DE1234391B - Process for the production of polymers from ethylenically unsaturated hydrocarbons - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

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C08f

German: 39 c -25/01

1234 391
B67848IVd / 39c
June 28, 1962
February 16, 1967

It is known that ethylenically unsaturated organic compounds with certain catalysts polymerize according to an anionic reaction mechanism. There are essentially two for this Groups of catalysts into consideration.

1. Organometallic compounds or alkali metals,

2. Catalyst combinations consisting of a compound of transition metals and an organometallic compound Connection.

Each of the two types of catalyst has a specific effect and is only intended for polymerization Kinds of monomers suitable. Polymerization and copolymerization present particular difficulties of monomers that contain oxygen in the molecule.

The catalysts are also mostly air and water sensitive, and their handling is dangerous, z. B. due to the self-igniting in air. There is another disadvantage to using this Catalysts that the monomers undergo a technically complex purification before the polymerization must be subjected.

It was also already known to polymerize olefins with catalysts by irradiating chelate complex compounds in solutions that must be free of water, oxygen and polar compounds with high-energy rays such as X-rays, β- and γ-rays, neutron and proton rays were obtained. However, the production of the catalysts and the purification of the solvents suitable for the production of catalysts are technically complex and laborious, especially since working with high-energy radiation requires expensive protective measures. In addition, it is disadvantageous that the polymerization must be carried out in the absence of water and atmospheric oxygen. Furthermore, high-energy rays initiate the polymerization of ethylenically unsaturated compounds, so that different polymerization mechanisms are superimposed and non-uniform polymers are formed.

It has now been found that you can polymers of ethylenically unsaturated hydrocarbons or Copolymers made from mixtures of ethylenically unsaturated hydrocarbons with or with one another other copolymerizable ethylenically unsaturated monomers, in the presence of organic Complex compounds as polymerization catalysts which can be applied to supports, especially can advantageously produce if the polymerization catalysts used are chelate complex compounds Process for the production of polymers from ethylenically unsaturated hydrocarbons

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Herbert Naarmann,

Dr. Christoph Berding, Ludwigshafen / Rhine;

Dr. Hermann Reis, Limburgerhof;

Dr. Ernst-Günther Kastning, Assenheim;

Dr. Nikolaus von Kutepow, Karlsruhe-Rüppurr

of metals of group VIII of the periodic table with diketones, oxyketones, ketocarboxylic acids and their esters, polyketene, ketoaldehydes, dialdehydes, aldehyde carboxylic acids and oxyaldehydes, where in these compounds the keto and aldehyde groups are replaced by ketimine or aldimine groups can be replaced, as well as oxycarboxylic acids, aminocarboxylic acids, aminophenols, oxyquinoline or Dipyridyl, optionally with the addition of amines or unsaturated carboxylic acids or their amides, used.

Suitable chelating agents are, for. B. acetylacetone, benzoylacetone, cyclohexanedione-l, 3, __ tropolone, acetoacetic ester, Lactic acid, glycolic acid, malic acid, citric acid, salicylaldehyde, glycocoll, histidine, anthranilic acid, Diaminobutyric acid.

The chelate complex compounds of / 3-diketones and such /? - diketones, in where a keto group has been replaced by a ketimino group or by a ketoximino group. These can be represented using the example of acetylacetonate by the following formula:

CH, -C

CHo-C

CH

Me ⁿ

CH

C -CHo.

C-CH,

709 509/447

3 4

In this formula, Me ^{11 means} a divalent hydride, maleimide, fumaric acid, crotonic acid

Group VIII metal. However, Me can also and itaconic acid and its esters; Vinyl ester, like

be one, three or more valued. Vinyl acetate, vinyl propionate, vinyl benzoate; Vinyl ether,

Compounds of monovalent metals of the VIII. Group such as vinyl methyl ether, vinyl n-butyl ether, vinyl chloride

of the periodic system are, for example, 5 rid, vinylidene chloride, acrylonitrile, methacrylonitrile,

ben in "Advanced Inorganic Chemistry", London, 1962. Acrylamide, methacrylamide; Vinyl ketones, such as methyl

Some of the major or minor valences of vinyl ketone, isopropenyl vinyl ketone; Vinyl pyrrolidone,

Metals can also be saturated by other ligands vinylcaprolactam, vinylimidazole and vinylcarbazole,

be. Such ligands are, for example, CN ^- , OH ~, with the catalysts to be used according to the invention

CO, O—, primary, secondary or tertiary organic iosators, monomers can be copolymerized,

Amines such as trimethylamine, pyridine, diethylamine. which are incomplete with previously known catalysts

Particularly suitable chelate complex compounds come or cannot be copolymerized, for example, acetylacetonates, benzoylacetonates, th. Ethylene with vinyl ether, propylene with acrylic as well as complexes of acetoacetic esters of methanol, acid, styrene with ethylene in practically every proportion of ethanol, propanol, propargyl alcohol, 3-methyl-copolymerize.
buten- (l) -ols with the metals mentioned. Some of the polymers are steric

The catalysts are generally made up in an ordered manner. For example, after the

between 0.0001 and 5, preferably between 0.01, polyethylene made by the process of the invention

and 1 percent by weight, based on the monomeric high crystalline proportions. The density is above 0.95.

Connections, used. In the polymerization of dienes, the 1,4-cis and

The chelate complex compounds can be favored by the 1,4-trans linkage. The modular

Implementation of metal salts with the organic weights of the polymers obtained can depending on

Complexing agents according to known methods vary over a wide range

be asked. Such methods are e.g. B. in the be.

Works by F. G Oh in "Wiener Monatshefte" The polymerization may intergovernmental 50 and +250 ⁰ C

Vol. 21 (1900), p. 89, and by G. U r b a i η and can be made. The preferred ones to use

A. Debierne in Compt. Rend. «, Vol. 129 (1889), temperatures depend on the polymeric

P. 203, as well as in "Inorganic Synthesis", Vol. 2, pp. 10, 30 sizing monomers. So ethylene becomes preferred

and Vol. 5, p. 105. at 50 to 150 ° C, styrene, butadiene and isoprene at 20

The catalytic effectiveness of this chelate complex is homo- and co-polymerized up to 160 ° C. One can at

Connections can be increased if you work any pressures, if necessary you can

use organic amines such as pyridine, piperidine, triethyl pressures up to about 4000 atmospheres and even more,

amine, or unsaturated carboxylic acids or their 35 With the catalysts used according to the invention

Amides, such as acrylic acid, methacrylic acid, acrylamide, can gates the monomers in the block homo- and

Methacrylamide, are generally copolymerized in a ratio of 1:10. But you can too

up to 10: 1, based on the chelate complex compound, to polymerize the monomers in indifferent

clogs. Dissolve or suspend auxiliary fluids. Such

The chelate complex compounds are usually 40 auxiliary liquids are, for example, aliphatic, in organic solvents and also in the cycloaliphatic and aromatic hydrocarbons, Soluble monomers. They can be safely used on such as n-pentane, η-hexane, isohexane, n-heptane, n-octane, Handle air. It is also not necessary to use extremely isooctane, cyclohexane, methylcyclohexane, benzene, to use pure monomers and auxiliaries. Toluene, o-, m-, p-xylene, ethylbenzene, cumene, iso can i.e. in the presence of water and small amounts of propylbenzene, tetrahydronaphthalene or decahydro polymerize in atmospheric oxygen. The chelating naphthalene. Halogenated derivatives of these carbon complex compounds are already in extremely low hydrogens are also suitable. Such Verbin concentrations catalytically effective. Used fertilizers are, for example, chloroform, methylene lowers Quantities of the catalysts, it is usually not chloride, ethylene chloride, chlorobenzene or bromine required them after polymerization from the 50 benzene. Ethers, such as diethyl ether, are also suitable Remove polymers. Sometimes it is possible to use dibutyl ether, tetrahydrofuran, dioxane, glycolide Chelate complex compounds on carriers, such as methyl ether or methyl phenyl methyl ether, and also alcohols Activated carbon, soot, aluminum oxide, silica gel, aluminum and ketones, such as methanol, ethanol, propanol, to apply miniumsilicates and the like. Isopropanol, butanols, cyclohexanol, benzyl alcohol,

According to the method of the invention, for. B. 55 acetone, and water.

The following ethylenically unsaturated hydrocarbons: The polymerization can be continuous or also

are polymerized: olefins, such as ethylene, propylene, are carried out batchwise. The cataly-

Butene-1, isobutylene, n-pentene-1; Dienes, such as butadiene, can be used in continuous polymerization

2-methylbutadiene, 2-phenylbutadiene, 2,3-dimethyl in a mixture with the monomers or an auxiliary

butadiene, 2-methylbutadiene; Trienes, such as n-octatriene; 60 liquid can be introduced into the reaction vessel.

Styrene, α-methylstyrene and core-alkylated styrene. The parts mentioned in the examples are weight

Mixed polymerisation components come out of the box. The K values were determined by the method

the one in question: halogenated styrene, styrene sulfonic acid; by H. F i k e η t s c h e r, who wrote in "Cellulose-Chemie",

Acrylic acid, methacrylic acid, acrylic acid or meth. Vol. 13, 1932, p. 58, is published.

acrylic acid esters of alcohols with 1 to 18 carbon atoms, 65.

such as methyl acrylate, ethyl acrylate, acrylic example 1

acid n-butyl ester, acrylic acid tert-butyl ester, meth- In a pressure vessel 1000 parts of hexane and

acrylic acid methyl ester, maleic acid, maleic acid an- 5 parts of cobalt (III) acetylacetonate introduced and

Ethylene pressed on up to a pressure of 1000 atmospheres. Thereafter, 8 hours heated to 14O ⁰ C. This gives 540 parts of polyethylene having a K value 87.2 (l ° / _o solution in decahydronaphthalene).

Example 2

1000 parts of cyclohexane, 1 part of cobalt (III) acetylacetonate and 100 parts of maleic anhydride are introduced into a pressure vessel and ethylene is injected at 26 ° C. up to a pressure of 1200 atmospheres. After 5 hours of heating at 15O ⁰ C 400 parts are obtained of a white powdery polymer whose K value is the 77th It contains 25 percent by weight of maleic anhydride polymerized into it.

Example 3 Example 7

0.2 parts of iron (III) -

acetylacetonate and 30 parts of acrylic acid dissolved in 60 parts of cyclohexane and ethylene up to a pressure of 900 atmospheres pressed on. Polymerization is then carried out at 150 ° C. for 8 hours.

40 parts of a copolymer are obtained in which 75 percent by weight of acrylic acid is polymerized. The K value is 87 (1% in 5% NH ₃ solution).

If, instead of the iron (III) acetylacetonate, nickel (II) acetoacetic acid ethyl ester is used 49 parts of a copolymer in which 61 percent by weight acrylic acid are polymerized.

150 parts of vinyl ethyl ether, 800 parts of η-hexane and 1 part of cobalt (III) acetonate are introduced into a pressure vessel and ethylene is injected at room temperature up to a pressure of 760 atmospheres. The mixture is then heated to 145 ° C. for 2 hours and 280 parts of a finely powdered white copolymer, the melting range of which is around HO ⁰ C and the K value of 39, are obtained. The softening point is -5 ° C. The copolymer contains 50 percent by weight of vinyl ethyl ether as polymerized units.

Example 4

300 parts of n-butyl acrylate, 800 parts of benzene and 1 part of cobalt (III) acetylacetonate are introduced into a pressure vessel and ethylene is injected up to a pressure of 1000 atmospheres at room temperature. It is then ^{heated to 140 °} C. for 3 hours. The pressure rises to 1850 atmospheres. 450 parts of a white copolymer with a K value of 65 (1% in decahydronaphthalene) are obtained. The copolymer contains 48.9 percent by weight of butyl acrylate polymerized into it.

Example 5

In a pressure vessel to a pressure of 740 atmospheres gauge pressed at 30 ⁰ C in a solution of 80 parts of n-heptane and 0.1 part of cobalt (III) benzoylacetonate ethylene. Polymerization is carried out at 135 ° C. for 2 hours. 34 parts of a polymer with a K value of 92 are obtained.

Example 6

In a pressure vessel respectively to a solution of 80 parts of n-octane, 0.1 part of cobalt (III) acetylacetonate and certain amounts of the additives specified in the following table at 30 ⁰ C ethylene pressed atm to a pressure of 740th They polymerized for 5 hours at 15O ⁰ C.

Tabel

Without addition

1 part acrylic acid

1 part methyl methacrylate

0.5 part of methyl methacrylate

1 part triethylamine

yield
in pieces

35
47

56

53
42

K value
(l% igin
Decahydronaphthalene)

Example 8

0.1 part of propargylic nickel (II) acetoacetate is dissolved in 60 parts of cyclohexane in a high pressure vessel and ethylene is injected up to a pressure of 900 atmospheres. Is polymerized for 3 hours at 15O ⁰ C and 11 parts of polyethylene receives a K value of 80 (l ° / _o solution in decahydronaphthalene).

Example 9

0.1 part of rhodium (III) acetylacetonate is placed in a high pressure vessel Dissolved in 60 parts of cyclohexane and injected ethylene up to a pressure of 900 atmospheres. Polymerization is carried out for 5 hours at 150 ° C. and 14 parts of polyethylene with a K value of 83 (1% in decahydronaphthalene) are obtained.

Example 10

a) A solution of 140 parts of butadiene, 25 parts Fumarsäurediäthylester and 0.3 parts of cobalt (III) acetylacetonate in 80 parts of η-hexane is heated in a pressure vessel for 3 hours at 16O ⁰ C. 163 parts of a copolymer are formed which contain 15.2% of fumaric acid diethyl ester in copolymerized form. The product has a softening point of -65 ° C and a K value of 85 (1% in benzene). 50% of the polymer has a 1,4-cis structure.

b) Under the same conditions as specified under a), the monomers are 6.3 parts Polymerized cobalt (III) acetylacetonate and 0.1 part pyridine. 160 parts of a copolymer result with a softening point of -80 ° C and a K value of 87 (1% in benzene). That 85% of the polymer has a 1,4-cis structure. Both products are soluble in cyclohexane without gel.

Example 11

140 parts of butadiene, 80 parts of η-hexane and 0.02 part of cobalt (III) benzoylacetonate are on for 5 hours 100 ° C heated. 81 parts of a polymer with a K value of 80 are obtained. The polymer is soluble in a gel-free manner.

35

40

45

87 82

83

85
76

Example 12

In a pressure vessel, 0.1 part of cobalt (III) acetylacetonate in 80 parts of cyclohexane is injected into a solution of 100 parts of butadiene up to a pressure of 400 atmospheres. Is polymerized for 5 hours at 150 ⁰ C and obtained 111 parts of a copolymer having a K value 79, which is up to temperatures of -80 ° C elastic.

Example 13

100 parts of butadiene are polymerized at room temperature in 100 parts of η-hexane with 0.5 part of cobalt (III) acetylacetonate and 0.3 part of piperidine. There are formed 70 parts of a gel-free polybutadiene with a K Wert25 that up to temperatures of - 80 ⁰ C elastic. 90% of the polymer has a 1,4-cis structure.

Example 14

IO

20 parts of butene- (I) are mixed in a pressure vessel with 10 parts of acrylic acid, 0.03 part of cobalt (III) acetylacetonate and 100 parts of n-heptane. Is polymerized for 5 hours at 150 ⁰ C and is obtained 28 parts of a copolymer having a K value 95 (in l ° / _o aqueous solution) containing the polymerized units 35.5 weight percent acrylic acid.

Example 15

20th

^: 30 parts of acrylic acid, 200 parts of n-heptane and 0.025 part of cobalt (III) acetylacetonate are mixed ^{in a pressure vessel and propylene is injected at 30 °} C. up to a pressure of 15 atmospheres. Polymerization is carried out for 3 hours at 86 ^° C. and 45 parts of a copolymer with a K value of 113 (in 5% NH ₃ solution) which contains 66 percent by weight of polymerized acrylic acid are obtained.

30 Example 16

A mixture of 30 parts of propylene, 25 parts of acrylic acid amide with 0.05 parts is placed in a pressure vessel Polymerized cobalt (III) acetylacetonate in 100 parts of cyclohexane at 155 ° C. for 6 hours. There will be 45 parts of a copolymer with a K value of 76 (in 1% aqueous solution), which is 55 percent by weight Contains acrylic acid amide polymerized.

40

Example 17

A mixture of 50 parts of isobutylene, 10 parts of acrylic acid and 35 parts of ethyl acrylate with 0.1 part of cobalt (III) acetylacetonate in 100 parts of benzene is ^{polymerized at 150 °} C. for 10 hours in a pressure vessel. 65 parts of a polymer with a K value of 68 are formed (1% strength in a cyclohexanone-dimethylformamide mixture 1: 1). The copolymer contains 32 percent by weight of isobutylene, 15 percent by weight of acrylic acid and 53 percent by weight of ethyl acrylate in copolymerized form.

Example 18

55

50 parts of styrene and 50 parts of n-butyl acrylate are polymerized ^{with 0.1 part of cobalt (III) acetylacetonate at 150 ° C. in a pressure vessel for 2 hours.} 80 parts of a copolymer with a K value of 69 (10% strength in cyclohexanone), which contains 40 percent by weight of styrene as polymerized units, are obtained.

Example 19

50 parts of styrene and 50 parts of vinyl acetate are polymerized ^{with 0.1 part of cobalt (III) acetylacetonate at 150 ° C. in a pressure vessel for 5 hours.} 73 parts of a copolymer with a K value of 54 (1% strength in cyclohexanone), which contains 41 percent by weight of styrene as polymerized units, are obtained.

Example 20

0.1 part of cobalt (III) acetylacetonate is dissolved in a mixture of 50 parts of styrene and 50 parts of benzene in a high pressure vessel. Ethylene is injected up to a pressure of 800 atmospheres. Thereafter, polymerization is carried out at 150 ^° C. 81 parts of a copolymer with a K value of 68 (1% in benzene) are obtained. As shown by infrared spectra, the copolymer contains 20 percent by weight ethylene polymerized into it.

Comparative experiments

1. 30 parts of styrene are mixed with 0.03 parts of cobalt (III) acetylacetonate mixed and the mixture heated to 100 ° C for 60 minutes. After that, the solution after cooling in ten times the amount Poured methanol at room temperature. There are 13 parts of a polymer with a K value 67 failed.

If the same amount of the hemiporphyrazine cobalt (III) salt is used instead of the acetylacetonate, no polymer is formed in this way.

2. Following the procedure described in Example 7, ethylene is used with acrylic acid copolymerized by iron (III) acetylacetonate. A copolymer is obtained in the 75 percent by weight of the acrylic acid are polymerized.

If the hemiporphyrazine iron (III) salt is used instead of the acetylacetonate, none takes place Polymerization.

3. Using the procedure described in Example 11, butadiene is converted with cobalt (III) benzoylacetonate polymerized.

If the cobalt (III) hemiporphyrazine salt is used instead of the benzoylacetonate, this takes place no polymerization.

4. According to the procedure described in Example 16, propylene is polymerized with acrylic acid amide using cobalt (III) acetylacetonate as the polymerization catalyst.
If the hemiporphyrazine cobalt (III) salt is used instead of the acetylacetonate, no polymerization takes place.

Claims (1)

Claim: Process for the production of polymers from ethylenically unsaturated hydrocarbons or of copolymers from mixtures of ethylenically unsaturated hydrocarbons under themselves or with other copolymerizable ethylenically unsaturated monomers, in the presence of organic complex compounds as polymerization catalysts on supports can be applied, characterized in that the polymerization catalysts Chelate complex compounds of metals of Group VIII of the Periodic Table with Diketones, oxyketones, ketocarboxylic acids and 9 10 their esters, polyketene, ketoaldehydes, dialde addition of amines or unsaturated carbon hyden, aldehyde carboxylic acids and oxyaldehydes, acids or their amides, are used. where in these compounds the keto and Aldehyde groups through ketimine or aldimine. Publications considered: groups can be replaced, as well as Oxycarbon- 5 Deutsche Auslegeschriften No. 1 073 664.1 081 880; acids, aminocarboxylic acids, aminophenols, British Patent No. 845903; Oxyquinoline or dipyridyl, optionally under U.S. Patent No. 2,976,285. 709 509/447 2.67 © Bundesdruckerei Berlin