DE2051798C3 - - Google Patents

Description

characterized in that as a catalyst component C) a monocarboxylic acid having 1 to 20 carbon atoms which is soluble in the reaction mixture, which is substituted by halogen or an optionally substituted aryl or cycloalkyl radical can be used and the catalyst component B) is basically added as the last component will.

2. The method according to claim 1, characterized in that the monocarboxylic acids are formic acid. Acetic acid, propionic acid, monochloro, dichloro and trichloroacetic acid, benzoic acid, palmitic acid, Stearic acid can be used.

3. The method according to claim 1 to 2, characterized in that the molar ratio of organoaluminum Connection to monocarboxylic acid 1: 0.1 to 1:! amounts to.

4. The method according to claim 1 to 2, characterized in that the molar ratio of organoaluminum Connection to monocarboxylic acid is 1: 0.25 to 1: 0.75.

5. The method of claim 1 to 4, characterized in that the reaction temperatures in the range of - 50 to 40 are ⁰ C.

The invention relates to a process for the preparation of polyoctenamers by ring-opening Polymerization of cyclooctene in a solvent using catalysts consisting of several components.

It is known that cyclic olefins, which at least have an unsubstituted ring double bond, can be polymerized with opening of the ring. The catalysts used for this ring-opening polymerization contain metals of the 5th to 7. Subgroup of the periodic table or its compounds. Both Supported catalysts are used (cf. German Auslegeschrift 10 72811) and, preferably, reaction products of compounds of the metals mentioned with organometallic compounds or hydrides of Metals of the 1st to 3rd main group or the 2nd subgroup of the periodic table and, if applicable Compounds containing one or more Hydroxyljiud / or Contain sulfhydry groups (see the French Patent documents 13 94 380 and 14 67 720 and the laid-out documents of the Dutch patent applications 65-10331, 66-05 105, 66-14413, 67-04424, 68-06 208 and 68-06 211).

The catalysts described there contain compounds of molybdenum or tungsten and as organometallic compounds primarily those of the

ίο aluminum. According to the documents laid out by Dutch patent applications 67-H559 and 68-06 209 can also contain vanadium, niobium. Tantalum.

_ ■ rhenium, technetium or manganese components of the Be catalyst systems. According to DT-OS 19 09 226

Catalyst systems can also be used which

a halide or oxyhalide of molybdenum or tungsten, in which the oxidation state of the metal is 4, 5 or 6 is. and an aluminum trihalide.

It has now been found that polyoctenamers with an increased cis content can be obtained by ring-opening polymerization of cyclooctene in a solvent by means of a catalyst consisting of

A) a tungsten halide or tungsten oxyhalide, where the tungsten is o-valued,

B) an organoaluminum compound of the general formula AlR "X (3-n). in which n- is 1 or 1.5. R represents an alkyl radical with ί to 4 carbon atoms and X represents chlorine or bromine, and

C) an organic compound containing an OH group

can be produced by using a monocarboxylic acid which is soluble in the reaction mixture as catalyst component C) with 1 to 20 carbon atoms, which by halogen or an optionally substituted aryl or Cycloalkyl radical can be substituted, used and the catalyst component B) basically last Component is added.

As component A) tungsten halides or oxyhalides come into question, the tungsten 6wtig is available. Representatives of these compounds are

z. B. tungsten hexachloride, tungsten oxytetrachloride, tungsten hexabromide. Are preferably used WoIfram (VI) chloride and tungsten oxytetrachloride.

For component B, organoaluminum compounds of the general formula are used

AlR _n X (3-n)

used.

Here, η can assume the value for 1 or 1.5. R stands for an alkyl radical with 1 to 4 carbon atoms. X means chlorine or bromine.

Typical representatives of such organoaluminum compounds are, for. B. Ethylaluminium dichloride,

Ethyl aluminum dibromide, ethyl aluminum sesquichloride. Ethyl aluminum dichloride is preferably used. Such monocarboxylic acids come as component C in question, which are soluble in the reaction mixture. So it may be necessary if a certain monocarboxylic acid is to be selected that an appropriate solvent must be selected. It has been found necessary that a monocarboxylic acid selected according to the invention in the reaction

tion medium must be soluble. otherwise the catalyst system is not fully activated and the yield of polyalkenamers decreases monocarboxylic acids used have 1 to 20 carbon atoms, which are optionally replaced by halogen or a substituted aryl or cycloalkyl radical can be substituted. So z. B. formic acid. Acetic acid, Propionic acid, chloro- and dichloroacetic acid, benzoic acid, Palmitic acid, 0-naphthoic acid. Stearic acid can be used. to

Acetic acid and chloroacetic acid are preferably used.

The tungsten halides become the organoaluminum Compounds in a molar ratio of 1: 2 to 1:30. preferably in a ratio of 1: 4 to 1:20, used. The molar ratio of organoaluminum compound to monocarboxylic acid used is 1: 0.1 to 1: 1, preferably 1: 0.25 to 1: 0.75. Care must be taken that the use ratio of 1: 1 in the direction of an excess Monocarboxylic acid is not exceeded, otherwise the yields drop very sharply. To achieve For good yields, the amount of monocarboxylic acid used should not be too low. If, however, for procedural reasons, the amount of monocarboxylic acid is maintained while maintaining the amount of tungsten reduced, a good yield can still be obtained within certain limits, if the amount of organoaluminum compound is increased for this. The specified ratios must, however, be observed in any case.

The molar ratios of cyclooctene to tungsten halide are generally in the range from 100: 1 to 4000: 1, preferably in the range from 500: 1 to 2000:!. Elected.

The reaction temperatures can be selected in the range from -50 to 40 ^° C., preferably in the range from -40 to 20 ^° C. Although lower temperatures are also possible, there are usually difficulties in still sufficiently dissolving the catalyst. If the temperatures chosen are too high, the catalyst begins to decompose.

It is surprising that the catalysts used according to the invention can be prepared since it is known that organoaluminum compounds decompose in the presence of acids.

When preparing the catalyst, care must be taken that the organoaluminum compound is always added as the last component.

The process according to the invention is carried out in solution, including inert solvents such as benzene, Toluene, cyclohexane, methylcyclohexane, isopropylcyclohexane, decalin, hydrogenated kerosene, paraffin oil or Trichlorethylene, preferably hexane, heptane, octane, Methylenchloi id or perchlorethylene, in amounts of 5 up to 1000, preferably from 50 to 500% by weight, based on the monomer used, can be used.

A particular advantage of the method is that the polymerization is carried out than usual already at lower temperatures can be ^ _0, without the yields fall sharply. This can cause undesirable side reactions such. B. the gelation of the polymers or the alkylation of an aromatic solvent can be avoided. A further advantage of the process according to the invention is the possibility of obtaining products with an increased cis content with the same conversions as in processes according to the prior art.

After the polymerization has ended, the polyoctentanamers isolated and purified in a known manner If the polyoctenamers in solution or occur in liquid form, the catalyst residues are removed after stopping the polymerization with an alcohol or another H-acidic compound by washing out the polymer-containing phase with an aqueous or Aqueous-alcoholic solution of agents which dissolve initially as alcoholates or compounds the H-acidic substances present catalyst residues act. Such dissolving substances are z. B. acids, alkalis or complexing agents, such as acetylacetone, citric or tartaric acid, ethylcndiamintciracetic acid. Nitrilotriacetic acid, etc. The polymers are then separated by precipitation (/ _ B. Pouring into a precipitant such as methanol, isopropanol or acetone) or distilling off the solvent (λ B. by blowing steam or spraying the polymer solution into hot water). If the polymers precipitate in flake or powder form from the solution of the monomer, they can be used also by filtration. Separate the liquid by centrifugation or decanting and only then the Subject treatment to remove the catalyst residues. To protect against oxidation, gelation and other signs of aging can be seen in the polyalkenamers in various stages of work-up Stabilizers e.g. B. from the class of aromatic amines or sterically hindered phenols add. You can also carry out a further purification by falling over soluble polymers, if this should be necessary. After these operations, the polymer is also known in the art dried.

Examples

The experiments are carried out according to the following procedure: In a triple tubed 1 -! - glass flask or chlorination pot with stirrer and reflux condenser and attached dropping funnel, the specified amount of cyclooctene and hexane was brought to the reaction temperature under pure nitrogen by cooling or heating and with the components of the polymerization catalyst offset. After the specified reaction time, the catalyst was destroyed by adding 50 ml of methanol, which contained 3 g of potassium hydroxide and 2 g of 2,6-di-tert-butyl-p-cresol, and the reaction mixture was used to wash off the catalyst residues one hour after the addition of 100 ml of distilled water and 50 ml of methanol - so that a second phase of 50% methanol is formed - continued to stir and then the polymer was precipitated by pouring the organic phase into 2 l of methanol. After the polymer had been boiled for two hours with 500 ml of pure methanol, it was dried to constant weight for about 40 hours in a vacuum drying cabinet at 50.degree. The polymer thus obtained was used to determine the yield and the analytical data. A blank test was carried out in order to eliminate sources of error from changing impurities in the solvent, the monomer or the catalyst components, in each case parallel to the investigation of the examples according to the invention. Unless otherwise indicated, all RSV values are in decalin at 135 ⁰ C.

Table 1 ^# )

Venish No.

Monomer

acetic acid [mmol]

polymer yield

[G]

RSV

St.

trans salary

A x «

Cyclooctene

0.0 6.6 0.65 48 0.5 13.6 0.76 42 1.0 16.7 1.65 37 1.5 27.1 insoluble 31 2.0 332 332 37 2.5 0.0 - -

*) In all experiments the polymerization temperature was VC and the reaction time 45 minutes. The reaction mixture in the experiments consisted of 50 ml of monomer and 200 ml of hexa Acetic acid used **) χ = blank tests

Table U ')

Attempt no.

RCOOH

[mmol]

Polymer yield

[G]

RSV FdI

trans salary

A. x ") 0.0 6.0 0.66 1 1.0 palmitic acid 18.0 1.60 2 0.5 chloroacetic acid 11.4 0.79 3 1.5 dichloroacetic acid 32.0 2.60 4th 1.5 benzoic acid 39.8 insoluble 5 0.5 formic acid 17.4 039 B. X 0.0 0.9 insoluble 1 0.5 14.7 2.28 2 13th 17.0 237 3 2.0 163 3.17 C. X 0.0 28.8 2.84 1 392 insoluble 2 2.0 33.7 537 D. X 0.0 1.7 - 1 4.0 403 insoluble 2 5.0 41.0 2.67 E. X 0.0 5.0 0.42 1 8.0 39.3 insoluble 2 9.5 28.9 134

66 60 42 47 67 51 56 35 32 28 36 46 41 51 55 52 65 33 63

*) In all experiments, 50 ml of cyclooctene in 200 ml of hexane were reacted at 0 ° C. in 45 minutes (test series B in 15 minutes) In each case, 05 mmoles of WCU (test series C: WOCU) were used. In test series A and C, 2 mmoles were used for the test series D used 5 mmol and E 10 mmol ethylaluminum dichloride; in test series B 2 mmol- (C2Hi) i.5AICli, i were used. Acetic acid was used in series B to E **) χ = blind tests.

Table III ·)

Attempt no.

Polym. Temp. Catalyst addition ° C [mmol]

polymer yield

[G]

trans salary

1 0 4.5 acetic acid 160.7 insoluble 50 2 (comparison) 0 4.5 ethanol 162.5 insoluble 88 3 20th 43 acetic acid 1612 insoluble 50 4 (comparison) 20th 43 ethanol 1642 insoluble 92

*) In all experiments, 200 ml of cyclooctene in 400 ml of hexane were used in 45 minutes

In addition to the third component mentioned, the catalyst contained 1.5 mmol WOe and 6 mmol C2H5AICI2.

j *

Table IV)

Attempt no.

Polym. Temp. Catalyst ^{addition 0} C [mmol]

Polymer yield

RSV Tdf

trans salary

1 -40 ° 0.0 acetic acid 0.3 - . - 2 -40 ° 1.5 acetic acid 2.3 insoluble 20th 3 -20 ° 0.0 acetic acid 1.1 2.47 25th 4th -20 ° 1.5 acetic acid 6.7 4.71 23

*) In all experiments, 200 ml of cycloocene were reacted in 400 ml of hexane at the specified temperatures within 60 minutes. The catalyst used was 0.5 mmol of WCIe and 2.0 mmol of ethylaluminum dichloride; in experiments 2 and 4 the catalyst was prepared by adding 1.5 mmol of acetic acid.

<09686Ali

Claims (1)

Patent claims: 1. Process for the production of polyoctenamers with increased cis content due to ring-opening polymerization of ": n cyclooctene in a solvent by means of express. ■ Catalyst consisting of A) a where?> A- ^ halide or tungsten oxyhalide. wc t «c that tungsten is essential, B) an alup ^ aemorganic compound of the general formula AlR _n Xp-B). in which n = i or Ιφ is K $ for an alkyl radical with 1 to 4 carbon atoms j, '- d> X stands for chlorine or bromine, and C) an organi containing an OH group