DE1301491B - Process for the preparation of 1,3-diene polymers - Google Patents

Description

It is known to make 1,3-dienes using catalysts Compounds of the transition metals of the VIII and VIII group of the transition metals stable in water Polymerize the periodic table in aqueous emulsion. To achieve good However, conversions are very large amounts of catalyst, based on the amount of catalyst obtained Polymer, e.g. B. about 15 parts of catalyst per 100 parts of polymer required. A further disadvantage is that the polymerization is caused by very small amounts of oxygen is sensitively disturbed.

It is also known to use butadiene or mixtures of butadiene and styrofoam uriter use of 1,3-dicarbonyl compounds of divalent cobalt and of Polymerize peroxides in an aqueous emulsion. In doing so, however, you already get from sales of about 20% 1, 3-diene polymers, which make up a considerable proportion contained on gel bodies, and the polymerization is difficult to control will.

It has also been suggested using 1,3-dienes Metal chelate compounds of metals of groups IV to VIII of the periodic System of elements to produce in the presence of water. Also in this case it is however, the polymerization is difficult to control and it is already forming for conversions from about 30% gel body.

The subject of patent 1251536 is a method of manufacture of 1,3-diene polymers by polymerizing 1,3-dienes or mixtures thereof with other ethylenically unsaturated monomers using catalysts from transition metal chelate complexes and optionally cycloalkenes, organic Halogen compounds and / or salts of transition metals from I. to III. Group of the Periodic Table of the Elements, which is characterized in that transition metal chelate complexes derived from 1,3-thiocarbonyl compounds are used derive.

It has now been found that the activity of these complexes is considerable is increased when it is on substrates with a large internal surface have been knocked down. At the same time it results that the stereospecificity the polymers can be influenced more strongly.

Suitable carrier materials are, for example, diatomaceous earth, quartz powder, Kaolin, aerosols, Chinaclay, carbon black and finely divided ion exchangers.

These substances are expediently in a ratio of 1: 100 to 100: 1 mrt the metal chelate compounds are used, preferably in amounts that are between 1: 10 to 10: 1.

It is through the use of substrates with a large surface possible to increase the catalyst yield considerably, e.g. B. on the 2-to about 4 times comparable catalyst yields without the addition of the large surface area Carrier materials.

In general, the metal chelate compounds and the large surface area Carrier materials by simply grinding or mixing in the desired proportions brought together. They can then be used as polymerization catalysts without further processing can be used.

An additional activator effect can be achieved through the use of Cycloalkenes, organic halogen compounds and / or salts of dissolving metals the I. to III. Group of the Periodic Table of the Elements.

The 1,3-thiocarbonyl compounds can, for example, according to S. H. H. C haston and S. E.

L i v i n g s t o n e, »Pr. Chem. Soc. "(1964), No. 4, p. 111, by Addition of hydrogen sulfide to 1,3-dicarbonyl compounds in the usual way getting produced. By subsequent reaction with transition metal salts the thiocarbonyl chelate compounds are obtained therefrom.

The catalysts can be used individually or in mixtures with one another will. Polynuclear chelate complex compounds are also suitable. Except 1,3-thiocarbonyl compounds The transition metal chelate compounds can additionally also contain sulfur-free 1,3-dicarbonyl compounds contain bound .. In addition, the 1,3-thiocarbonyl chelate compounds can also are used as catalysts in a mixture with transition metal chelate compounds, which are only derived from sulfur-free 1,3-dicarbonyl compounds. Sulfur-free 1,3-dicarbonyl compounds are e.g. B. acetylacetone, benzoylacetone, dibenzoylmethane and acetoacetic acid esters, e.g. B. of ethyl alcohol and 3-methylbutene- (l) -ol- (3), as well as compounds, such as salicylic acid and salicylaldehyde, in a mesomeric Limit form have 1,3-dicarbonyl structure.

As 1,3-thiocarbonyl compounds for the thiocarbonyl chelate compounds are suitable e.g. B. 1,3-thioketones, such as thioacetylacetone, thiobenzoylacetone, dithioacetylacetone, Dithiobenzoylacetone and dithiodibenzoylmethane, ß-thiocarboxylic acids or their derivatives, such as methyl thioacetoacetate, ethyl ester, propyl ester, butyl ester, -3-methylbutene (1) ol (3) ester and -oxy-ß-thiosuccinic acid, ß-thioaldehydes, such as ß-thiobutyraldehyde, and mesomers Compounds which in at least one mesomeric limit form 1,3-thiocarbonyl structure such as thiosalicylic acid and thiosalicylaldehyde.

Mixtures of the thiochelate compounds can also be used.

Thiocarbonyl chelate compounds of transition metals of the input and or or bivalent copper, silver and mercury, the one and or or trivalent thallium, trivalent chromium, manganese, vanadium, gold, cobalt and ruthenium, tetravalent cerium, titanium and / or divalent nickel, platinum and palladium and / or pentavalent vanadium, niobium and tantalum have themselves particularly proven as catalysts.

Particularly suitable thiocarbonyl chelate compounds are e.g. B. Copper (II) thioacetoacetic ester, cobalt (III) thioacetylacetonate, manganese (III) thiobenzoylacetone, Cerium (IV) -di-thiobenzoylmethane, chromium (III) -thioacetoacetic acid-3-methylbutene- (l) -ot- (3) ester and thallium (I) thioacetylacetonate.

Examples of suitable cycloalkenes are cyclopentadiene, cyclohexadiene, Cycloheptadiene, Cycloheptatriene, Cyclooctatetraene, Cyclooctadiene-1,5, Cyclooctadiene-1,4, Cyclooctadiene-1,3, the cyclododecatrienes-1,5,9, e.g. B. Cyclododecatriene-1,5,9 (trans, trans, trans), cyclododecatriene-1,5,9 (cis, trans, trans), cyclododecatriene-1,5,9 (cis, cis, cis) and cycloheptatriene. If cycloalkenes are used as cocatalysts, in general, between 0.3 and 40 mol, preferably between 0.5 and 20 moles of cycloalkene per mole of thiocarbonyl chelate compounds. If you use more than 40 moles of cycloalkenes per mole of thiocarbonyl chelate compounds are obtained Polymers, their K values are below about 40 and the have no rubber-elastic properties.

Suitable organic halogen compounds which, in a mixture with the Thiocarbonyl chelate compounds which can be used are e.g. B. halogenated Hydrocarbons such as methylene chloride, chloroform, bromoform, iodoform, carbon tetrachloride, Trichlorethylene, ethyl bromide, ethyl iodide, n-butyl chloride, n-butyl bromide, tert-butyl chloride, n-amyl chloride, iso-amyl chloride, 1,2-dichloroethane, 1,4-dichlorobutane, 1,4-dichlorobutene-2, i, 1 ', 2,2'-tetrachloroethane, hexachloroethane, 1,2-dichloroethylene, tetrachloroethylene, Cyclohexyl chloride, cyclohexyl bromide, chlorobenzene!, Bromobenzene, iodobenzene, fluorobenzene, Xylylene dichloride, o-, m- and p-diclilorbenzól, sym.

Trichlorobenzene, hexachlorobenzene, hexachlorocyclohexane, also 2-amino-5-iodo-pyrimidine, 2,4-dinitrofluorobenzene, cyanuric chloride, chloropyridines, and halogenated carbonic acids and their derivatives, halogenated alcohols, ketones and ethers, such as chloroacetic acid, bromocaproic acid, co-bromoacetophenone, pentachloropropanol and dichlorodimethyl ether. Be organic Halogen compounds used as cocatalysts are preferably used 1 part of thiocarbonyl chelate compound, 0.01 to 20 parts of organic halogen compounds a.

Furthermore, salts can also be used as cocatalysts in the new process of transition metals from I. to III. Group of the Periodic Table used be e.g. B. halides, sulfates, nitrates, oxalates and acetates of copper, zinc, Mercury, silver and gold. Examples of suitable salts of this type are Copper (II-chloride, gold (IIl) -bromide, silver (I) -nitrate, gallium trichloride and Thallium (I) chloride.

The amount of thiocarbonyl chelate compound required will generally range between 0.001 and 3 percent by weight, preferably between 0.01 and 1 percent by weight, based on the amount of monomers.

The temperature and pressure conditions can vary widely in the process Limits can be varied. In general, the polymerization is carried out at temperatures between 0 and 100 ° C and pressures between normal pressure and 16 atmospheres. In special cases but higher pressures and temperatures can also be used. Preferably polymerized one at temperatures of 20 to 80 ° C.

The polymerization can take place in bulk, solution, suspension or emulsion be performed. The solvents used are preferably aromatic and / or cycloaliphatic hydrocarbons such as benzene, toluene and cyclohexane in question. The method is preferably in aqueous emulsion using the usual Emulsification auxiliaries, such as emulsifiers and protective colloids, worked. examples for Such emulsification auxiliaries are alkali salts of paraffin sulfonic acids or sulfated ones Alkylphenols, also alkali salts of higher fatty acids or so-called resin acids (Dresinate) as well as dextrans, cellulose ethers and polyvinyl alcohols. As an emulsifying aid are saturated and / or ethylenically unsaturated carboxylic acids with 8 to 30 carbon atoms such as oleic acid, stearic acid and linolenic acid are preferred. she are used in the amount customary for emulsion polymerization, e.g. B. between 0.5 and 20 percent by weight, based on the monomers. In addition, the aqueous Phase buffer substances such as phosphates or compounds of the ethylenediaminotetraacetic acid type and / or controller, e.g. B. dodecyl mercaptan included.

In addition, ethylene may still be saturated with ethylene during the polymerization oily polymers, such as those obtained in the processing of petroleum by distillation and are commercially available as Weictunacher, or butadiene or isoprene oils be. The oily additives can be used in quantities of up to 25 percent by weight on the polymer.

According to the procedure can I; 3-dienes, such as butadiene, isoprene 2,3-dimethylbutadiene, 2-phenylbutadiene and chloroprene alone or in any desired mixing ratio homo or. are copolymerized. To be able to serve with. other ethylenically unsaturated Polymerize compounds. will.

The diene content in the reaction mixture should, however, be at least 50 percent by weight, based on the total monomers. Suitable for mixed polymerisation Ethylenically unsaturated compounds, especially esters, ß-ethylenically unsaturated compounds Carboxylic acids, such as methyl, ethyl, propyl, n-butyl, iso-butyl, tert-butyl, 2-ethylhexyl ester of acrylic and methacrylic acid, esters of fumaric and maleic acid, especially the ethyl and n-butyl esters of these dicarboxylic acids, acrylic and methacrylic acid, Acrylonitrile, methacrylonitrile, vinyl aromatic compounds such as styrene and methyl styrenes, Vinyl ethers, such as vinyl methyl ether, vinyl n-butyl ether and vinyl isobutyl ether, as well Vinyl esters, such as methyl, ethyl, propyl, n-butyl and tert-butyl vinyl ethers.

The process can be carried out continuously or batchwise will. If you work continuously, then as reaction vessels z. B. a trickle furnace or several boilers arranged one behind the other can be used. In general polymerized to a conversion of about 70%. However, you can also go up to higher sales, e.g. B. to 90% and more polymerize without gel fractions obtain. This is a particular advantage of the method according to the invention.

A. The advantage of the procedure is that you can do it before or during the polymerization the polymerization approach to stabilize poly-1a3-diene suitable compounds, such as trnonylphenyl phosphite, which do not polymerize can disturb, inflict.

This allows an optimal stabilizing effect to be achieved and that technically much more complex subsequent incorporation of stabilizers saved If the process is polymerized in an aqueous emulsion, it is of Advantage of the catalyst components in part of the aqueous reaction medium to, emulsify and feed the catalyst emulsion to the polymerization vessel. However, you can also add the individual catalyst components to the polymerization vessel feed separately.

In the case of emulsion polymerization, the polymers fall in the form of a aqueous dispersion, which is generally between 5 and 50 percent by weight polymer contains. It is preferable to give a strong one before the polymer is precipitated Complexing agent for the dispersion, which the metal ions of the catalyst in the form of water-soluble, more stable complex compounds. Alkali cyanides are particularly suitable for this, Alkali phosphates or compounds of the type of ethylenediaminetetraacetic acid or their derivatives. Virtually catalyst-free is then obtained without special purification and optionally stabilized polymers.

The process generally gives high molecular weight rubber-elastic ones Polymers whose K values are generally between 50 and 150. You wise a particularly small content of polymers with 1,2-linkage, between about 5 and 15 percent by weight, compared to over 300 / o in the case of polymers that are made using peroxide catalysts. The polymers are suitable e.g. B. for the production of car tires or as an additive to other plastics, like polyolefins.

The parts and percentages given in the examples relate to each other on weight. The K values given therein are determined according to H. F i k e n t s c h e r, Cellulosechemie 13,58 (1932), in 1% solution in benzene, the solution viscosities measured in 5 "/ piger solution in toluene.

Example 1 a) 400 parts of water and 25 parts are placed in a pressure vessel a 20% aqueous solution of the sodium salt of paraffin sulfonic acid with 8 to 12 carbon atoms, 0.2 part cobalt (III) thioacetylacetonate, 0.1 part Manganese (III) acetylacetonate, ground with 5 parts of aluminum oxide and 0.5 parts Cyclooctadiene-1,5. 150 parts of butadiene are added to the mixture with stirring. Man polymerized for 20 hours at 60 ° C. and obtained a dispersion with a dry content of 25.4 ° lo. This corresponds to a conversion of ~ 93%. The 1,2-bound portion the butadiene units in the polymer is, according to the IR analysis, at 8 ° lo, while one produced without a carrier material (aluminum oxide), but otherwise under the same conditions Polymer has a 1,2-bonded fraction of 1111 / o and also a broader one Has molecular weight distribution.

0.3 part of trinonylphenyl phosphite is added to the dispersion as a stabilizer added. After precipitation, work-up and drying, the polymer is in the usual manner Solvents gel-free and has a K value of 86 and a solution viscosity from 59 cP. The Mooney plasticity ML-4 '/ 100 ° C' (ASTM 927-57 T) is 38.5 and the defo values at 30 ° C 1260/37, at 80 ° C 725/33 (measured according to DIN 53514). b) The butadiene is added gradually over the course of 5 hours with stirring to the Catalyst dispersion, a polymer dispersion is obtained under otherwise identical conditions with a dry matter content of 23 ° lo. This corresponds to a conversion of 85% The K value of the polymer is then 81 and its solution viscosity is 45 cP. c) Emulsified on the other hand, the butadiene is in the aqueous phase and a mixture of the cobalt is added (III) thioacetylacetonate, ground with 5 parts of aluminum oxide, cyclooctadiene-1, 5 and trinonylphenyl phosphite gradually increase over the course of 4 hours under otherwise identical conditions, a dispersion with a dry content of 25% corresponding to a conversion of 0 / o. The K value of the polymer is then 106, its solution viscosity 170 cP.

Example 2 The polymerization is carried out as indicated in Example 1, a), used but instead of cobalt (III) thioacetylacetonate manganese (III) thioacetoacetic ester as a catalyst component and obtained under otherwise identical conditions, but within a dispersion with a dry content of 25.2% for 16 hours.

This corresponds to a conversion of ~ 96 ° lo. The product obtained is Completely gel-free soluble in common solvents.

Example 3 The polymerization is carried out as indicated in Example 1, a), used however, instead of butadiene, a mixture of 95 parts of butadiene and 5 parts of styrene and instead of the cobalt (III) thioacetylacetonate, nickel (II) thioacetoacetic acid ethyl ester. A dispersion with a dry content of is obtained within 17.5 hours 18%, corresponding to a conversion of ~ 96.5%. The K value of the in the usual Solvent gel-free soluble polymer is 81, its solution viscosity 43 cP, its tensile strength 228 kg / cm2 (measured according to DIN 53504) and its elongation 480 ° / o (measured according to DIN 53504).

Example 4 The polymerization is carried out as indicated in Example 1, a), used however, instead of butadiene, a mixture of 145 parts of butadiene and 5 parts of vinyl ethyl ether and rhodium (III) thiobenzoylacetonate instead of cobalt (III) thioacetylacetonate and uses diatomaceous earth as a carrier material. A dispersion with a dry content is obtained of 26 corresponding to a conversion of 94%. During the polymerization, one sets 2 parts of ß-naphthylamine. The K value of the gel-free in the usual solvents soluble polymer is 97 and its solution viscosity is 134 cP.

Example 5 500 parts of water are successively added to a pressure vessel, 40 parts of a 20% solution of potassium salts of resin acids, intimately with each other ground mixture of 0.5 parts cerium (IV) thiosalicylate, 5 parts carbon tetrachloride and 15 parts of Aerosil and also 100 parts of styrene and 100 parts of isoprene. One polymerizes 25 hours at 60 ° C and receives a dispersion which has a dry content of 26.5 <'/ o has, corresponding to a conversion of -950 / o. The K value of the gel-free soluble Polymer is 87, its solution viscosity is 111 cP.

Example 6 The polymerization is carried out as indicated in Example 5, used however, instead of 100 parts of styrene, a mixture of 50 parts of styrene with 50 parts Acrylonitrile and instead of the cerium complex a mixture of equal parts of titanium (IV) thioacetylacetonate and ruthenium (III) thioacetylacetonate. A polymer dispersion is obtained with a dry content of about 26 11 / o, corresponding to a conversion of ~ 95 ° lo.

Example 7 One brings into a trickle furnace continuously every hour a) a mixture of 500 parts of water and 25 parts of a 25% solution of the sodium salt a higher fatty acid having 12 to 20 carbon atoms and b) a mixture of 0.5 Parts of copper (I) thioacetoacetic acid 3-methylbutene (1) ol (3) ester, 1 part of chloroform, 1 part trinonylphenyl phosphite, deposited on 25 parts quinaclay, and 120 Share butadiene.

Polymerization is carried out at 35 ° C. and the reaction mixture has an average residence time in the trickle oven for 2.5 hours. A dispersion is obtained which has a dry content of 12.5%, corresponding to a conversion of ~ 60%. The K value of the gel-free soluble polymer is 92, its solution viscosity is 70 cP.

If the polymerization is carried out at 50 ° C. under otherwise identical conditions, then so a dispersion is obtained with a dry content of 15.6 I / o, corresponding to one Conversion of ~ 73 ° / o. The K value of the gel-free soluble Polymer is then 89, its solution viscosity 52.5 cP.

Claims (1)

Claim: Further configuration of the manufacturing process of 1,3-diene polymers by polymerizing 1,3-dienes or mixtures thereof with other ethylenically unsaturated monomers using catalysts from transition metal chelate complexes derived from 1,3-thiocarbonyl compounds, and optionally cycloalkenes, organic halogen compounds and / or salts of abandoned metals from I. to III. Group of the Periodic Table of the Elements according to Patent 1251536, characterized in that the transition metal chelate complexes used as catalysts deposited on substrates with a large internal surface area are.