tungsten and molybdenum salts are preferred, especially WClβ and WOCI 4 . But such halides of a transition metals, if added to the mixture of metathetically polymerized monomers, initiate very rapid cationic polymerization. Therefore, they must be in advance suspended in an inert solvent and solubilized by the addition of alcoholic and phenolic compound (called also modifiers) . Thereby, their activity is decreased. As solvent benzene, toluene, chlσrobenzene, dichlorσbenzene, etc. 3.r-*≡ used as solvents. Suitable phenolic compounds are phenol, halσgenated phenolo and alkylphenols, especially tert--butylphenσl , tert--σctyl ~ phenσl and nσnylphenol. Molar ratio [tungsten compound] / [phenolic compound] ranges from 1:1 to 1:3. Phenolic componen is added to the suspension of tungsten compound in organic solvent. Reaction is carried under mixing and bubbling by a stream of inert gas to remσ-'e the HC1 being formed . Alternatively, also phenolic sa.lt can be used, e.g. Li- or Na- phenσxide and the formed inorganic compound is filtered off or centi-i uged. All such operations have to be carried out in the absence of air and moisture i o prevent deactivation of catalys (US 4,507.453, US 4,469.809) . Patent sspecificatiσn EP 304 900 discloses the use of 2, 6-dihalo— 4-alkyl henol, where the alkyl group contains 1 to 18 carbon atoms; especially suitable is 2, G— ibrσmo-4—alkylphenσl with 1 to 12 carbon atoms containing alkyl. The catalytic WCle and 0Cl_ι mixture shows high activity and polymerization proceeds very rapidly. Ratio of WC1© to WOCI4 in the range from 9:1 to 1: 3 is used. To prevent premature reaction of the catalytic precursor with the monomer that forms the first component of the poly¬ merization system, it is necessary to use an inhibitor. Inhibitors are chelating agents or Lewis bases as e.g. acetylacetσne, alkylesters, tetrahydrofuran, benzσnitrile, etc. in the amount 1 to 5 mσl/mol of tungsten compound. As cocatalyBts in the metathetical polymerization organσmetalic compounds are used, i.e. alkyls of metals of the I - III group of the periodic system, especially alkyl ompounds of aluminium, tin, eilicσn and zinc. The cocatalyst is dissolved in the norbornene hydrocarbon and forms the second reaction solution. Patent specifications EP 222 432 and EP 336 486 disclose polymerization of dicyclσpentadiene by means of a ca.talytic system containing: a) tungsten compound of the general formula where X is chlorine, R is alkyl group or hydrogen, R 1 is alkylgroup with 1 to 10 hydrocarbon atoms or hydrogen. b) compound of the general formula R2 M ■ H 2 where M is tin or silicon, R 2 is alkyl group containing 1 - 10 carbon atoms . or phenyl. In contradiction to organoaluminium compounds, this compound is substantially less sensitive to the oxygen presence. This means that it is not necessary to work with it in an inert atmosphere. Polymer is obtained by blending two reaction solutions. The former contains monomer, catalytic precursor and inhibitor and the latter monomer and cσσatalyst. As blending of both solutions results in instantaneous polymerization, what ie not desirable in case of RIM equipment application, a so called modifier is added to the latter solution. Usually Lewis bases, e.g. ethers, esters, nitriles, etc. are used (EP 280 247). E.g., EP 259 215 describes polymerisation without the use of moderator. The induction period of this catalytic system can fluctuate in the range 1 - 20 minutes, what is being technologically optimal. Patent specification EP 385 274 discloses as catalyst tungsten compound of the general formula. where X is chlorine ΌΪ- bromine, n =■- 2 or 3, R 1 is alkyl group having 1 — 10 hydrocarbon atoms, alkσxy group having 1 — 8 hydrocarbon atoms or phenyl, hydrocarbon or chlorine; B 2 is alkyl group having 1 ' - 10 aluminium atoms or hydrogen and B 3 is alkyl group having 1 — 10 hydrocarbon atoms or hydrogen. From the mixture of tungsten compounds reacted to different degree the one is separated that is stable in the air. But this operation is considered as a complication and results in losses of tungsten compound. The σrganometallic compound used in this case is tributyltinhydride. The disclosed phenolic modifiers are well applicable in the polymerization of norbσrnenic monomers, but owing to small differences in chemical structure they do not allow greater modification of catalytic system properties. Catalysts based on not modified tungsten compounds polymeri ¬ ze the monomer at a high rate what is technologically un- desirable. Modified cata.lysts based on WCle, where chlorine is substituted by phenolic compound in a low degree, are sufficiently active in polymerization, but they form soJu- tions of low stability with monomer and easily react also with atmospheric oxygen, this being accompanied by deactivatiσn. If reaction with a phenolic derivative is carried out up to the higher degree by using higher ratio of the phenolic compound to WCle , catalyst stability is increased but at the same time also its activity is decreased. In an extreme case, when WCle is reacted to such a degree that the resulting product is in reality inert to atmospheric oxygen, decrease in the activity is so high that it results in substantial deterioration of polymeric- material properties. Now, it has been surprisingly found that sterically hindered amines that form nitroxile radicals and are called by the abbreviation HALS (Hindered Amine Light Stabilizer) of general formula where B 1-4 are identical or different alkyl groups with 1 - 6 hydrocarbon atoms; B» is OH, COOH, CN, NHR . NR R", CONHR (where B and B" are alkyls with 1 to 18 carbon atoms) r heterocycle with N, 0 or S in ring; R 6 can be hydrogen σr chemical bond connected with R 5 to a heterocycle; W is hydrogen, alkyl group with 1 to 18 carbon atoms or mono- ethylsuccinyl, where X is , S, NB or CO; R 1-2 are identical or different alkyl groups with 1 — 6 carbon atoms; R 7 is hydrocarbon, alkylgroup with 1 to 18 carbon atoms or monσethylsuccinyl, where X is O, S, NB or CO; R*~ 4 are identical or different alkyl groups with 1 to 6 ca-rbon atoms; R 5 ' 6 are hydrocarbon atoms, groups COOB, NHB, NBR- , CN, OH, CONHR (where R and R' are alkyls with 1 to 18 carbon atoms) or heterσcycles with O, S, N in ring and R 7 is hydrocarbon, alkylgroup with 1 to 18 hydrocarbon atoms or monσethylsuccinyl, 3.r<a very advantageous modifiers as they remove a. number of existing technological problems. Syfoiegfr of frhg -juiven ion Subject of the invention is a method of metathetical poly¬ merization of cycloσlefins of norbornene type by the appli¬ cation of sterically hindered amines as modifiers of the catalytic tungsten compounds. The subject matter of this invention consists in that at least one monomer containing at least one norbornene group is polymerized in the presence of catalytic precursor prepared by reaction of at least one tungsten compound containing chlorine, bromine and/or iodine with at least one compound containing sterically hindered aminσgronp, cocatalyst selected from the group of organic compounds of aluminium, tin, lead, silicon, lithium, magnesium, borone, zinc and/or germanium. To prepare catalytic precursor at least one tungsten compound of general formula [I] WO Λ X- > [I] is used, where 0 is oxygen; x is chlorine, bromine or iodine; a is integer number 0 or 1; b is integer number 4 or 6, whereby concentration of this compound is 0.01 to 50 milimols per mol of monomer. In the preparation of the catalytic precursor as a compound containing sterically hindered aminogroup is used: a) at least one compound of general formula [II] where B 1-4 are identical or different alkyl groups with 1 - 6 hydrocarbon atoms; B» is OH, COOH, CN, NHR . NR P.", CONHB ' (where B and B" are alkyls with 1 to 18 carbon atoms) or heterocycle with N, 0 or S in ring; E c can be hydrogen or chemica.1 bond connected with B 5 to a heterocycle; W is hydrogen, alkylgroup with 1 to 18 carbon atoms or monoethylsuccinyl; and/or b) compound of general formula [III] where X is , S NB or CO; R 1 " 2 are identical or different alkyl groups with 1 - 6 carbon atoms; R 7 is hydrocarbon, alkylgroup with 1 to 18 carbon atoms or monoethylsuccinyl; and/or σ) compound of general formula [IV] R 7 where X is O, S, NR or CO; Ri~ 4 are identical or different alkyl groups with 1 to 6 carbon atoms; B 5 " 6 . s hydrocarbon atoms, groups COOB, NHB, NBR' , CN, OH, CONHR (where B and R' are alkyls with 1 to 18 carbon a-toms) or heterocyσleε with 0, S, N In ring and R 7 is hydrocarbon, alkylgroup with 1 to 18 hydrocarbon atoms or succinyl, whereby molar ratio [tungsten] / [amine] is 0.010 to 1:5. s cocatalyst organometalic compound of general formula [V] is used where R are identical or different and mean alkyl, alkenyl, alkσxy, aryl, arylσxy and alkarylgroups, saturated or unsaturated cyclic compounds with 1 to 14 carbon atoms; M is tin, lead, Bilicon, lithium, magnesium, boron, zinc, germanium or possibly a mixture of such elements; H is hydrogen, X is chlorine, bromine and/or iodine; m is 1 o 6, n is 1 or 2, p is 0 to 3, q is O or 1, whereby mole ratio [tungsten compound] / [cocatalyst] in the range 1:1 to 1: 20. Solution of cocatalyst contains as moderator at least one compound selected from the group of ethers, esters, ketons or nitriles in mole ratio [cocatalyst] / [moderator] 1:1 to 1:10, preferably n-butyl ether, diisopropylether, diisσpropylketon and/or diglyme. Monomer contains at least one norbornene group of general formula [VI] is selected from the group of substituted and unεubstituted norbornens, dicyclopentadiens, dihydrodicyclopentadiens, trimers of dicyclopentadienes, tetramers of σyclopentadienes, tetraσyclododeceneB, hexacyclododecenes, ethylidennσrbornenes, vinylnorbornenes or their mixture, whereby substituents of said monomerB are alkyls with one or two carbon atoms. The mixture of monomers contains up to 20 % wt of vinylic The mixture of monomers contains 0.1 to 20 2s wi" <>f monome of general formula [VII] where B 1 ' 2 is norbornenecarboxyl; B 3 is nσrbσrnenecarboxs'l, hydrogen or OH; B 4 is hydrogen or OH. Solutions of catalytic precursor, cocatalyst and monomer are transferred as separate streams and their mixing is carried out before filling into a mould having the desired semi product or product shape. Cocatalyst is dosed togerher with monomer as one stream. In the preparation of catalytic presursσr and diluting of cocatalyst cycloolefInic monomer of nσnbornene type is used, possibly in a misture with vinylic monomer. In the preparation of catalytic presursor and diluting of cocatalyst inert solvent is used selected from the group of benzene, toluene, xylene, chlorobenzene, trichlorobenzene, pentane, heptane, oktane and their mixture. Into any of the streams is admixed 0.01 to 2 2- wt of light stabilizers and or antiσxidants, 2 to 30 5s wt of blowing agents, 0.01 to \ 8 % wt of dispergators, 0.01 to 20 % wt of pigments, 1 to 75 % of fillers, 0.1 to 5 % wt of elastomers or their mixture. As filler ground calcium carbonate, ground dolomite, ground slate, aluminium oxide, silicon oxide, aluminium hydroxide, magnesium hydroxide, ground talc, kaolin, asbestos, mica, glass fibres, natural or synthetic fibres, carbon black, iron triσxlde, wood flour or their mixure is used. In any of the streams is dissolved 0.1 to 5 ?* wt of an additive from the group of elastomers pol isoprene, pσlybutadiene, pσlyσhlorσprene, styre ebutadiene copσlymer, butadiene—aerylonitrile copσl mer, ethyl n- ropyl n copolymer, butyl rubber or their mixture. The polymer in the shape of the final product is? thermally stabilized at temperature 50 to 350 °C for the period of to 120 minutes. As it has already been mentioned, in most cases chel ting a.gents or Lewis bases have to be added to the solu ion of tungsten compound to prevent premature monomer polymeriza¬ tion. But the hindered amines used according to t ip invention are Lewis bases themselves. Reaction solution containing monomer and catalytic component modified by a. hindered amine according to this invention is sufficiently stable and does not polymerize spontaneously. Even after- 48 hours exposition to the atmospheric oxygen and moisture the polymerization solution keeps its high activity and after it has been heated up to 80 °C it polymerizes (see examples No. 15 and 17) . A serious drawback is usually unpleasant smell of polymers caused by unreacted monomer. It has been found that some catalyst types prepared by means of modifiers according to this invention provide polymers with substantially lower smell. Moreover, discoloration is also negligible what is an advantage for products of light colour tinge or in some special applications, e.g. in optics. Not in the last, new possibilities are also opened in controlling the ratio gelling time / reaction time that reaches by the phenolic- modifiers the value about 0.1 and is a disadvantage in the BIM technology. The most preferable compounds of tungsten i i- preparation of the catalytic precursors In combination with the above mentioned compounds are WCle and/or WOCl_t or eventually their mixture. The starting material in preparation of the catalytic solu ¬ tion Is the suspension of tungsten compound in small quanti ¬ ty of a suitable solvent. The solvent must not react with the tungsten compounds; e.g. benzene, toluene chlorobenyene, dichlorσbenzene, trichlorobenzene, hexane, etc. are used. Concentration of the tungsten compound is somewhere in the range of 0.1 to 0.7 mσl/1 of solvent. A modification of tungsten compound Is carried out by addition of the solution of the hindered amine in the same solvent as is the one used in the suspension preparation. Preferable aminocompounds are : 2,2,6, 6-tetramethyl-4-hydrσxy-4-cyanσpiperidine, 2,2,6,6-tetramethyl-4-stearoylpiperidine, 2,2,6, 6-tetramethyl-4-hydroxy-4-aminσcarbσnylpiperidine, 2,2,6, 6-tetramethyl-4-σximinopiperidine, poly-[2—C.N,N ' -di (2,2,6,6-tetramethyl-4-piperidyl)hexanedi- amino>-4-<amino-l,l,3,3-tetramethybutyl>sym-triazine] : bis-(2,2,6,6-tetramethyl)-4-pi pe idylsebacate. H pσly- (N-β-hydroxyethyl ) -2, 2, 6, 6-tetra_methyl-4-hydroxypiperidyl- succinate o—4-[mσrpholine-4-yl3-sym-triazine in molar ratio [tungsten compound] / [hindered amine] approximately 1:0.015 to 1:5. The second part of the polymerization system contains a mix— ture of monomer with initiator. A suitable initiator is tri— alkylaluminium, dialkylaluminiumhalσgenide, alkylaluminium- dihalogenlde or their mixture (whereby alkyl contains 1 — 12 carbon atoms) , nd/or organic tin compounds of general formula- E 3 SnH (where B is alkylgroup with 1 - 10 carbon atoms or phenyl) . The most suitable is diethylalumlniumchlo ide in mole ratio to monomer 1:100 to 1:2000. Molar ratio of the tungsten compound to the Initiator is ranging from 1:2 to 1:20. To set required initiation periods, moderators are added to this solution. Moderators are ethers, esters, ketons or nitriles in molar ratio [organoaluminium compound] / [moderator] 1:1 to 1:5. The course of polymerization and polymer properties can be controlled also by the addition of suitable activators (e.g. alcohols, epichlorohydrin, tetrahydrofuran, etc.) and additives, e.g. fillers (glass fibres, mica, woll s onite, carbon black, talc, calcium carbonate, etc.), elastomers (natural rubber, butyl rubber, polyisoprene, ethyl-propylene copolymer, etc.) pigments, plasticizers, foaming agents, flame retardants, light stabilizers and antioxidants. Such additives are added to one or to both solutions. The invention is further illustrated by the following examples. Embodiments of the invention Abbreviations used in the specification of invention: CPD cyclopentadiene DCPD dicy lopentadiene DE C diethylaluminiumchlσride Example 1 Solution containing I .23 g ol 2 , , 5, S-tetramethyl-4-hydroxy- 4-amir_ocarbσnylpip ridine in 300 ml of toluene was gradually added by syringe to suspension of WCle in 50 ml toluene containing 6.163.10 -3 mol of tungsten. Consequently, molar ratio of both components in the course of reaction was 1:1. Toluene used as solvent was stripped by dry nitrogen and distilled under vacuum above natrium. The solution obtained was bubbled by inert gas for several hours to remove liberated HCi . Tungstic component concentration i'n the so prepared solution of catalytic precursor was about 0.1 M. Example 2 Solution containing 0.28 g of 2, , 6, 6-tetramethyi-4-hydrσxy- 4-cyanopiperIdine in 35 ml of toluene was admixed as in Example 1 to 50 ml of WCls suspension in toluene containing 6.163.10 -3 mol of tungsten. Molar ratio of both components was 1:0.25. Concentration of tungsten component in the so prepared solution of catalytic precursor was 0.1 M. The method of toluene drying and HCl removal from the reaction mixture were Identical as that in example 1. Example 3 Solution containing 5.21 g of 2,2,6,6-tetrameth " yl—4-stearoyi- oxypiperidine In 20 ml of toluene was admixed as in Example 1 to 50 ml of WC1« suspension in toluene containing 6.163.10 -3 mol of tungsten. Molar ratio of tungsten to modifier was 1:2. Concentration of the tungsten componerr. in the solution of catalytic precursor was approximately 0.1 M. The method of toluene drying and HCl removal from the reaction mixture were identical as that in example 1. Example 4 Solution containing 1.30 g of 2, 2, 6, 6-tetramethyi-4-stearσyi- oxypiperl lne in 5 ml of toluene was admixed as in Example 1 to 50 ml o WCIc suspension in toluene containing 6.153.10 -3 mol of tungsten. Moiar ratio of tungsten to modifier was 1:0.5. Concentration of the tungsten component- in the solution of catalytic precursor was approximately 0.1 K. The method of toluene drying and KCI removal from the reaction mixture were identical as that, in Example I. Example 5 Solution containing 0,244 g of 2, 2, 6,6-tetramethyl-4-σximino- piperidine in 75 ml of toluene was admixed as in example 1 to 50 ml of WCle suspension in toluene containing 6.163.10-3 mol of tungsten. Molar ratio of both components was 1:0.2. Concentration of the tungsten component in the solution of catalytic precursor was approximately 0.1 M. The method of toluene drying and HCl removal from the reaction mixture were identical as that in example 1. Example 6 Solution containing 0,25 g of bis-[l , , 2, 5, 6-pentamethyl- piperidine-4-yl]-sebacate in 67 ml of toluene was admixed gradually . by a syringe to 50 ml of WCle suspension in toluene containing 6.163.10 -3 mol of tungsten. Molar ratio of both components during the reaction was 1:0.1. The solution obtained was bubbled by inert gas for several hours to remove the liberated HCl. Concentration of the tungsten component in the so prepared solution of catalytic precursor was approximately 0.1 M. The method of toluene drying and HCl removal from the reaction mixture were iden¬ tical as that in example 1. Example 7 Under inert atmosphere, 0.73 ml of the solution of catalytic precursor prepared according to example 1 was admixed to 10 mi of dicyclopentadiene (DCPD) in a special test tube. 4 mi of this mixture was admixed to 4 ml of the solvent containing 0.13 ml of 1.388 M solution of DΞAC and 0.105 mi of di-n-buthylether as moderator, in DCPD. Exact admixing of the moderator was carried out by a dosing syringe. Molar ratio DCPD:W:DEA -'moderator after admixture of both solutions was 2000:1:3:20. Immediately, this mixture was shaken shortly but Intensively. At the laboratory temperature, polymerisation was not initiated (gel formation) not even after 10 minutes. After Immersion Into a bath heated up to 60 °C the reaction commenced rapidl ; maximum temperature of the polymerizing mixture, indicated by a thermocouple, was reached within 50 ε. A hard, nσnεσluble polymer was formed and conversion, determined gravimetrically CIS minutes at 175 β C) was 97.8 % Example 8 Under inert atmosphere, 0.73 ml of the solution of catalytic precursor prepared according to example 2 was admixed to 10 ml of dicyclσpentadlene (DCPD) in a special test tube. 4 ml of this mixture was admixed to 4 ml of the solvent containing 0.13 ml of 1.888 M solution of DEAC in toluene and 0.105 ml of di-n-butylether as moderator, in DCPD. By • polymerization at laboratory temperature a hard, nonsσluble polymer was formed. Maximal temperature of the polymerizing mixture was obtained within 50 s after the solutions have been mixed. Example 9 Under inert atmosphere, 0.73 ml of the solution of catalytic precursor prepared according to example 3 was admixed to 10 ml of dlcyclopentadlene (DCPD) in a special test tube. 4 mi of this mixture was admixed to 4 mi of the solvent containing 0.13 ml of 1.888 M solution of DEAC and O.iOo ml of dl—n—butylether as moderator, in DCPD. Poiymet-iza ion was ca-rrled out at 5C " °C. Maximal temperature was reached within 50 s after the solutions hav been mixed. nversion 3?.5 s and glass transition temperature .measured by Ξ?C e od 11 °C were reached. Example 10 Under inert atmosphere, 0.73 ml of the precursor solution prepared according to Example 4 was admixed in a special tube to 10 ml of DCPD containing 8 %■ of pentaerythritσl-tris-(bicyclo[2, ,1]hept-2-en)-5-carboxylate, which being a conomer prepared by reaction of pentaerythritolaerylate with CPD, that was generated by dissociation of DCPD at its boiling point, i.e. 175 »C. 4 ml of this mixture was admixed to 4 ml of the solvent containing 0.13 ml of 1.888 M solution of DEAC and 0.105 ml of di-n-butylether as moderator, in DCPD. Polymerisation does not run at laboratory temperature. At the temperature 80 β C this polymerization is virtually finished within ' 120 s. Example 11 (comparative experiment to Example 10) In this example WCle modified by p-tert-butylphenσl in molar ratio 1:1' according to patent US 4,400.340 was used as catalytic precursor. Tungsten concentration in catalytic precursor and monomer composition were the same as in the Example 10. The polymerisation does not run at laboratory temperature. Example 12 (comparative experiment) Under conditions specified in the Example 11 but at 1/3 higher concentration of the catalytic precursor and cocatalyst only thin gel is obtained after 15 minutes of polymerisation at 80 °C. Example 13 (comparative experiment) Under conditions specified in the Example 11 but at cσmσnσmer content decreased to 1/2 (i.e. to 4 % wt) polymerization runs at 80 °C and maximum temperature of polymerization mixture is obtained after 450 s. Example 14 (comparative experiment) Under conditions specified in the Example 13 but with by 1/3 increased amount of catalytic precursor and cocatalyst the maximum temperature was rea.ched after 140 s. Example 15 Precursor prepared according to the Example 3 was left in the test tube under air access for 48 hours. 4 ml of the solution containing 0.13 ml of 1.888 M DEAC solution and 0.105 ml of di—n—butyl-ether solution as moderator, in DCPD. Molar ratio DCPD:W:DE C.-moderator was 2000 :1 :8 :-20. Polymeri¬ sation does not run at the laboratory temperature within reasonable time, but at 70 β C the maximum polymerization temperature was reached within 70 s after the reactor was immersed in a. thermostating bath. Conversion 99.67 % was reached. Example 16 v Under Inert atmosphere, 0.73 ml of the solution of catalytic precursor prepared according to Example 4 was admixed to 10 ml of dicyclopentadiene (DCPD) in a special test tube. 4 ml of the solvent containing 0.12. ml of 1.888 M DEAC solution and 0.105 mi of i-n-butyie".her as moderator, in DCPD. Molar ratio DCP :V:DEAC:moderator wa 2000:1:3:20. By poly¬ merization at laboratory temperature gel was formed after 60 s. Maximal temperature was reached within 22C s. Example 17 Catalytic precursor prepared according to the Example 4 was left in a test tube under air access for 48 hours and thereafter used to repa e reaction solution. Molar ratio DCPD:W:DEAC :mσderatσr in the polymerization test was 3000:1:5:5. In polymerization at laboratory temperature gel was formed within 100 ε and maximum temperature was reached within 460 s. Conversion was 98.4 % . Example 18 Under inert atmosphere, 0.73 ml of the solution of catalytic precursor prepared according to Example 5 was admixed to 10 ml of dicyclopentadiene (DCPD) in a special test tube. By polymerization at laboratory temperature maximum temperature was reached within 60 s. Light coloured and soft polymer was obtained. Example 19 . comparative experiment) Under conditions specified i the Example 18 but at polymerization temperature 80 »C the maximum temperature was reached within 10 s. Light coloured and hard polymer was obtained. Conversion was 99.53 . Example 20 Under inert- atmosphere, 0.73 mi of the solution of catalytic pr<5- < rscr ρr< p3. d according to example 6 was admixec. to 10 mi oi dicyclopentadiene (DCPD' in a special test ube. 4 ml cf this mixture was added to 4 ml oi the sol en containing 0.13 mi of. 1.838 M DEAC solution and G.1C5 ml cf di-n-butyiether as moderator, in DCPD. Molar ratio DCFD:W: DE C:moderator after a>_lmixing both solutions was 2000:1:8: 20. The mixture was immediately shortly but intensively shaken. At laboratory temperature gel was formed after -50 s. After immersing In a bath heated up to 50 °C the reaction started quickly; maximum temperature of polymerization mixture, indicated by a thermocouple, was reached within 140 s. Example 21 Under Inert atmosphere, 0.73 ml of the solution of catalytic precursor prepared according to example 6 was admixed to .10 ml of dicyclopentadiene (DCPD) in a special test tube. 4 ml of this mixture was added to 4 ml of the solvent containing 0.13 ml of 1.888 M DEAC solution and 0.038 ml of diisσpropylether as moderator, in DCPD. Moderator was dosed by amicrosyrIng . Molar ratio DCPD:W: DEAC:moder tor after admixing both solutions was 2000:1:8: 20. The mixture was immediately shortly but intensively shaken and the test tube was immersed In 60 °C warm bath. Maximal temperature was reached within 130 s after the reactor was immersed into the thermostating bath. Example 22 Under Inert atmosphere, C.~3 ml of the solution of -ra aly-i precursor prepared according to example 5 was admixed to IC ml of dicyclopentadiene (DCPD) In a. special test tube. 4 ml of this mixture was added to 4 ml of the solvent containing 0.13 ml of 1.583 M DEAC solution and 0.08" ml of diiεσprσpyIketone as moderator, in DCPE r . Moderator was dosed by a syringe. Molar ratio DCPD': * .*: DEAC :moderator after admixing both solutions was 2000:1:9: 20. The mixture was i mediat ly short1" ut 1—. e si ei s a and the s u was immersed In a '30 =-3 wa m bath. Polymerization w s -carri¬ ed out at 60 °C. Maximal temperature was reached within 270 s after the reactor was immersed into the thermostating bath. Example 23 The example 8 was repeated with the exception that hexane was used as cocatalyst diluent. Polymerization course and polymer properties were practically identical with those of the Example 8. Example 24 Polymerisation test simulating RIM technique was carried out using catalytic system according to the Example 3 as follows : 600 ml of catalytic precursor solution according to example 3 and 600 ml of cocatalyst, containing 19.5 ml of 1.888 M DEAC solution and 13.2 ml diglyme (diethylenglycol- dimethylether) as moderator, in DCPD was charged in two tem¬ pered storage vessels with volume 1000 ml. Molar ratio of DCPD:W:DEAC .-moderator was 2000:1:8:20. Solutions were pumped from storage vessels to a mixing head and from this head injected to glass moulds previously dried in a drier. Dimensions of moulded pieces were 180x160x4 mm. Temperature of polymerisation solutions before mixing was 26 °C, polymerization temperature was 60 °C, reaction time was 30 s. The following properties were determined on the moulded pieces: Tensile strength 46.2 MPa Elongation 3.8 « Modulus of elasticity in tension 1910.0 MPa Heat deflection temperature (1.80 MPa) 73.0 °C (0.45 MPa) 82.0 » C Hardness 81.3 Sh D Industrial Ap lic tions Metathetical polymerization and cσpσlymerizatiσn of cycio- al enes of norbornene type or of a mixture with vinyl monomers and other additives is used in reaction injection moulding (RIM) production of thin-walled products or semiproducts of complicated shape. The principal application fields are: production of automobile body parts where surface treatment by baking enamels is carried out, thermally stressed parts of complicated shape in the electronic industry, boards for printed circuit boards, etc.

Claims: l a i m s Method of production of polymers a cσpolymers of cyclσ¬ alkenes of norbornene type by metathetical polymeriza¬ tion in the presence of catalysts based on tungsten compounds, which comprises that at least one monomer containing at least one norbornene group is polymerized in the presence of catalytic precursor prepared by reaction of at least one tungsten compound containing chlorine, bromine and or iodine with at least one compound containing sterically hindered aminogroup, co¬ catalyst selected from the group of organic compounds of aluminium, tin, lead, silicon, lithium, magnesium, bσrσne, zinc and/or germanium. Method according to claim 1 which comprises that to prepare catalytic precursor at least one tungsten compound of general formula [I] WO a X & [I] is used, where 0 is oxygen; x is chlorine, bromine or iodine; = is integer number 0 or 1; b is integer number 4 or 6, whereby concentration of this compound is 0.01 to 50 miiimois per mol of monomer. Method according to claim 1 to 2 which comprises that in the preparation of the catalytic precursor as a com¬ pound containing sterically hindered aminogrσup is use : a) at least one compound of general formula [III where R 1-4 are identical or different alkyl groups with 1 - 5 hydrocarbon atoms; R5 is OH, COOH, CN, NHR . MS R", CONHE ' (where R and R" are alkyls with I to IS carbon atoms) or heterocycle with N, 0 or S In ring; S 6 can be hydrogen or chemical bond connected with R 3 - to a heterocycle; R 7 Is hydrogen, alkylgroup with 1 to 18 carbon atoms or monoethylsuccinyl; and-'cr compound of general formula wn e NS different alkyl groups with J > ZSΓ-'-Ό-! ms; _ hy-drccarbor., alkylgroup with ϊ 5 a o atoms monoeth lsuccinyl; and/or c) compound of general formula [IV] where X is 0, S, NR or CO; R 1-4 are identical or different alkyl groups with 1 to 6 carbon atoms; R ε« s are hydrocarbon atoms, groups COOR, NHR, NRR- , CN, OH, COMHR (where R and R« are alkyls with 1 to 18 carbon atoms) or heterocycles with 0, S, N in ring and F7 is hydrocarbon, alkylgroup with 1 to 18 hydrocarbon atoms or monoethylsuccinyl, whereby mole ratio [tungsten] / [amine] is 0.010 to 1:5. Method according to any claim 1 to 3 which comprises that as cocatalyst organometalic compound of general formula [V] Ό _ [V] is use where __. are identical or different and mean alkyl, alkenyl, a_.kcxy, aryl, aryl xy and alkary1groups, saturated or ur.satura.ted cyclic rσmp '_.nds with i — » ' carbor. Etcms; M leaα, .=.__ con. .ithi m, magnesium, boron, zinc, germanium o possibly a mixture f rn. - . r*. elements; H is hycrcg r., X is rniorine, rcir.i e and/ r iodine; π. is 1 -_._: i , r. is 1 z-r , p is 0 to Ξ, ■ J is o 1, e eb mole ratio I tungsten compound] [cocatalyst, in the range 1:1 tc 1 : 21. 5, Method according to any claim 1 to 4 which comprises that solution of cocatalyst contains as moderator at least one compound selected from the group of ethers, esters, ketons or nitriles in mole ratio [cocatalyst] / [moderator] 1:1 to 1:10, preferably n—butyl ether, dllsopropylether, diisopropylketon and. / or diglyme ' . 6. Method according to any of claims 1 to 5 which comprises that monomer contains at least one norbornene group of general formula [VI] Is selected from the group of substituted and nεub- stituted norbornens, dicyclopentadlens, dihydrodicyclo— pent-adiens, trimers of dicyclopent.adier.es, t tramers of c clcpentadi ne , tetracyc1ododecenes, hexacyciododece— nes, ethylidennσrbornenes, vinylnorhorner.es or their mixture, whereby substituents of said monomers are alkyls with one or two carbon atoms. Method according to any claim 1 to which comprises that the mixture of monomers contains up to 20 :•:-. c£ vin iic monomer that does not contain norbornene group- Method according to any claim 1 to 7 which comprises tthhaatt tthhee mmiixxttuurree ooff mmoonnoommeerrss ccoonn.tains O.i to 20 monomer of general formula [VII] where R 1 ' 2 is norbornenecarboxyl ; R 3 is norbσrnene- carboxyl, hydrogen or OH; R 4 is hydrogen or OH. 9. Method according to any of claims 1 to 8 which comprises that solutions of catalytic precursor, cocatalyst and monomer are transferred as separate streams and their mixing is carried out before filling into a mould having the desired semi product or product shape. 10. Method according to any of claims 1 to 9 which comprises that cocatalyst is dosed together with monomer as one stream. 11. Method according to any of claims 1 to 10 which comprises that in the preparation of catalytic precursor and diluting of cocatalyst cycloolefinic monomer of norbornene type is used, possibly in a mixture with vinylic monomer. 12. Method according to any of claims 1 to 10 which comprises that in preparation of catalytic precursor and diluting of cocatalyst inert solvent is used selected from the group of benzene, toluene, xylene, chlσrobensene, dichiorobenzene, triσhlσrσber.zene, pentane, heptane, oktane and their mixture. 13. Method according to any of claims 1 to 12 which comprises th t into any of the streams is admixed 0.01 to 2 % wt of light stabilizers and/or antiσxidants, 2 to 30 % wt of blowing agents, 0.01 to S % wt ci dispergators, 0.01 to 20 wt of pigments, 1 to 75 % c i fillers, 0.1 to 5 wt of elastomers or their mixture. 14. Method according to claim 13 which comprises that as filler ground calcium carbonate, ground dolomite, ground slate, aluminium oxide, silicon oxide, aluminium hydroxide, magnesium hydroxide, ground talc, kaolin, asbestos, mica, glass fibres, natural or synthetic fibres, carbon black, iron trioxide, wood flour or their mixture is used. 15. Method according to any of claims 1 to 14 which compri¬ ses that in any of the streams is dissolved 0.1 to 5 9S wt of an additive from the group of elastomers polyisoprene, polybutadiene, polychloroprene, styrene- butadiene copolymer, butadiene-acrylonitrlle copoly er, ethylen- propylene copolymer, butyl rubber or their mixture. 16. Method according to any of claims 1 to 15 which comprises that the polymer in the shape of the final product is thermally stabilized at temperature 50 to 350 °C for the period of 5 to 120 minutes.

Inventors: BALCAR HYNEK, HELLER GERHARDT, KRAFIAT MIROSLAV, LEDERER JAROMIR, MEJZLIK JIR I, ONDRUJ JIRI, STOHANDL JIRI, STPANEK KAMIL, VAREKOVA IRENA, VOZKA PAVEL, BALCAR, HYNEK, HELLER, GERHARDT, KRAFIAT, MIROSLAV, LEDERER, JAROMIR, MEJZLIK, JIRI, ONDRUJ, JIRI, STOHANDL, JIRI, STPANEK, KAMIL, VAREKOVA, IRENA, VOZKA, PAVEL
Applicants: CHEMOPETROL S P LITVINOV VYZKU, CHEMOPETROL, S.P. LITVINOV VYZKUMNY USTAV MAKR
Application year: 1992
Main classification: C08G61
IPC codes: C08F4, C08G61