DE1595739A1 - Process for polymerizing cycloolefins with ring opening - Google Patents

Description

Patent attorneys Dipi.-ing. Walter Meissner Dipi.-ing. Herbert Tischer

1 BERLIN 33, Herbertstrasse 22 MUNICH

Telephone: 8 87 72 37 - Wired word: Invention Berlin
Postal checking account: W. Meissner, Berlin West 122 82

Bank account: W. Meissner, Berliner Bank A.-Q., Depka 36,,

Berlln-Halenaee, KurfUrstendamm 130 Account No. 96 716 1 BERLIN 33 (GRUNEWALD), the * QQ (^

Herbertstrasse 22

P 1595 739.8 5786 GE

THE GOODYEAR TIRE AND
RUBBER COMPANY

Process for polymerizing cycloolefins under

Ring opening

The invention relates to a method for producing polymers from unsaturated, alicyclic compounds and in particular from unsaturated alicyclic compounds that are unsaturated in their rings due to a double bond between two carbon atoms.

According to the invention it has been found that polymers of unsaturated alicyclic compounds can be prepared which have at least one alicyclic ring, this being Ring has at least 8 carbon atoms and the 1 to 3 carbon to carbon double bonds in the alicyclic Have ring by subjecting the alicyclic compound to polymerization in the presence of a catalyst system which contains at least one organometallic compound of a metal selected from groups Ia, Ha, Hb and HIa des Periodic Table and contains at least one salt of metals from Group VIb of the Periodic Systems are selected. The periodic table of the elements referred to here can be found in the handbook of Chemistry and Physics, 44th Edition, Apr. 1962, p. 448.

Typical examples of metals from which the organometallic compound can be made are lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, zinc, cadium, mercury, aluminum, gallium, indium and thallium . The preferred organometallic compounds are compounds of lithium, sodium, magnesium, aluminum, gallium, indium, zinc and cadmium. 009818/1631

New documents (type (β **** im * 2

Typical examples of organometallic compounds are aluminum compounds which have at least one aluminum-carbon bond such as trialkylaluminum compounds, e.g. trimethylaluminum, triethylaluminum, Tri-n-propyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, Trihexyl aluminum, trioctyl aluminum and the like. Dialkyl aluminum halides, such as diethyl aluminum chloride, di-n-propyl aluminum chloride, diisobutyl aluminum chloride, Diethyl aluminum bromide, diethyl aluminum iodide, and the like, Alkyl aluminum dihalogen compounds such as ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum iodide and the like, dialkyl aluminum hydrides such as diethyl aluminum hydride, di-n-propyl aluminum hydride, dibutyl aluminum hydride and the like, the triaryl aluminum compounds such as triphenyl aluminum and the like, the aryl aluminum hydrides and dihydrides such as diphenyl aluminum hydride and phenyl aluminum dihydride. Other organometallic compounds, in particular those which are capable of a metal salt, can also be used to reduce group VIb to a lower valence level. Typical examples for such organometallic compounds are alkyl lithium compounds, such as ethyl lithium, butyl lithium and the like, lithium aluminum tetralkyls such as lithium aluminum tetrabutyl, Lithium aluminum tetraethyl and the like., Alkalimetallalky-Ie, and aryls such as amyl sodium, phenyllithium and the like., Alkyls and aryls of the metals of the group Ua such as diphenylmagnesium, diethyl calcium and the like., Alkyls of the metals Group Hb such as diethyl zinc, diethyl cadmium and the like, and Grignard compounds such as phenyl magnesium bromide and the like. Mixtures of such compounds can optionally also be used. It is usually preferred to use trialkylaluminum compounds, such as triethyl aluminum, tri-npropyl aluminum, triisobutyl aluminum, trihexyl aluminum and like. to apply.

The metal salts used in the catalyst according to the invention are salts of the metals of group VIb des Periodic Table and include chromium salts, molybdenum salts

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and tungsten salts. Typical examples of such salts include the halides, such as the chlorides, Bromides, iodides and fluorides, to which compounds such as chromium chloride, chromium trichloride, chromium hexachloride, molybdenum pentachloride, Molybdenum hexachloride, tungsten hexachloride, Chromium d'ibromide, chromium tribromide, chromium hexabromide, molybdenum pentabromide, Molybdenum hexabromide, tungsten hexabromide, chromium iodide, Chromium triiodide, chromium hexaiodide, molybdenum pentajodide, molybdenum hexaiodide, tungsten hexaiodide, chromium difluoride, chromium trifluoride, Chromium hexafluoride, molybdenum pentafluoride, molybdenum hexafluoride and tungsten hexafluoride. More distinctive Salts are those of the acetates, benzoates, acetylacetonates, sulfates and the like, to which compounds such as chromium acetate, molybdenum acetate, tungsten acetate, chromium benzoate, molybdenum benzoate, tungsten benzoate, chromium acetylacetonate, molybdenum acetylacetonate, Include tungsten acetylacetonate, chromium sulfate, molybdenum sulfate, and tungsten sulfate. Mixtures of these salts can also be used. With regard to the same, it is usually preferable to use tungsten halide and molybdenum halide Tungsten hexachloride and molybdenum pentachloride are applicable and characteristic of the same.

According to the invention, various unsaturated alicyclic Connections are applied. These unsaturated alicyclic compounds are also sometimes called cyclialiphatic and cycloolefinic compounds. These unsaturated alicyclic or cycloaliphatic compounds include compounds that are cyclooefinic compounds as well as compounds that are substituted cycloolefinic Have rings, these rings having at least 8 carbon atoms and Ibis having 3 carbon atoms Have carbon double bonds in the rings. The term cycloolefinic or cycloolefin thus includes cyclomonoolefins, Cyclodiolefins and cyclotriolefins.

The cycloolefinic rings can be replaced by groups such as alkyl, aryl, aralkyl, alkaryl, acyl, alkoxy, cyano, halogen, Carboalkoxy, aryloxy, acyloxy, and aroyloxy groups substituted be. One or more of these groups can be present on the cycloolefinic ring.

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The preferred alicyclic compounds of the present invention are cycloolefins having a single ring of 8 or more Has carbon atoms and 1 to 3 carbon-carbon Has double bonds in the ring. Characteristic cycloolefins of this type are 8 carbon atoms in the ring Cyclooctene, 1.3-, 1.4- and l.S-cyclooctadiene, and the 1.3.5- and 1,3-6-cyclooctatrienes. Characteristic cycloolefins are with 9 carbon atoms in the ring cyclonones, 1.3-, 1.4- and 1.5-cyclononadiene and the cyclononatrienes, such as 1.3.5- and 1.3-6, 1.37- and 1.4.7-cyclononatrienes. Typical examples for cycloolefins with 10 carbon atoms in the ring are cyclodecenes, 1.3-, 1.4-, 1.5- and 1.6-cyclodecadienes and the cyclodecatrienes such as 1.3.5-, 1.3.6-, 1.3.7-, 1.3.8-1.3.9-, 1.4.6-, and 1.4.7-cyclodecatrienes. Distinctive Examples of cycloolefins with 11 carbon atoms in the ring are cycloundecene, 1.3-, 1.4-, 1.5- and 1.6-cycloundecadienes and the cycloundecatrienes, such as 13.5-, 1.3.6-, 1.3.7-, 1.3.8-, 1.3.9, 1.3.10, 1.4.6, 1.4.7 and 1.4.8 cycloundecatriene. Characteristic cycloolefins with 12 carbon atoms in the ring are cyclodecene, 1.3-, 1.4-, 1.5-, 1.6- and 1.7-cyclododecadiene and the cyclododecatrienes, such as 1.3.5-, 1.3.6-, 1.3.7-, 1.3.8-, 1.3.9-, 1.3.10-, 1.3.11-, 1.4.6-, 1.4.7-, 1.4.8-, 1.4.9- and 1.5.9-cyclododecatriene. Mixtures of these various cycloolefins can also be used.

The particularly preferred cycloolefins had 1 to 3 carbon-atom-carbon double bonds in the ring, and the double bonds are relative to one another such that they are non-contiguous and non-conjugate to each other. Typical examples of such cycloolefins are cyclooctene, cyclododecene, 1,5-cyclooctadiene, and the 1.5.9-cyclododecatrienes, in the trans-, trans-, transund Cis, Trans, Trans configurations.

The various alicyclic ones contemplated by the present invention Compounds can also be substituted with various groups on the cycloolefinic ring. It it goes without saying that the cycloolefinic rings are mono- or multi-substituted.

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Typical examples of substituted alicyclic compounds are alkyl-substituted cycloolefins, such as 1.5.9-trimethylcyclododecatriene, Aryl-substituted cycloolefins, such as 3-phenylcyclooctene-1, aralkyl-substituted cycloolefins, such as 3-benzylcyclooctene-l, alkaryl-substituted cycloolefins, such as 3-methylphenylcyclooctene-1, acyl-substituted cycloolefins, such as 5-acetylcyclooctene-1, alkoxy-substituted cycloolefins, such as 5-methoxycyclooctene-1, cyano-substituted Cycloolefins, such as 5-cyanocyclooctene-l, 3-cyanocyclooctene-l, 5. g-dicyanocyclododecene-l, and ii-cyanocyclododecadiene-l, 5, halogen-substituted cycloolefins in which the halogens are iodine, chlorine, bromine and fluorine, such as S-chlorocyclooctene-1, S-bromocyclooctene-1, S-chlorocyclododecene-1, and 5,6-dichlorocyclooctene-1, carboalkoxy-substituted cycloolefins, such as 5-phenoxycyclooctene-1, acyloxy-substituted cycloolefins, such as 5-benzoylcyclooctene-1, and aroyloxy-substituted Cycloolefins such as 5-acetoxycycloofctene-1 and aroyloxy substituted Cycloolefins such as 5-benzoylcyclooctenl. Mixtures These alicyclic compounds with substituted cycloolefinic rings can be used as well as mixtures the alicyclic compounds with cycloolefinic rings and alicyclic compounds with; substituted cycloolefinic Wrestling.

The catalysts according to the invention are produced by means of mixing the components in generally known procedures manufactured. No special order of blending is required. The catalysts can be "preformed" or "in situ". In the preforming, the catalyst components are mixed together before each Component is brought into contact with the monomer to be polymerized. In the in situ process, the catalyst components added separately to the monomers. The catalyst components can either be used as pure compounds or are mixed as suspensions or solutions in liquids that do not adversely affect the polymerization. The amount of catalyst used in the polymerizations according to the invention can be used within relatively large concentrations

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areas of concentration are changed and has not proven to be critical. There must of course be a catalytic amount of the catalyst can be used to cause the polymerization of the monomer. The optimal amount of catalyst depends on a number of factors, such as the temperature, the reactants used, such as the degree of purity the reactants, desired reaction time and like. from. For the person skilled in the art, there are no difficulties whatsoever with finding the optimal catalytic ranges ascertain. If there is a maximum catalytic level, the polymerizations can still be carried out where the amount of total catalyst is about 0.001 to about θ 5.0 parts by weight per 100 parts by weight of the applied Monomers, although a range of about 0.01 to about 1.0 thereof is not appropriate and a The range from about 0.05 to about 0.2 is usually more convenient. The term "total catalyst" as used herein is to be understood to include the weight of both the organometallic compound and the metal salt. Quality Polymerization rates for bulk polymerization have been obtained where a mixture of 0.05 wt. Parts of tungsten hexachloride and 0.04 parts by weight of triisobutylaluminum have been used for polymerizing 100 parts by weight of cyclooctene.

With regard to the catalyst composition, the molar ratios of the organometallic compounds to the metal salts of group VIb in a range from about 0.1: 1 to can be changed about 30: 1 or higher. However, a molar ratio of from about 0.25: 1 to about 15: 1 is usually preferred. For those skilled in the art, it goes without saying that the optimum molar ratio of the catalyst components depends on the application the specific combinations of the catalyst components, the monomer to be polymerized and the polymerization conditions can fluctuate. In the polymerization of cyclooctene e.g. with a catalyst consisting of a mixture of trialkylaluminum and tungsten hexachloride are usually preferred that the molar ratio of aluminum compound to the metal salt amounts to about 0.4: 1 to 2.5: 1.

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The polymerizations according to the invention can be carried out in solution or in bulk. When the polymerization is in solution is carried out, solvents are useful that do not adversely affect the polymerization. Distinctive Examples of suitable solvents are liquid aromatic hydrocarbons such as benzene and toluene, hydrogenated aromatic hydrocarbons such as tetralin, liquid aliphatic Hydrocarbons such as pentane, heptane, hexane, petroleum ether, decane and liquid cycloaliphatic hydrocarbons, such as cyclohexane, decalin and cyclooctane. Mixtures of these solvents can also be used.

The temperatures at which the polymerization reaction is carried out can vary within a wide range. Usually, the temperature may range from extremely low temperatures such as -6O ⁰ C up to high temperatures, such as 100 ⁰ C or changed higher. Thus temperature is not a critical factor. It is generally preferred to carry out the reaction at a temperature of about -20 ° C to about 8O ⁰ C. The puck at which the polymerization is carried out can be varied within a wide range. The reaction can be carried out under normal pressure or, if appropriate, under reduced pressure or elevated pressure. In general, a satisfactory polymerization is achieved when the reaction is carried out at about the autogenous pressure developed by the reactants under the chosen operating conditions.

The polymerization time will vary and can range from a few seconds to 24 hours or more depending on the polymerization conditions and the degree and extent of the desired polymerization.

The polymerization reaction can be carried out as a batch or continuous process. During execution the polymerizations of the present invention can accomplish this of the monomer, the catalyst and the solvent, if a solvent is used, alternately, intermittently and / or continuously introduced into the reaction zone.

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It is assumed that the polymerizations according to the invention via a polymerisation mechanism that opens the ring to run. Such ring-opening polymerizations of cycloolefins can be used to produce a number of alternating Copolymers and terpolymers are used, which one could not produce so far. For example, the ring-opening polymerization of cyclooctene leads to a Polyoctenamer, which is considered to be the alternating copolymer of a butadiene unit and two ethyl units can.

The ring-opening polymerization of 1,5-cyclooctadiene leads to a polybutenamer which is equivalent to the 1,4-addition polymer of 1,3-butadiene. Such a thing Polybutadiene can be rubbery and can be made to be less than 1% and even less than the same has about 0.2% 1.2 or vinyl structure. According to the invention, polybutenamers can be prepared, their structure alternating cis and trans vinyldene groups in successive, have repeating polymer units, and this is equivalent to the polymer produced by 1.4-addition Polymerization of 1,3-butadiene is obtained, being successive 1,3-butadiene units are obtained, namely alternately in cis and trans configuration. A such polymer can be viewed as an alternating copolymer of cis- and trans-1,4 poly (butadiene-1,3).

The ring-opening polymerization of 5-methylcyclooctene-1 would lead to the alternating terpolymer of 1,3-butadiene, propylene and ethylene. In the same Way, 5-phenylcycloocetene-1 would become the alternating one 13-butadiene terpolymer, styrene and ethylene lead. the polymerization of 5-methyl-cyclooctadiene-1,5 taking place with ring opening would lead to the alternating copolymer of 1,3-butadiene and isoprene. The under ring opening subsequent polymerization of 1,5-cyclooctadiene would lead to lead a polybutadiene that has less than about 0.2% 1,2-configuration, and the remainder, or 99.8%, of the 1,4-configuration, from about 20 to about

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BATH ORIGINAL

1395739

90% are cis-1,4 configuration, or it is a polybutadiene which is about 20 to etsa 75 or 80% 1,4 configuration in the cis-1,4 configuration, or even a polybutadiene with less than about 0.2% 1,2-configuration, where the remainder or 99.8% has the 1,4-configuration and here about 70 to about 80 or 90% are in the cis-1,4 configuration. The polymerization that takes place with ring opening from substituted cyclododecenes can lead to even more complex, alternating copolymers, terpolymers and even lead to quadripolymers.

The ring-opening polymerization also makes it possible to produce copolymers and terpolymers that contain have not yet been obtained by means of conventional addition polymerizations. A typical example for such a polymerisation the under ring opening polymerisation of cyclonones which results in perfectly alternating copolymers of butadiene 1.3 and pentamethylene leads.

Cycloolefins with groups other than hydrocarbon radicals are substituted and undergo polymerization with ring opening, lead to copolymers and terpolymers that have a high degree of order in terms of alternation. Some examples are in Table I below reproduced. In Table I there is an indicative list of examples which are within the scope of the invention.

Table I.

Polymer obtained by ring opening is polymerized ^ monomer equivalent to an alternating interpolymer of

5-cyanocycloocetene-1 butadiene-1,3 + acrylonitrile + ethylene S-chlorocyclooctene-1 butadiene-1.3 + vinyl chloride + ethylene 5-acetoxycyclooctene-1 butadiene-1,3 + vinyl acetate + ethylene 5-carbomethoxycyclo-

octene-1 butadiene-1,3 + methyl acrylate + ethylene

9-cyanocyclododecadiene-butadiene-1.3 + acrylonitrile + ethylene 1.5 + butadiene-1.3

S ^ -DScyanocyclododecen- butadiene-13, + acrylonitrile + ethylene 1 + acrylonitrile + ethylene

S-BroiTioycloocten-l Btitadten- ethylene + bromobutadiene-1.3 +

Ethylene

3-cyanocyclooctene-1 ethylene + 1-cyanobutadiene ~ 1, 3 + ethylene 5-chlorocyclododecene-1-butadiene-1,3 + vinyl chloride + 3-ethylene.

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The ring-opening polymerization of cycloolefins, which contain 8 or more carbon atoms in the ring, leads to high molecular weight polymers with superior Resistance to oxidative aging. The bulk polymerization can be considered convenient from a process standpoint because it is relative little heat per mole occurs in the polymerization of the cycloolefin. This represents a great benefit for this one Ring opening represents polymerization compared to conventional addition polymerization.

The slight reduction in volume that occurs with ring-opening polymerization is one Another important advantage over conventional addition polymerization, especially where Cycloolefins polymerized in bulk to form embedding products and various other products in bulk corresponding examples are deformed plastic objects, rubber-like objects, shoe soles and hoes, industrial tapes and vehicle tires are.

In these areas of application, the monomer can be used in the presence of one or more reinforcing carbon blacks, pigments or synthetic resins and certain antioxidants are polymerized. The ones gained through this way of working Products can be made by adding polymerizable, polyfunctional Cycloolefins such as bicyclopentadiene can be crosslinked to the main monomer. The molded products, which have been produced by means of the polymerization which takes place with ring opening can thereby be crosslinked that they are exposed to ionizing radiation such as y-radiation, X-rays or electron beams will. These molded products can also be crosslinked or vulcanized by incorporating certain compounds that during the heating during and after the polymerization to the conventional crosslinking ter or vulcanization of such polymers lead. The person skilled in the art can, through suitable selection of the polymerisation

- II -

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tion conditions, the catalyst or the by-products to use the catalyst production for the crosslinking of the polymer molded into the shape of the finished article. A prolonged exposure of the polymers according to the invention to active catalyst apparently leads to it an isomerization of the polymer into the thermodynamically more favorable configuration, which is usually the trans configuration and thus causes increased crystallinity

The polymerization reaction can be controlled by the incorporation of various compounds which, when heated, give off products which deactivate the catalyst. Characteristic examples of such compounds are the ammonium salts, such as Amnoniumchlorid, ammonium carbonate, ammonium acetate, ammonium oleate, Amraoiniumsulfat and ammonium phosphate, as well as further amnoniakabgebende compounds such as Tetraalky! Ammonium halides, such as zBTEtramethylammöniumchlorid, water-releasing agents, such as salts containing crystal water, such as Al ₂ ( SO ₄ ) .17 H ₂ O, NH ₁ Al (SO ₄ ) ₂ · 12 H ₂ Q, FeSO ₄ . 7 H ₂ O, MgHPO ₄ . 7 H ₃ O, KAL (SO _{4 I 2.} 12 H ₃ O, KNaCO _3. 6 H ₂ O, Na ₂ B ₄ O _7. 10 H ₂ O, Na ₃ CO _3. 10 H ₂ O, Na ₃ HPO _4, 12 H ₃ O, Na ₂ SO _4, 10 H ₂ O and ZnNO _3, 6 H ₂ O.

The following exemplary embodiments serve to further explain the subject matter of the invention. Parts and percentages are based on weight, unless otherwise noted.

Examples 1, 2 and 3

In the following three examples of the polymerization of cyclooctene taking place with ring opening are given, the the following general polymerization method is used.

All work is carried out under nitrogen. It will a 1 liter glass bottle is charged with commercially available pentane, which is washed with sulfuric acid and dried over Sillkagel has been cleaned. Commercial grade cyclooctene is then added to the pentane. In this mixture the catalyst components are injected in the following order. 1/3 of the triisobutylaluminium then tungsten

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hexachloride and the remainder of the triisobutyl .aluminum. You can run the polymerization as long as it is shown in Table I, namely at one Temperature of about 24 ° C, and then a solution to terminate the polymerization is added, the 0.1 molar solution of tetraethylene pentamine in benzene and also contains 4 g of 2,6-di-tert-butyl-p-cresol per 100 cm of benzene. That Polymer is separated off by means of coagulation in an excess of isopropanol.

The corresponding numerical values for the polymerization process and the properties of the polymer are given in the table II summarized:

Table II Polymerization
conditions . example
1 1/0 example
2 example
3 Cyclooctene (g) 212 24 85 85 Pentane (ml) 6OO 27 min. 250 250 Tungsten hexachloride (g) 1/5 25th 0.6 0.6 Triisobuty! Aluminum (g) too
set as a 25% solution
in hexane 0.736 78 0.295 0.295 Al / W molar ratio 1.0 1/0 Temperature ⁰ C rubber-
good 24 24 Polymerization time 2.7 50 min. 16 h Interruption solution (ml) 14.0 10 10 % (Attack 41 89 94 Polymer properties 0 physical appearance balata-
good fiber
good basal viscosity
in benzene at 30 ° C 3.16 1/47 Hedgehog 13.0 4/9 t trans-vinylene 74 78 % Vinyl 0 0

% of theoretical unsaturation by means of nuclear magnetic resonance analysis 93

relative crystallinity index based on X-ray analysis 0

Fiber repeat distance Ä Melting point ⁰ C 22.5 Crystallization halftime at

17.9 C below the melting point (min.) * 3000

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90

100

29 35 8th 9.8 9, 53 59 32 16 13 -

The intrinsic molar viscosity of the polymers is determined using a solution of 0.1 g of dry polymer in 100 ml of benzene determined at 30 ° C.

The gel content analyzes of the polymers are obtained by determining the percentage of polymer that is insoluble if 0.1 g of dry polymer is allowed to stand in 100 ml of benzene at 30 ° C. for 2 days.

The percentage of the trans-vinylene and vinyl content of the polymers is determined by means of infrared analysis, such as it was developed for measuring these groups in polybutadiene. It is assumed that the remaining portion of the double bonds is in the cis-vinyl configuration.

The trans-vinylene content of any given polymer is the number of trans-vinylene groups as found in finds in each case 100 repeating units (or per 100 · monomer units) which are present in the polymer, expressed as a percentage (with respect to the specific case of the polyoctenamer, an extinction coefficient becomes at 1.138 L / g polyoctanamer / cm used for the absorption that occurs at 10.35 microns so as to reduce the trans-vinylene content to calculate).

The percentage of theoretical unsaturation is determined by means of nuclear magnetic resonance analysis and shows that these polymerizations proceed almost exclusively via a ring-opening mechanism and lead to a linearly unsaturated polymer which has repeating units of the following structural formula: - ((CH ₂ ) ^ CH ₂ -CH = CH-CH ₂ - (CH ₂ ) _4m ), where m = 0, 1, 2, 3 or 4.

The polymers prepared according to these three examples

o show that a large number of polyoctenamers are possible. ^ Polyoctenamers with more than 75% trans-vinylene content are - * fibrous and crystalline and should find applications in deformed products. Polyoctenamers with an area of about _m 60 to 75% trans-vinyl content are thus indicates overall ^ that the same high impact resistance have MiÄ should be applied in products such as coatings for GoIMlIe and cables. - 14 -

Polymers with less than about 60% trans-vinylene content, such as those with more than about 40 tons cis-vinylene content rubbery and can be used to make a variety of rubber products such as pneumatic tires, in particular Running surfaces of the same and deformed rubber articles, such as seals, bushings, hoses and weatherproof Objects are applied. Polyoctenamers with trans-Viny lencontents in a range from about 25 to about 50% and preferably about 25% or less are usually rubbery products with good strength properties so that they are useful as such in combination with other rubbers in tires. Characteristic for other types of rubber are the rubber-like polymers and copolymers, such as natural rubber, as well synthetic rubbers, such as styrene-butadiene copolymers with styrene contents of about 5 to about 60% by weight and polymers from oil hydrocarbons such as butadiene and isoprene .

Polyoctenamers with trans-vinylene contents of about 30 to After compounding and vulcanization, about 50% have the physical properties as they are for motor vehicle tire treads with long service life and cold running properties are required.

The range of physical properties as exhibited by these polyoctenamers is likely to vary to the extent of the crystallinity, as reflected by their different trans-vinylene contents results. Since there is only a small difference in the percentage conversion, shows the large difference in the trans-vinylene contents that isomerization occurs under these polymerization conditions, whereby the polymer moves towards an equilibrium composition changed, which has a high trans-vinylene content.

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The dependence of the melting point on the trane vinylene content shows that a lOOIiges trans-polyoctenamer Melting point of 72 ° C and a heat of fusion of 3.5 kcal / hol which has calibrated repeating units.

Example 4

A 113 9 glass bottle is flushed with nitrogen and with 80 ml of purified pentane were charged under a nitrogen atmosphere. 8.7 g of cyclododecene are more commercially available than pentane Added variety. The catalyst components are then injected into the mixture in the following order. 0.159 g Tungsten hexachloride and 0.059 g triisobutyl aluminum. One lets the reaction takes place under nitrogen at about 24 ° C for 10 minutes long play. The polymerization is then interrupted by injecting 10 ml of methanol into the reaction vessel and then kept the mixture agitated for 10 minutes. The reaction product is by means of coagulation with additional Separated methanol. The yield is 95% solid polymer, which crystallizes to form a tough, flexible product, which is similar to balata or polyethylene 1st in physical properties.

Example 5

A 113 g glass bottle is placed under a nitrogen atmosphere with 8.7 g of commercial grade cyclododecene loaded. Then add 1 ml of a 0.1 molar benzene solution of tungsten hexachloride added to the olefin and then 0.75 ml of a 0.1 molar solution of triisobutylalurainium in heptane, everything introduced under nitrogen. The polymerization mixture is converted into a hard solid mass in one minute.

Example 6

A 113 g glass bottle is charged with 22.1 g of commercially available cyclododecantriene under nitrogen. Then 4 ml of one 0.33 molar heptane solution of triisobutylaluminum the monomer added and then 1.0 ml of a 0.1 molar Bensol solution of tungsten hexachloride, all under nitrogen, introduced. An immediate polymerization occurs with the formation of a high molecular weight polymer.

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Example 7

A number of 113 g nitrogen-containing glass bottles are made with 25.5 g of cyclooctene charged, which has been purified by means of sodium distillation and 70 ml of pentane are introduced, the was passed over silica gel. After draining about 10 ml of pentane, the bottles are filled with 4.5 ml of a 0.1 molar solution of holfram hexachloride (WCIg) in benzene and a 0.1 molar Solution of an organometallic compound in heptane, see table below. The polymerization is allowed to take place 24 ° C for about 5 hours.

organometallic millimoles of the applied% yield of compound organometallic compound polymer

Butyllithium 0.5 6.65 Diisobutyl aluminum hydride 0.45 11.70 Ethyl aluminum dichloride 0.45 26.50 Example 8

A mixture of cyclooctene and pentane with a volume ratio of 1: 7 is passed over silica gel under nitrogen. Portions of this mixture, each in an amount of 90 ml, are introduced into 11 small glass bottles and then 10 ml of pentane was blown from each of the bottles. The bottles are then first filled with triisobutyl aluminum and then with Tungsten hexachloride using the aluminum to tungsten ratios given in Table III. All reactions are carried out at about 50 ° C for a period of 24 hours, and then polymerization is carried out with addition interrupted by methyl alcohol. The polymer is then separated off with an excess of methyl alcohol:

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Table III

Pentane solution of cyclooctene with different Al / W ratios

■ nits

Implementation (0.1 molar) No. ml ++ TIBA (in heptane)

(0.1 molar) Al / W MoI-ml WCl ₆ (in ratio benzene;

% Yield of polymer

1 0.50 2.00 0 1 1 , 250 14th , 2 2 1.00 2.00 0 1 , 800 34 , 0 3 1.50 2.00 0 2 , 750 33 , 0 4th 1.75 2.00 0 , 875 33 , 0 5 2.00 2.00 1 , 000 96 , 3 6th 2.25 2.00 1 , 125 80 , 0 87 2.50 2.00 1 , 250 . 53 , 2 8th 2.75 2.00 , 375 27 , 9 9 3.00 2.00 , 500 18th , 5 10 3.50 2.00 , 750 16 , S. 11 4.00 2.00 , 000 11 , 4

+ Aluminum to tungsten

++ Abbreviation for triisobutyl aluminum.

Example 9

A 113 g glass bottle is flushed with nitrogen and charged with 30 ml of cyclooctene, which is poured over silica under nitrogen has been conducted. Then 5.0 ml of a 0.1 molar triisohutylaluminum in heptane and then 4.0 ml are added to the cyclooctene 0.1 molar tungsten hexachloride in benzene was added. A relatively high molecular weight polymer is obtained after the Reaction has been carried out for approximately 60 seconds. The bottle and its polymerization content exceeds one Temperature of 50 ° C, which indicates a very low heat of polymerization.

Example 10

A 113 g bottle is charged with 14.5 g of 1,5-cyclooctadiene and 75 ml of pentane, which have been passed as a mixture through a silica gel column under nitrogen. Approximately 10 ml of solvent are blown off before the bottle is closed

009818/1631 - X8 -

- 18 - · and is cooled ^{to -20 0 C.} 4.0 ml of a WC1 _C -

Solution with 0.1 molar concentration in benzene in the bottle and then 2.0 ml of a 0.1 molar solution of triisobutylaluminum in heptane at -20 ° C was added. One lets the polymerization takes place at this temperature for 65 hours. The polymer mass is in a 1% strength Solution of 2,6-di-tert-butyl-p-cresol in methanol coagulated. After drying, 3.48 g of polymer are separated off, and this corresponds to a yield of 24%. The polymer is khutschuk-like and has an intrinsic viscosity of 0.69 Deciliters per gram and 4.5% gel. The intrinsic molar viscosity and the gel content are determined by means of the methods according to the Examples 1, 2 and 3 determined.

The infrared analysis shows that the polymer has a spectrum identical to that of a polymer of 1,3-butadiene with a cis content of 78.9%, a trans content of 16.4% and has a 1,2-vinyl content of less than 0.1%.

The above embodiment thus explains the production of polymers, the repeating units from four Have carbon atoms, each 'a carbon-carbon - have double bond. These polymers contain at least 75% of these units in a cis-1,4 structure and have less than 0.2 or 0.1% of these units in a 1,2 structure. Such polymers are called a Considered polybutadiene in which at least 75% of the units are in the cis-1,4 configuration and less than 0.2 or 0.1% of the Units are in 1,2 configuration. Such polymers are also considered to be a polybutadiene in which at least 90% of the units have a 1,4 configuration or less as 0.2 or 0.1% of the units are in the 1,2 configuration.

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009818/1631

Example 11

In a 113 g bottle, 8.5 g of cyclooctene and 0.86 g of 1,5-cyclooctadiene are introduced under nitrogen, each purified by means of passage over silica-under nitrogen have been. 80 ml of pentane, which has been purified by washing with acid and drying over silica, is introduced into the bottle. The bottle and its contents are then heated to about 50 ° C and blown about 10 ml of pentane from the bottle. The bottle and its contents are on cooled about 24 ° C. 2 ml of a 0.1 molar benzene solution of tungsten hexachloride are introduced into the bottle and then 1.75 ml of a 0.1 molar heptane solution of triisobutylaluminum was added. The copolymerization is applied using sufficient methanol to coagulate the copolymer! brought to a conclusion. 8.1 g of a rubbery product are obtained.

009818/1631

Claims (28)

Claims 1. A process for the preparation of polymers from unsaturated alicyclic compounds, the at least one alicyclic ring, and the ring at least 8 carbon atoms and 1 to 3 carbon-carbon double bonds possesses, with ring opening, characterized in that the polymerization in the presence of a catalyst is carried out, which in the mixture (a) an organometallic compound in which the metal from the group consisting is selected from metals of groups Ia, Ha, Hb and IHa of the Periodic Table, as well as the organometallic Compound has at least one metal-carbon bond and (b) a salt of a metal selected from the group is selected from chromium, solybdenum and tungsten. 2. The method according to claim 1, characterized in that dadurc h a cycloolefin is used as the alicyclic compound, as well as the organometallic compound selected from the group consisting of from trialky aluminum compounds, dialkylaluminum halides, Alkyl aluminum dihalides, dialkyl aluminum hydrides, alkyl aluminum dihydrides, triarylaluminum compounds, Aryl aluminum hydrides and aryl aluminum hydrides, alkyllithium compounds, lithium aluminum tetraalkylene, alkaline earth metal aryls, Zinc alkylene and Grignard compounds is selected. 3. Process according to Claims 1 and 2, characterized in that a metal halide is used as the metal salt. New documents (Art 7 % 1 Paragraph 2 No. 1 Clause 3 of the amendment of September 4 , 19671 _ ₂ - 009818/163 1 BATH ORIGINAL - 2- 4. The method according to any one of the preceding claims, characterized characterized in that a molar ratio of the organometallic compound to the metal halide of about 0.1: 1 to about 30: 1 is applied. 5. The method according to any one of the preceding claims, characterized in that the cycloolefin and / or gpclododecene 1.5-cyclooctadiene and / or 1.5.9-cyclododecatriene and / or Cyclooctene is used. 6. The method according to any one of the preceding claims, characterized in that a catalyst is used in which the molar ratio of trialkyl aluminum to tungsten hexachloride is 0.1: 1 to about 30: 1. 7. The method according to claims 1 to 5, characterized in that a catalyst is used in which the molar ratio of trialkyl aluminum to molybdenum pentachloride is 0.25: 1 to about 5: 1. 8. The method according to claim 2, characterized in that cyclooctene is used as the alicyclic compound and the Catalyst triisobutyl aluminum and tungsten hexachloride in has a molar ratio of about 0.5: 1 to about 2 ©: 1. 9. The method according to claim 2, characterized in that the catalyst triisobutylaluminum and molybdenum pentachloride in a molar ratio of from about 0.25: 1 to about 5: 1. 10. Polymer, characterized in that the same is derived from an unsaturated cycloaliphatic compound, this unsaturated cycloaliphatic compound having at least one cycloaliphatic ring, this ring having at least 7 carbon atoms and 1 to 3 carbon-carbon double bonds in the cycloaliphatic ring are present. 11. Polymer, characterized in that the same is derived from a cycloolefin which has at least 7 carbon atoms in a ring, this ring having 1 to 3 carbon- carbon double bonds. 009818/1631 12. Polymer, characterized in that the same is a linear Has a structure derived from a cycloolefin, wherein the cycloolefin has at least 7 carbon atoms in a ring, the ring having 1 to S carbon-carbon double bonds having. 13. Tire, characterized in that the rubber-like material for the same is at least partially made of a polymer is composed according to claim 12. 14. Polymer, characterized in that the same in its structural formula repeating units -CH ₂ -CH = CH-CH ₂ - (CH ₂ J ₄ . 15. Tire, characterized in that the rubber-like material for the same is at least partially made of a polymer according to claim 14, is composed. 16. Polymer according to claim 14, characterized in that the same has a trans-vinylene content of about 25 to about 80 percent. 17. Polymer according to claim 14, characterized in that the same has a trans-vinylene content of at least about 15%. 18. Polybutenamer, characterized in that its structure has alternating cis and trans vinylene groups. 19. Terpolymer, characterized in that the same three various alternating repeating units having at least 7 total carbon atoms in the three repeating units Has units. 20. Polymer, characterized in that the same from a cycloolefin by ring-opening polymerization of this cycloolefin is derived, wherein the cycloolefin has at least 7 carbon atoms in a ring and this ring 1 to Has 3 carbon-carbon double bonds. 21. Polymer, characterized in that the same by means of polymerization of an unsaturated, alicyclic compound is produced, the unsaturated alicyclic compound - * - 008813/1831 has at least one alicyclic ring, the ring has at least 8 carbon atoms and there are 1 to 3 carbon-carbon double bonds in the alicyclic ring, 22. Polymer according to claim 21, characterized in that the unsaturated alicyclic compound is a cycloolefin having at least 8 carbon atoms in the ring, the ring Has 1 to 3 carbon-carbon double bonds. 23. Polymer according to claim 22, characterized in that the polymer has a linear structure. 24. Terpolymer, characterized in that the same three different, alternating, repeating units with a total of at least 8 carbon atoms in the main chain which has three repeating units. 25. Polybutadiene, characterized in that the same has less than about 0.2% 1,2-configuration, with the remainder Share is in 1,4 configuration, with about 20 to about 90% are in the cis-1,4 configuration. 26. Polybutadiene according to claim 25, characterized in that * less than about 0.2% 1,2-configuration, the remaining portion is in a 1,4-configuration, of which about 70 to about 90% are in the cls-1,4 configuration. 27. Polymer, characterized in that the same agent Polymerization of a cycloolefin has been produced by ring-opening polymerization thereof, the cycloolefin having at least 8 carbon atoms in a ring, this ring has 1 to 3 carbon-carbon double bonds. 28. Tire, characterized in that the rubber-like mass of the same is at least partially a polymer Claim 23 represents. DjeJ ^ teoiamvälte " .. ..- ^ - oipPlr ^ W. Meissner S * Dipl.-ing. H.TisCTier A6 No. 24/69 C ^ 43 Pat Ap) 009818/1631 _