DE1570336A1 - Process for the defined increase in the molecular weight of unsaturated polymeric hydrocarbons - Google Patents

Description

Process for the defined increase in the molecular weight of unsaturated polymeric, meric hydrocarbons

In the production of polymeric hydrocarbons by. catalytic ^ polymerization generally increases with increasing conversion, the viscosity of the reaction mixture. The increase in viscosity depends on the concentration and the molecular weight of the dissolved polymer. As the viscosity increases, it becomes more difficult to carry out the polymerization and stirring! Dissipate heat. The polymer concentration is therefore normally kept at values between 5 and 20 %.

Further, there are a number of polymerization methods by which the technically increasingly interesting today • high molecular weight polymers produced with great difficulty be ^N. For example, it is not uncommon for the reaction components and the solvents to be extremely pure if one wishes to avoid low space-time yields or unfavorable reaction conditions.

In addition, it is known to the molecular weight of polybutadiene or. Polyisoprene on the. Way to increase that one adds arylazo or aryl hydrazo compounds in an amount of 0.2 to 3 percent by weight to the polymerization mixture containing the polymer. However, in the case of most unsaturated, polymeric hydrocarbons, these compounds cause only a small or no increase in molecular weight.

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increase. . '.

Finally, there are already butadiene copolymers containing nitrile groups with a metal halide of the Lewis acid type and a liquid halogen compound having at least two mobile halogen atoms with mixing of the two types of compounds in the solvent-free liquid polymer, optionally after. Mixing of carbon black and heating to 150 "C, cross-linked / i.e. converted into solid, insoluble products.

It has now been found that the molecular weight of unsaturated, polymeric hydrocarbons can increase to a certain extent, if the specified, anhydrous, unsaturated, polymeric hydrocarbons with molecular weights from 1,000 to 1,000,000, preferably from 100,000 to 800,000 and in particular from 200,000 to 600,000, treated in solution with a catalyst system that

a) consists of a compound of the general formula R MeX,

α β η y-ii

in the Me »B, Al, Ga, Be, Mg, Ca, Zn, Si, Sn, Ae, Sb, Ti, Zr, P, Mo, W, Bi, Fe, Hg, Cd, V, U, VO; X »F, Cl, Br, J; R is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, Sulfoxy radical or a carboxylate anion, where y is the valence of the respective central atom Me and η is a value between 0 and the valence of the central atom means, and

b) consists of an active hydrogen containing compound, wherein the catalyst component a) in concentrations of 0.01 to 10 Percent by weight, preferably from 0.01 to 5 percent by weight and in particular 0.2 percent by weight, based on the polymer used, and the catalyst component b) in amounts from 0.002 to 2 mol, preferably from 0.005 to 1 mol and in particular from 0.01 to 0.6 mol, based on the catalyst component a), was added will.

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Suitable, unsaturated polymeric hydrocarbons are, for example, polybutadienes. It is irrelevant which method is used the polybutadiene was made. It can e.g. B. in emulsion with radical catalysts, with lithium / lithium alkylene ale catalyst or with so-called "Ziegler" catalysts, e.g. with the Kataly sat orey stern en titanium compounds or cobalt compounds be produced together with organometallic compounds in solution.

Other suitable polymers are the z. B. with vanadium contacts known in connection with organoaluminum compounds Way producible ethylene / propylene copolymers, the one unsaturated third component, such as biscyclopentadiene, contain.

Finally, unsaturated polymeric hydrocarbons are suitable for example polybutadienes, polyisoprenes and copolymers of, for example, butadiene or isoprene with monoolefins, such as styrene, which are produced with Ziegler catalysts or with alkali metals, such as in particular lithium, sodium and / or potassium or their organic compounds, as well as all other unsaturated polymeric hydrocarbons. Special Mention should be made here of the isobutylene / isoprene copolymer, the so-called Butylkatuschuk.

For some of these procedures it now prepares considerable technical Difficulties in producing polymers with viscosities significantly higher than ML-4 «50. Such polymers are but today mainly for the production of oil-plasticized rubbers of particular interest, with ML-4 viscosities being preferred between 90 and 140 are required.

According to the present process, it is now possible in a simple manner to determine the Mooney viscosity of the polymers

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e.g. from 20 to 50 or from 20 or 50 to 90 to 140 to increase. The advantage of this process is therefore that the molecular weight during the polymerization can be kept low. This advantage is particularly effective in solution polymerization, in which the resulting Polymers remain in the solution and thus with increasing conversion and with increasing molecular weight the viscosity of the reaction mixture increases.

As the figure (see attachment) shows, e.g. during polymerization of butadiene with a cobalt compound / dialkylaluminium chloride catalyst system by reducing the molecular weight during the polymerization of the solid j Substance content is greatly increased with the same solution viscosity and thus the performance of a polymerisation system accordingly can be increased.

The main solvents used for this are hydrocarbons "in question> such as aliphatic ^ and cyclic saturated hydrocarbons, open-chain and cyclic unsaturated hydrocarbons, as well as aromatic hydrocarbons such as benzene, its homologues and their isomers, hexane, butane and Isopropylcyclohexane.

The catalyst system to be used according to the invention consists of two components. The first component a) is defined by the general formula R _n MeX ^ _n , in which Me «B-, Al, Ga, Be, Mg, Ca, Zn, Si, Sn, As, Sb, Ti, Zr ,. P, Mo, W, Bi, Fe, H &. Cd, V, U, VO; XF, Cl, Br, J; R is hydrogen, alkyl. Cycloalkyl, aryl, aralkyl, alkoxy, sulfoxy radical, or a j carboxylate anion means _7, where y is the valence of the particular central atom of 'Me and η a value between 0 and the valency of the central atom means. '

Compounds of this type are, for example, uniform boron halides or boron halides in which one or two

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Halogens are replaced by the radical R, such as BP ^, BCIU, 'R-BCl ₀ , - R ₀ BCl., R, B _o Br ,; the same conditions apply to Me »Al or Ga.

• Further compounds are Grignard compounds, such as alkyl or aryl magnesium halides, such as the corresponding compounds of Be, Ca and Zn; further silicon and tin tetra-halides, such as SiCl ₂ ^ or SnGl ^ and corresponding compounds in which one or more halogens are replaced by the radical R, such as phenyl or alkyl silicon or tin tri-halide, further titanium - and zirconium tetra halides and titanium and zirconium oxy halides, vanadium tetra halides, vanadin oxy halides and anhydrous iron 3 halide and their corresponding compounds in which one or two halogen atoms are replaced by the radical R. '

Prerequisite for a flawless and reproducible i 'Veruphsführung. is the solubility of these compounds in the organic solvent in question for the specific reaction. Since many of these connections are a Have electron gaps, it is in a known manner by addition of, for example, ethers, amines or phosphines possible to make such compounds soluble. If the effectiveness is weakened somewhat as a result, it is in the in most cases no disadvantage, since such reactions are easier to handle because they are not too stormy ' get lost. The structure of the ethers and amines plays a role practically no role; i.e. it is almost irrelevant whether you use diethyl ether or tetrahydrofuran, for example.

Suitable compounds containing active hydrogen are for example water, alcohols, mercaptans, inorganic and organic acids, also phenols »thiophenols, enolizable Carbonyl compounds and imides. · '

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The alcohols are ζ. B. methanol, ethanol, n-propanol, isopropanol, Butanol and its isomers, benzyl alcohol, triphenyl carbinol, naphthyl ethyl carbinol, glycol, propylene glycol, nonanediol, Glycerine, allyl alcohol, 2-butynediol-1,3, ethanolamine, diethanolamine, Triethanolamine and trichloroethanol into consideration. Suitable Mercaptans are methyl and ethyl mercaptans and their homologues.

Inorganic acids are to be understood as meaning nitric acid, nitrous acid Acid, sulfuric acid, sulphurous acid, phosphoric acid, phosphorous acid, nitrogen-hydrogen acid, halogenated oxygen acids, such as e.g. perchloric acid.

Suitable organic acids are e.g. B. formic acid, acetic acid, propionic acid, oleic acid, stearic acid, trichloroacetic acid, linolenic acid, Propargylic acid, phenylacetic acid, naphthalenecarboxylic acids Cinnamic acid, adipic acid, alginic acid, phthalic acid, acetylenedicarboxylic

hv acid, naphthalenedicarboxylic acid, tricarballylic acid, Crotonic acid, vinyl acetic acid, acrylic acid, lactic acid, aminoacetic acid, aminovaleric acid, and ricinus acid, benzenesulfonic acids, toluenesulfpic acid ^ sulfonic acid, sulfinic acids such as benzenesulfinic acid and naphthalenefic acid as well as all homologous compounds which easily split off samples.

Suitable phenols are phenol itself, pyrocatechol, resorcinol, hydroquinone, Pyrogallol, phloroglucinol, oxyhydroquinone, inositol, l-Is, q, prQpyl- -4-oxybenzene, salicylic acid, naphthol, nitronaphthol, thipphenql and its homologues as well as polythiols.

Acetylacetone should be mentioned as enolizable carbonyl compounds and aci -nitro compounds.

Suitable imides are ditosylimide and di-trichloroacetylimide.

Polymers that contain the functional groups mentioned, such as copolymers of vinyl chloride with maleic acid,

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are suitable. Only the presence of the functional group is decisive for triggering this reaction. The on The organic radical located in the functional group does not have any or only a very small influence on the reaction.

This catalyst component b) is used in far lower concentrations as the catalyst component a) required. They are between 0.002 and 2 moles, but usually between 0.005 moles to 0.6 moles per mole of the catalyst component a).

The first catalyst component is used in concentrations of 0.0 1 to 10 percent by weight. Usually enough however, concentrations of 0.2 to 2 percent by weight, based on the polymer used;

The second catalyst component, of course, from the first must be different, is usually required in far lower concentrations. In order to be able to give precise information, are this is given in moles per mole of the first catalyst component; they are between 0.002 and 2 moles, but normally between 0.005 and 0.6 moles.

The unsaturated polymeric hydrocarbons dissolved in an organic solvent or in solvent mixtures will be the first first. Catalyst component, preferably in dissolved form, added and mixed with the polymer solution. Subsequently, the corresponding amount of the second ^ catalyst component, advantageously in dissolved form, in

be added in one portion or in portions. at

^{Adding 0} ^ in portions results in a somewhat greater increase in molecular weight

^ a.

The increase in molecular weight is the greater, the greater the amount used on the catalyst component b) is.

BATH ORIGINAL

The temperature of the reaction mixture may be between ⁰ -5o C and 100'C. The catalysts are expediently added at room temperature. After an exposure time, which can be up to 10 hours, in particular up to minutes, preferably up to a minute, the reaction mixture is in a manner known per se, optionally by destroying the catalyst with alcohol or ketones, precipitating the polymer with alcohol or stripping of the solvent with steam, worked up. This process has the advantage that the polymers in question can be dissolved in a suitable solvent and placed in front with the corresponding, easily accessible catalyst components and thus a defined increase in molecular weight can be achieved without additional gelation. In addition, the properties z. B. in the case of polybutadiene to the effect that the vulcanizates produced from these polymers have an improvement in structural strength. Another essential advantage of the process is that this reaction decisively reduces the tendency of the crude polymers to flow.

example 1

A 10% benzene solution of 1,4-cis-polybutadiene with a cip content of about 98% is prepared in a polymerisation vessel filled with nitrogen by dissolving the polymer in benzene. 0.8 parts by weight of diethylaluminum chloride per 100 parts by weight of polymer are added to this solution and then four times 0.1 mole of acetic acid, based on one mole of diethylaluminum chloride, is added every 30 minutes. One hour after the last addition, the catalyst is prepared by adding 2 parts by weight of acetone, based on polymer, decomposed, the polymer is worked up _t by evaporation of the solvent using water vapor and then dried.

Water content in the reaction mixture: 67 ppm ML-4 viscosity before the reaction: 38 ML-4 viscosity after the reaction: 81

When using formic acid and stearic acid, one obtains similar results.

The reactions are carried out as in Example 1 / with a

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Lithiumbutyl is used as a «catalyst-made» polybutadiene will. .

Water content dt "reaction mixture": 79 ppm ML-4 viscosity before reaction: 41

ML-4 viscosity after reaction: 117 Example 3

A 10% strength hexane solution of an ethylene-propylene-biscyclopentadiene terpolymer with about 4 double bonds per 1000 carbon atoms is introduced into a polymerization vessel filled with nitrogen. This solution contains 165 ppm water. At a lateral distance of 30 minutes, twice O ₁ S parts by weight and then 0.3 parts by weight of ethylaluminum dichloride, based on the polymer, are added. 30 minutes after the last addition, the catalyst is decomposed by adding 1 part by weight of acetone, and the polymer is isolated by stripping off the solvent with steam and dried.

ML-4 viscosity before reaction: 47 ML-4 viscosity after reaction: 100

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Claims (1)

CX Z, IMl 22.1.Il Claim Process for the defined increase in the molecular weight of unsaturated polymeric hydrocarbons, characterized in that the specified, anhydrous, unsaturated polymeric hydrocarbons with molecular weights of 1,000 to 1,000,000, preferably from 100,000 to 800,000 and in particular from 200,000 to 600,000, treated in solution with a catalyst system that a) consists of a compound of the general formula R MeX, in which Me ■ B, Al, Ga, Be, Mg, Ca, Zn, Si, Sn, As; Sb, Ti, Zr, P, Mo, W, Bi, Fe, Hg, Cd, V, U, VO; X * F, Cl, Br, J; R is hydrogen, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, SuIfoxy bed or a carboxylate anion denotes, where y is the valence of the respective central atom Me and η is a value between 0 and the valence of the central atom means and b) consists of an active hydrogen-containing compound, wherein the catalyst component a) in concentrations of 0.01 up to 10 percent by weight, based on the polymer used, and the catalyst component b) in amounts of 0.002 to 2 mol, based on the catalyst component a), is added j 909833/13 13 BATH ORIQINAL.