DE1495403A1 - Process for the defined increase in the molecular weight of unsaturated polymeric hydrocarbons - Google Patents

Description

CHEMISCHE WERKE HÜLS AG. Marl, December 7, 1964

- Patent Department - 1405 / Br

U95403

Our reference: O.Z. 1924

Process for a defined increase in molecular weight unsaturated polymeric hydrocarbons

In the production of polymeric hydrocarbons by catalytic polymerization, the viscosity of the reaction mixture generally increases with increasing conversion. Included the increase in viscosity depends on the concentration and the molecular weight of the dissolved polymer. With increasing Viscosity it becomes more difficult, the polymerization 'and heat of stirring “The polymer concentration is therefore normally maintained between 5 and 20%.

There are also a number of polymerization processes, according to which the high molecular weight polymers, which are becoming more and more interesting from a technical point of view, can only be found with great difficulty can be produced. For example, it is not uncommon for the reaction components and solvents to be extremely pure required if you want to avoid low space-time yields or unfavorable reaction conditions.

In addition, it is known the molecular weight of polybutadiene or to increase polyisoprene in such a way that the Polymer-containing polymerization mixture arylazo or aryl hydrazo compounds in an amount of 0.2 to 3 percent by weight clogs. However, these compounds have only one effect on most unsaturated polymeric hydrocarbons little or no increase in molecular weight.

Finally, nitrile group-containing butadiene copolymers with a metal halide of the Lewis acid type and a liquid halogen compound with at least two mobile halogen atoms with mixing of the two types of compound into the solvent-free liquid polymer, given

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if cross-linked after adding carbon black and heating to 150 ° C., i.e. converted into solid insoluble products.

It has now been found that the molecular weight is more unsaturated polymeric, preferably elastomeric hydrocarbons, produced by polymerizing diolefins or copolymerization ▼ on mono- with diolefins or mixed polymerisation of different diolefins with one another in inert organic solvents metallic sodium and / or potassium or their organic compounds as a catalyst, with molecular weights from 1000 to 1,000,000, preferably from 100,000 to 800,000 and especially from 200,000 to 600,000, can be increased in a simple manner if the reaction mixture or the mixture of different reaction mixtures after completion of the polymerization or after reaching the desired conversion before or after decomposition of the polymerization catalyst with a catalyst system which

a) consists of a compound of the general formula R MeX « in the Me ■ B, Al, Ga, Be, Mg, Ca, Zn, Si, Sn, As, Sb, Tl, Zr, P, Mo; W, Bi, Fe, Hg, Cd, V, U, VO; X = F, Cl, Br, J; R is a 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 Central atom means, and

b) consists of an active hydrogen-containing compound, where the catalyst component a) in concentrations of from 0 to 10 percent by weight, preferably from 0.01 to 5 percent by weight and in particular from 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 0.1 oil to 0.1 β mol, based on the Kktalysatorkoxnponente a), is added.

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Suitable unsaturated polymeric hydrocarbons are, for example, polybutadienes, polyisoprenes and copolymers of for example butadiene or isoprene with monoolefins such as styrene, those with sodium and / or potassium or their organic Connections can be made.

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, however today of particular interest for the production of oil-plasticized rubbers, 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 the polymers z. B. from 20 to 50 or from 20 or 50 to 90 to 140 to increase. The advantage of this procedure is that that the molecular weight can be kept low during the polymerization. This advantage is particularly effective in solution polymerizations, in which the resulting polymer is in solution remains and as a result, the viscosity of the reaction mixture increases with increasing use and with increasing molecular weight.

Suitable solvents for this are mainly hydrocarbons, such as. B. aliphatic ^ and cyclic, saturated hydrocarbons, open-chain and cyclic, unsaturated hydrocarbons, as well as aromatic hydrocarbons, such as. B. 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 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, VQ; X-F, Cl, Br, J; R a hydrogen, alkyl, cycloalkyl, aryl, Aralkyl, alkoxy, sulfoxy radical or a carboxylate anion means.

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where y is the valence of the respective central atom Me and η one Value between 0 and the valence of the central atom means.

Compounds of this type are, for example, uniform boron halides or boron halides in which one or two halogens have been replaced by the radical R, such as BF ₃ , BCl ₃ , R-BCl ₃₁ R ₂ BCl, R ₃ B ₃ Br ₃ ; the same conditions ^{exist with Me s} Al or Ga.

Other compounds are Grignard compounds, such as alkyl or Aryl magnesium halides, such as the corresponding compounds of Be, Ca and Zn; other silicon and tin tetrahalides, such as SiCl or SnCl. and corresponding connections, in where one or more halogens have been replaced by the radical R, such as phenyl or alkyl silicon or tin trihalide, further titanium and zirconium tetrahalides and titanium and zirconium oxyhalides, vanadium tetrahalides, vanadium oxyhalides and anhydrous iron-3-halide and their corresponding compounds, in where one or two halogen atoms have been replaced by the radical R.

This catalyst component a) is in concentration / from 0.01 to 10 percent by weight used. Normally, however, concentrations of 0.2 to 2 percent by weight, based on polymers, the end.

This catalyst component a) first reacts with the alkali catalyst in approximately equimolar amounts. The resulting reaction product alone is not effective for the molecular weight increase reaction. Eich therefore recommends for economic reasons the inactivation of the alkali catalyst by other agents. such as titanium tetrachloride.

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

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The alcohols are ζ. B. methanol, ethanol, η-propanol, isopropanol, butanol and its isomers, benzyl alcohol, triphenylcarbinol, naphthyl-äthylcarbiiiol, glycol, propylene glycol, nonanediol, glycerol, allyl alcohol, 2-butynediol-1, 3, ethanolamine, difithanolaxanolamine, triethanol and triethanol 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 acid, Cinnamic acid, adipic acid, azelaic acid, phthalic acid, acetylenedicarboxylic acid, naphthalenedicarboxylic acid, tricarballylic acid, methacrylic acid, Crotonic acid, vinyl acetic acid, acrylic acid, lactic acid, citric acid, aminoacetic acid, aminovaleric acid, thiopropionic acid and ricinus acid, benzenesulfonic acids, toluenesulfonic acid, naphthalenesulfonic acid, sulfinic acids such as benzenesulfinic acid and acid as well as all homologous compounds that easily split off protons.

Suitable phenols are phenol itself, pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, oxyhydroquinone, inositol, 1-isopropyl-4-oxybenzene. Salicylic acid, naphthol »nitronaphthol, thiophenol and its homologues as well as polythiols.

Acetylacetone should be mentioned as enolizable carbonyl compounds ad nitro compounds.

Suitable imides are ditosylimide and di-trichloroacetyUmid.

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U95403

Polymers that contain the functional groups mentioned, such as copolymers of vinyl chloride with maleic acid are suitable. Crucial for triggering this reaction is only the presence of the functional group. The organic residue on the functional group has none or only a very small influence on the reaction.

This catalyst component b) is used in far lower concentrations

trations as the catalyst component a) required. they lay between 0.002 to 2 moles, but usually between 0.005 moles to 0.6 moles per mole of the catalyst component a).

This reaction to increase the molecular weight is preferred

w '

wisely carried out so that at the end of the polymerization or after the desired conversion has been reached, the reaction mixture

different

or the mixture Xsx / reaction mixture first the catalyst component a) is added and stirred until a homogeneous mixture or solution is reached. Then the catalyst component b) is added all at once or in portions. When adding in portions there is generally a somewhat greater increase in molecular weight. . The increase in molecular weight is greater, the greater the amount of catalyst component b) used.

The temperature of the reaction mixture can be between -50.degree. C. and 100.degree. The catalysts are expediently added at room temperature or at the polymerization temperature. After a Exposure time up to 10 hours, but preferably less than 10 minutes, in special cases even less than 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 it off the solvent worked up with steam.

This process has the advantage that the polymers appropriate, usually easily accessible catalyst components to be added in a simple manner and a defined one without gelation

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Molecular weight increase can achieve. In addition, you can change the properties of polybutadiene, for example, in such a way that the volcanoes produced from these polymers even show an improvement in structural strength. Another essential advantage of the method according to the invention lies in the fact that the tendency of the crude polymers to flow is reduced to a considerable extent.

example 1

The polymerization of butadiene is carried out in a known manner with metallic sodium in hexane.

In the remaining polymerization solution is an equimolar

“Amount of TiCl, dissolved in hexane, introduced. After adding 1.8 g

Ethyl *

/ .aluminium sesquichloride (2%, based on butadiene) v / ird the Approach at room temperature with 0.07 ml of water (3.9 × nmol), dissolved in benzene, added. 1 hour after adding the water the highly viscous solution is stabilized and the polybutadiene is precipitated by adding methanol.

ML-4 before reaction: 7

ML-4 after reaction: 91 gel: "6 %

Similar results are obtained when using carboxylic acid, phenols and sulfonic acids as cocatalysts.

Example 2

The reaction solution of the one made with metallic sodium. Copolymer of butadiene and styrene (ratio 7p: 30). in hexane, the equimolar amount of TiCl ₄ , based on sodium, is added. After adding 1.8 parts by weight of ethylaluminum sesquichloride, based on 100 parts by weight of the copolymer, 0.179 g of formic acid are obtained at room temperature

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ν? .Si ', »'

added in the form of a 1% solution in benzene. The strong viscous solution is stabilized after the reaction has ended and precipitated with methanol.

ML-4 before reaction: Dec. ML-4 after reaction: 53 Example 3

The polymerization of butadiene is carried out in a known manner with metallic potassium in hexane. After adding 2.5 % of ethylaluminum sesquichloride (based on butadiene), a benzene solution of 0.55 mol of acetic acid per mol of ethylaluminum sesquichloride is added. After a reaction time of 1 hour, the catalyst of the viscous reaction solution is decomposed with 2 moles of acetone per mole of ethylaluminum β esquichloride and the polymer is precipitated with methanol. The dry product contains about 1% di-tert. -butyl-ρ-kr es oil as a stabilizer.

ML-4 before reaction: 37 ML-4 after reaction: 84.

Similar results are obtained when using carboxylic acid, phenols and sulfonic acids as cocatalysts.

Example 4

The polymerization approaches prepared according to Examples 1 and 3 are put together in equal parts and mixed together homogeneously. This reaction mixture 0.30 mol Formic acid was added per mole of ethylaluminum sesquichloride in 3 equal portions, each 30 minutes apart. 1 hour after the last addition, the catalyst is decomposed with 2 moles of acetone per mole of ethylaluminum sesquichloride and the polymer is filled with methanol. The dry product contains about 1% di-tert-butyl-p-cresol as a stabilizer.

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Claims (1)

■. 9 - 53 U95403 ο. ζ. 1924 91. 7.12. 64 ML-4 before reaction: - ML-4 after reaction: • Claim Process for the defined increase in the molecular weight of unsaturated polymeric, preferably elastomeric hydrocarbons «produced by the polymerisation of diolefins or mixed polymerisation of mono- with diolefins or mixed polymerisation of different diolefins with one another in inert organic solvents metallic sodium and / or potassium or their organic compounds as a catalyst, thereby marked cn η et, that the reaction mixture or the mixture of different reaction mixtures after the end of the polymerization or after Achieving the desired conversion before or after decomposition of the polymerization catalyst with a catalyst system implements the ■ a) consists of a compound of the general formula R MeX, Inder 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, Sulphoxy radical or a carboxylate anion, where y is the Valence of the respective central atom Me and η a value between O and the valence of the central atom means, and b) consists of an active hydrogen-containing compound, "where the catalyst component a) in concentrations of 0.01 to 10 percent by weight, based on the polymer used, and the catalyst component b) in amounts of 0.002 to A mol" based on the Catalyst component a), is added | 9098U / 1 102