DE2619197A1 - Cyclooctadiene polyalkenamer prepn. - by polymerising in the presence of tungsten hexachloride catalyst and e.g. cyclodecadiene or cyclodecatriene cocatalyst - Google Patents

Abstract

Cis,cis-cyclooctadiene-1,5(I) is polymerised in the presence of WCl6 catalyst and a cocatalyst chosen from cis, cis-cyclodecadiene-1,6 cis, trans,trans-cyclododecatriene-1,5,9, cis,cis-1,2-divinylcyclohexane and dicyclo-pentadiene opt. in the presence of a solvent pref. at -20 to +80 (10-35) degrees C. The catalyst has improved activity, solubility and selectivity. The polymers may be used as binders in coatings or a raw material for elastomeric or thermoplastic mouldings.

Description

Polymerization process

of cis, cis-cyclooctadiene- (1,5) The invention is a Process for the polymerization of cis, cis-cyclooctadiene- (1,5), if appropriate in the presence a solvent with the aid of a catalyst consisting of tungsten hexachloride and a cocatalyst.

The production of polyalkenamers from cycloolefins with the help of Metathesis catalysts are known (G. Dall'Asta in "Makromol. Chem. 154 (1972) t - 1911). Under metathesis catalysts, homophene and heterogeneous catalysts are grounded understood the compounds of metals of the 5th to 7th subgroup of the periodic System, principally of niobium, tantalum, molybdenum, tungsten and rhenium as well optionally compounds of the metals of the 1st to 3rd main group of the periodic Systems, e.g.

their alkyls or hydrides, optionally with other ligands, such as e.g. halogen, alkoxyl or carboxylate groups, or Lewis acids in their place contain. In addition, the metathesis catalysts are known to have further activating agents Additives such as alcohols, epoxides, tert. -Butyl hypochlorite, peroxides, carboxylic acids, aromatic nitro compounds, vinyl halides, vinyl and allyl ethers and esters etc. included (BT-AS t 072 811, FR-PSS 1 394 380 and 1 467 720, Dutch Patent applications 65-10331, 66-05105, 66-14413, 67-04424, 67-14559, 68-06208, 68-06211 and 68-06209).

Since the common alkyl or hydride compounds of the 1st to 3rd Main group of the periodic system on the one hand expensive and on the other hand im are generally difficult to handle, attempts have been made without Addition of such compounds to carry out metathesis reactions.

So it is known that when exposed to Wolframhexachloricj a small amount of polymer is obtained on cyclopentene after long reaction times (IT-PS 784 307).

The leader is from DT-OS 1 909 226 a process for polymerisation various cycloolefins are known, including, inter alia. Tungsten hexachloride and an aluminum trihalide can be used as a catalyst system.

It is known that one can use cyclooctadiene- (1,5) with a combination from tungsten hexachloride and phenyldiazomethane into polynesians (Eur. Polym. J. 10 (1974) 901).

Finally, it is known from DT-OS 2 332 564 that cyclooctadiene (1,5) with halides of tungsten, molybdenum, tantalum or rhenium as a catalyst in The presence of certain bicyclo- [2,2,1] -heptadiene- (1,5) can be polymerized.

All of these prior art methods have at least one the following disadvantages: 1. Low activity of the catalyst system used and as a result, a high catalyst requirement, which inevitably leads to high ash contents in the polymers.

2. Poor solubility of the catalyst components and thus difficulties when metering the catalyst.

3. Low selectivity of polyalkenamer formation by favoring undesirable side reactions.

4. Use of expensive or difficult to make connections as cocatalysts.

The object of the invention was therefore to overcome these disadvantages of the process to reduce or overcome the relevant level of technology.

It has now been found that cis, cis-cyclooctadiene- (1,5), if appropriate in the presence of a solvent with the aid of a tungsten hexachloride catalyst and cis, cis -cyclodecadiene (1,6), cis, trans, trans -cyclododecatriene- (1,5,9), cis, cis-1,2-divinylcyclohexane or can polymerize dicyclopentadiene as a cocatalyst.

The cis, cis-cyclooctadiene- (1,5) polymerizable by the process according to the invention is accessible by catalytic cyclodimerization of butadiene (Liebigs Angew. Chem. 727: 143 (1969)).

The process according to the invention can be carried out with or without an inert solvent be performed. Suitable solvents are those that the implementation of Allow thesis reactions with the catalysts which can be used according to the invention.

The most important representatives from the group of aliphatic, alicyclic, aromatic and halogenated hydrocarbons are: pentane, hexane, Heptane, n- and iso-octane, isononane (hydrogenated trimerpropene), n-decane, isododecane (hydrogenated tetramerpropene), cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, Ethylcyclohexane, isopropylcyclohexane, cyclooctane, decahydronaphthalene, hydrogenated Terpenes such as pinane and camphane, cyclohexene and its substitution products, benzene, Toluene, om-, p-xylene, ethylbenzene, o-, m-, p-diethylbenzene, n-propylbenzene, isopropylbenzene and other mono- to polyalkylbenzenes, tetrahydronaphthalene, methylene chloride, chloroform, Carbon tetrachloride, 1,2-dichloroethylene, trichlorethylene, tetrachlorethylene, Chlorobenzene, o-dichlorobenzene, trichlorobenzene (mixture of isomers), bromobenzene, fluorobenzene, 1,2-dichloroethane.

It is essential that the solvents and the reactants are free of water and other H-acidic compounds and compounds with donor functions (Lewis bases) and peroxides are used.

Except for very small quantities, which may be intended to be obtained When effects are added, such contaminants generally degrade the activity of the catalyst.

T) ie together with the commercially available and, if necessary, cleaned Tungsten hexachloride usable cocatalysts can be obtained in the following manner be: Cis, cis-cyclodecadiene (1,6) can be according to known methods of the prior art of technology. First cistrans-cyclodecadiene (1,5) from the inexpensive monomers butadiene, available in almost unlimited quantities and t-ethylene (G. Wilke and P. IIeimbSch, Angew. Chem.

75, (1963), page 10). Then this cis - trans-Cyclo decadiene- (1,5) converted into the cis, cis-cyclodecadiene- (1,6) with the aid of an isomerization catalyst (DT-PS 1 230 023 or dissertation II. G Nüssel, Ruhr University Bochum (1970), Page 89).

Cis, trans, trans -cyclododecadiene- (1,5,9) is by catalytic cyclotrimerization accessible from butadiene (Liebigs Angew. Chem.

727: 143 (1969)).

Cis, cis-1,2-divinylcyclohexane is obtained from cis, trans-cyclodecadiene- (1,5), the production of which has already been mentioned, by thermal Cope rearrangement (Angew. Chem. 76: 859 (1964)).

Dicyclopentadiene is formed as a Diels-Alder adduct from cyclopentadiene (See Houben-Weyl, methods of organ; Chemistry, Vol. V / 1 c (1970), 959), which in the C5-Lohlemcasserstoffgemischen the pyrolysis and cracking gasoline is included.

as well as the cis, cis-cyclooctadiene- (1,5) and to be polymerized if appropriate, the solvents must also be free of water and the cocatalysts other II-acidic compounds and compounds with donor functions and Be peroxides. this can e.g. . can be achieved by over aluminum oxide under dry inert gas immediately before use percolated.

The molar ratio of cisscis-cyclooctadiene (1.5) to tungsten hexachloride in the present process is generally between 50 and 7,000, preferably between 500 and 2,500, especially between 750 and 2,000. The lower limit the molar ratio is determined by the well-known Friedel-Crafts activity of tungsten hexachloride, which can lead to undesirable by-products, and the upper limit by the possible inactivation of the catalyst system determined by impurities.

The lower ratio of cocatalysts to tungsten hexachloride must be at least 2: 1 in the method according to the invention. It's preferably sol for cis, cis-cyclodecadiene- (1,6) and for divinylcyclohexane 5 to 25: 1, for cis, trans, trans-cyclododecatriene- (1,5,9) 40 to 6G: 1 and for dicyclopentadiene 10 to 15: 1.

The process according to the invention can be both batchwise and Carried out continuously at temperatures from -20 to + 80 ° C, preferably from +10 to + 35 ° C will. In general, one proceeds in a polymerization so that one to polymerizing cis, cis-cyclooctadiene- (1,5), optionally together with a solvent or solvent mixture and then initially the cocatalyst or a solution thereof and then a solution of tungsten hexachloride in a suitable one Solvents, e.g. B. Renzol admits. The order of addition of the catalyst components is not critical per se, but it is recommended, especially in the case of low monomer-tungsten hexa-chloride V ratios, first add the cocatalyst. Optionally one can use the molecular weight of the polyalkenamers which can be prepared by the process according to the invention by addition more suitable Connections, e.g. B. acyclic alkenes with one or more non-conjugated Double bonds which can be terminal or internal and which have no substituents should wear rules. Such compounds are e.g. B. Penten-1, Hexen-1, Hepten-i Octene-i, pentene-2 and tetradecene-7. The addition of the regulating compound should be possible before the addition of the second catalyst component, but in good time at the latest done before the inactivation of the catalyst that the intended scheme the molecular weight still occurs.

The polymerization takes place after the reaction time desired in each case terminated by the catalyst, for example by adding an H-acidic compound. The polymers are then isolated and purified in a known journey. If you occur in solution or liquid, the catalyst residues are removed after stopping the polymerization by washing out the polymer-containing phase with an aqueous one or aqueous-alcoholic solution of agents, which dissolve on the first as Compounds of the H-acidic substances present catalyst residues act. Such Solventing substances are z. B. acids, alkalis or complexing agents such as acetylacetone, Citric or tartaric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, etc. the polymers are then separated by precipitation (e.g.

Pouring into a precipitant such as methanol, isopropanol or acetone) or distilling off the solvent (e.g. by blowing in steam or Injecting the polymer solution into hot water). When the polymers are in pollen or powder form from the solution of the monomer precipitate, you can also through Separate the liquid by filtration, centrifugation or decanting and first then subject to the treatment to remove the catalyst residues. For protection Polyalkenamers can be used against oxidation, gelation and other signs of aging in various stages of work-up stabilizers z. B.

from the class of the aromatic amines or the sterically hindered Phenols add. Likewise, any further cleaning can be carried out by falling over the Perform polymers if this should be necessary. After these operations the polymer is dried in a likewise known manner.

The polybutene which can be produced by the process according to the invention are suitable e.g. B. in the low molecular weight range, optionally after further reactions as a binder for coating agents and in the high molecular range primarily as Raw material for the production of elastomeric or thermoplastic moldings.

The special purpose depends on the molecular weight and the Proportion of cis and trans double bonds.

The following examples serve to further illustrate the invention. The reduced specific viscosity (nsv) was in all cases at 135 ° C in Decalin determined. The absorption band was used to determine the cis-trans-C = C ratio evaluated at 730 cm in the infrared spectra of the polymers.

Example 1 In a dry three-necked flask, 1.5 ml of a 0.1 molar Solution of tungsten hexachloride in benzene with stirring to a cooled to 0 ° C Mixture of 30 ml (245 mmol) of cis, cis-cyclooctadiene- (1.5) and that given in Table 1 Amount of cocatalyst cis, cis-cyclodecadine- (1.6) added.

Peroxides and any existing traces of moisture were removed before the Use by percolation over aluminum oxide from the as ionomer or cocatalyst used alkenes removed.

The contents of the flask were then heated to the desired reaction temperature. The polymerizations, recognizable by an increase in viscosity, were interrupted at the latest when the stirrer got stuck by adding 2 ml of a 5 percent alkaline solution of 2,6-di-tert-butzl-p-Kresel (Ionol) in isopropanol. The polymers precipitated with an excess of isopropanol were then boiled for about 90 minutes with fresh isopropanol, dried to constant weight and analyzed. The results of experiments 1 to 11 and of comparative example A are summarized in Table I. Table I. Molver polymer yield Coca Ratio Molver Reaction Reaction RSV IR Vers. Lysator coca ratio temperature time (g) (% of theory) (dl / g) (% cis- No. (ml) analyzer / monomer / (° C) (min) C = C WCl6 WCl6 A - - 1 645 20 120 - - - - 1 0.06 2.6 1 645 20 34 1.8 6.8 3.0 90 2 0.09 4.0 1 645 20 34 3.5 13.2 insol. 90 3 0.12 5.3 1 645 20 11 21.7 81.6 insol. 80 4 0.25 11 1 645 20 11 23 86.5 insol. 73 5 0.5 22 1 645 20 11 19.5 73.3 insol. 65 6 1.0 44 1 645 20 11 5.6 21.1 insol. 89 7 1.5 66 1 645 20 34 0.6 2.3 2.25 89 8 0.25 11 1 645 0 14 12.1 54.5 insol. 90 9 0.25 11 1 645 20 14 19.4 72.9 insol. 90 10 0.25 11 1 645 50 14 3.0 11.3 insol. 91 11 0.25 11 1 645 80 14 2.2 8.3 1.98 88 Example 2 In the procedure described in Example 1, 30 ml of cis, cis-cyclooctadiene (1.5) with the amounts cis, cis-1,2-divinylcyclohexane and 0.15 ml of mol of tungsten hexachloride (0.1 m in Benzene) polymerized at the specified temperatures and reaction times. The results of experiments 12 to 20 are summarized in Table II.

Table II Molver polymer yield Coca Ratio Molver Reaction Reaction RSV IR Vers. Lysator coca ratio temperature time (g) (% of theory) (dl / g) (% cis- No. (ml) analyzer / monomer / (° C) (min) C = C WCl6 WCl6 12 0.06 2.6 1 645 20 102 3.1 11.7 1.23 89 13 0.09 4.0 1 645 20 102 6.7 25.2 1.22 90 14 0.12 5.3 1 645 20 109 9.2 34.6 1.20 89 15 0.12 5.3 1 645 0 111 7.4 27.8 1.19 92 16 0.12 5.3 1 645 20 111 4.8 18.0 0.53 86 17 0.12 5.3 1 645 20 111 2.6 9.8 0.32 80 18 0.25 11 1 645 20 109 7.5 28.2 0.46 89 19 0.5 22 1 645 20 109 7.0 26.3 0.21 84 20 1.0 44 1 645 20 109 3.3 12.4 0.14 85 Example 3 In the procedure described in Example 1, 30 ml of cis, cis-cyclooctadiene (1.5) with the amounts given in Table III of dicyclopentadiene and 0.15 mol of volfram hexachloride (0.1 mol in benzene) at 20 OC and polymerized for the specified reaction times. The results of tests 21 to 24 are shown in Table III.

Table III Molver polymer yield Coca Ratio Molver Reaction Reaction RSV IR Vers. Lysator coca ratio temperature time (g) (% of theory) (dl / g) (% cis- No. (ml) analyzer / monomer / (° C) (min) C = C WCl6 WCl6 21 0.09 4.3 1 645 20 48 0.1 0.4 ++ 22 0.12 6 1 645 20 45 0.7 2.6 2.75 81 23 0.25 12 1 645 20 45 3.7 13.9 3.90 88 24 0.5 24 1 645 20 45 0.1 0.4 ++ + was not determined. Polymerized 15 m mol of tungsten hexachloride (0.1 m in benzene) at the specified temperatures and reaction times. The results of tests 25 to 34 are shown in Table IV. Table IV Molver polymer yield Cokata- Ratio Molver Reaction- Reaction- RSV IR Vers. Lysator coca ratio temperature time (g) (% of theory) (dl / g) (% cis- No. (ml) analyzer / monomer / (° C) (min) C = C WCl6 WCl6 25 0.5 18 1 645 20 81 0.2 0.8 2.72 + 26 1.0 37 1 645 20 81 1.7 6.4 2.86 89 27 1.5 55 1 645 20 81 4.5 16.9 2.75 89 28 1.5 55 1 645 0 88 2.0 7.5 2.04 90 29 1.5 55 1 645 50 88 1.9 7.1 1.53 86 30 1.5 55 1 645 80 88 0.2 0.8 2.20 + 31 2.0 74 1 645 20 210 1.0 3.8 2.53 89 32 3.0 111 1 645 20 210 0.4 1.5 2.62 88 33 5.0 185 1 645 20 210 0.1 0.4 insol. + 34 10.0 370 1 645 20 210 0.1 0.4 2.90 + + was not determined Minutes was canceled.

The results of experiments 35 to 37 are summarized in Table V.

Table V Polymer yield RSV IR Vers. No. solvent (g) (% of theory) (dl / g) (% cis-C = C) 35 hexane 2.4 9.0 2.80 94 36 benzene 0.4 1.5 3.18 89 37 cyclohexane 0.9 3.4 2.75 87 Example 6 In the procedure described in Example 1, 30 ml each of cis, cis-cyclooctadiene (1.5) with the addition of various amounts of 1-octene to regulate the molecular weight and 0.15 mmol of tungsten hexachloride and 1.5 ml of cis, trans, trans-cyclododecatriene- (1,5,9) polymerized at 20 ° C within 85 minutes. The results of tests 38 to 41 are summarized in Table VI.

Table VI Octene-1 polymer yield RSV IR Vers. No. (ml) (g) (% of theory) (dl / g) (% cis-C = C) 38 0 5.2 19.5 1.85 89 39 0.03 2.6 9.8 1.15 89 40 0.06 2.0 7.5 0.85 88 41 0.12 2.2 8.5 0.62 88 Example 7 In the procedure described in Example 1, varying amounts of cis, cis-cyclooctadiene- (1,5) were added at 20 ° C. within 180 minutes with a catalyst made from 1.5 ml of cis, trans-cyclododecatriene- (1,5,9 ) and 1.5 ml of a 0.1 molar solution of tungsten hexachloride in benzene. The results of tests 42 to 44 are summarized in Table VII.

Table VII Molver Vers. Monomer ratio polymer yield RSV No. (ml) Monomer / (g) (% of theory) (dl / g) (% cis-C = C) WCl6 42 60 3 300 7.6 28.6 1.84 85 43 90 # 4 950 3.8 14.3 2.07 85 44 120 6 600 2.7 10.1 1.75 86

Claims (3)

Claims 1. Process for the polymerization of cis, cis-cyclooctadiene- (1,5) optionally in the presence of a solvent with the aid of a catalyst, consisting made from tungsten hexachloride and a cocatalyst, c h n e t that the cocatalyst cis, cis-cyclodocadiene- (1,6), cis, trans, trans-cyclododecatriene- (1,5,9), cis, cis-1,2-divinylcyclohexane or dicyclopentadiene are used. 2. The method according to claim 1, d a d u r c h g e k e n n z e i c h n e t that one polymerizes at temperatures from -20 to + 80 ° C. 3. The method according to claim 2, d a d u r c h g e k e n n z e i c h n e t that one polymerizes at temperatures from +10 to +35 0C.