DE1251534B - Process for the preparation of diene polymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08d

C08f
German class: 39 c -25/05

Number: 1 251 534

File number: B 73389IV d / 39 c

Filing date: September 5, 1963

Open date: October 5, 1967

A number of methods are known for removing butadiene at pressures up to about 25 atmospheres using catalysts made from nickel or cobalt compounds and organometallic compounds of elements from I. to III. Main group of the periodic table of the elements to high molecular weight, rubber-elastic polymers with predominantly 1,4-cis structure can be polymerized. Included For example, nickel acetylacetonate or nickel carbonyl are used as nickel compounds, and organometallic compounds are used preferably aluminum alkyl halides such as diethyl aluminum chloride are used. The organometallic compounds used however, they are mostly self-igniting and difficult to handle.

It is also known that butadiene with catalysts from carbon oxide compounds of the Nickel or cobalt, such as nickel carbonyl, and halogen compounds, such as aluminum halides, polymerize can. In these processes, however, the catalysts generally have to be grinded for a long time are activated, and in addition to linear polymers, crosslinked gel-like polymers are obtained, if water is not completely excluded from the polymerization.

It is also known from French patent specification 1,281,516 that butadiene can be mixed with a catalyst can polymerize from nickel carbonyl, boron fluoride diethyl ether and aluminum triethyl. Included elastomeric polymers are obtained, but only very low polymer yields can be achieved will.

It has now been found that 1,3-diene polymers can be used can be made by making 1,3-dienes using catalysts

A. a compound containing nickel in a zero-valent state,

B. boron fluoride or an addition complex of boron fluoride and if necessary

C. an aluminum halide

in the absence of organometallic compounds of metals from I. to III. Main group of the periodic System of the elements polymerized.

It is an advantage of the new process that no spontaneously flammable metal alkyls are used have to. Boron fluoride or complex compounds are used as the activator of the zero-valent nickel compounds of boron fluoride is used, which is responsible for the polymerization of butadiene to gel-like products do not catalyze. Undesired side reactions Process for the production of diene polymers

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Herbert Müller, Frankenthal;

Dr. Dietmar Wittenberg, Mannheim

will not take place. The catalysts used are readily soluble in the solvents suitable for the polymerization, and lengthy grinding and activation measures for the catalysts are not required.
In the process according to the invention, the degree of polymerization can be set as desired over a wide range, e.g. B. by choosing different solvents and catalyst components. If you work in the process z. B. in the presence of aluminum chloride, rubber-elastic polymers are obtained.

As dienes that can be polymerized by the new process are, for. B. straight-chain, branched and cyclic 1,3-dienes are suitable. Your double bonds can also be a straight chain or branched aliphatic radical and belong to a cycloaliphatic ring. Examples of suitable 1,3-dienes are: butadiene- (1,3), isoprene, 2,3-dimethylbutadiene- (1,3), 2-ethylbutadiene (1,3), pentadiene (1,3), hexadiene (1,3), hexadiene (2,4), cyclopentadiene (1,3), Cyclohexadiene-C1 ^) and vinylcyclohexene (l).

As 1,3-dienes, butadiene and cyclic dienes with 5 to 6 ring carbon atoms are preferred. In the process, the 1,3-dienes can also be used in a mixture with other substances which are inert under the conditions of the process. For example, instead of pure butadiene, a mixture of butadiene with butanes and butenes, as is obtained in the industrial dehydrogenation of C ₄ hydrocarbons, can be used. In addition, the 1,3-dienes can also be polymerized as a mixture with one another.

Copolymers of 1,3-dienes with other olefinically unsaturated monomers, such as vinyl-substituted monomers aromatic compounds, e.g. B. styrene, and / or with trienes, such as hexatriene (1,3,5), 3-methylheptatriene (l, 3,5) and octatriene- (1,3,6) can be made by the process.

709 650/403

3 4

As compounds, the nickel in zero-valent to- The polymerization can be advantageous in indifferent

contained, for example, nickel solvents are carried out with the dien

carbonyl and its substitution products, in which the polymers are miscible. Suitable solvents

one or more of the carbon monoxide ligands are for example aliphatic, cycloaliphatic and

other uncharged organic molecules have been replaced, 5 aromatic hydrocarbons, such as butane, butenes,

such as triphenylphosphine - nickel tricarbonyl, bis-tri-cyclohexane, heptane, octane, benzene, toluene, xylenes,

ethyl phosphite - nickel dicarbonyl, triphenylphosphite- chlorobenzene and p-chlorotoluene. The solvents

nickeltricarbonyl, tris-triphenylphosphite-nickel mono- can, for. B. in 0.1 to 10 times the amount, based on

carbonyl, triphenylarsine - nickel tricarbonyl, bis-tri-1,3-diene, can be used. Of course

phenylarsine - nickel dicarbonyl, bis - triphenylstibin- io can also solvent mixtures, eg. B. between

nickel dicarbonyl, tetrakis-phenylisonitrile nickel, tris-60 and 200 ⁰ C boiling hydrocarbon mixtures

methylisonitrile - nickel monocarbonyl, 2,2 - dipyridyl - from petroleum, can be used. Instead of solution

nickel dicarbonyl, ο-phenanthroline-nickel dicarbonyl, agents of the type mentioned can also lead to poly-

Tripyridine-dinel-tetracarbonyl and cyclooctadiene-merizing 1,3-diene in liquid form as a solution

(1.5) nickel dicarbonyl. . 15 remedies serve. It is also possible to

Other suitable nickel compounds are e.g. B. drive available liquid diene polymers as

Tetrakis-triphenylphosphite-nickel, nickel-bis-acrylic solvents to be used.

nitrile, nickel-bis-acrolein, nickel-bis-fumaronitrile, The polymerization can generally at Tem-cyclooctadiene nickel (l, 5) bis-triphenylphosphine, bis temperatures from -70 to 150 ⁰ C performed tri-o -tolylphosphite-nickel-acrylonitrile, nickel-bis-acryl- 20. Higher temperatures than 150 ⁰ C and deeper nitrile-dipyridyl, tris-tri-o-tolyl phosphite-nickel, bis temperatures than -70 ⁰ C in special cases triphenylphosphite-acrolein-nickel. . possible, but at low temperatures the well are suitable further zero-valent nickel compound reaction rate is very low and at altitudes that only have hydrocarbon radicals as higher temperatures to an increasing extent secondary ligands, such as cyclododecatriene- (l, 5,9) -nickel, 25 reactions take place. Dicyclooctadiene- (1,5) -nickel, dicyclopentadiene-nickel polymerizes preferably. one at temperatures between 0 and 100 ° C. One other suitable compounds, which may contain nickel in zero at normal pressure and under reduced or valued state, can merize poly of metallic nickel with aluminum halides by reacting elevated pressure up to about 10 atmospheres. Higher pressures are possible in the process, in particular aluminum trichloride, in aromatic 30, but are generally not required. Acid hydrocarbons, such as benzene, toluene and 1,3,5-substance and water, should be obtained in the polymerization of maximum trimethylbenzene. at least be present in such amounts that, in addition to the preferred nickel carbonyl as the technical amount of catalyst, the most readily available compound that contains nickel is preferably used under an inert zero-valent state. 35 gases, such as nitrogen, and preferably used as the second catalyst component boron solvent whose water content is less than I ⁰ I _00, fluoride or addition complexes of boron fluoride comparable to carry out the method, the Katawendet. Suitable complexes of boron fluoride are, for. B. lysator components generally combined in the solvent provided for those with aliphatic, cycloaliphatic or aro-polymerization, matic ethers, mono- or polyhydric alcohols 40 In exceptional cases, ζ. B. when using heavy or phenols, carboxylic acids, aldehydes, ketones soluble catalyst components, it is appropriate, and esters, also with water and halogen water, the mixture of catalysts and solvent substances. Even complexes with weak organic compounds for some time, e.g. B. 1 minute to about 10 hours, to nitrogenous bases such as aniline, 'diphenylamine, stir. The resulting catalyst solution can then phenyl-β-naphthylamine and phenothiazines can be used in the continuous operation of the process. In the process, it can also be added to the polymerization vessel. Complexing agents of the type mentioned can also be present in deficiency, for example in the case of the discontinuous addition of free boron fluoride. In addition, the process can be carried out in which an excess of the complexing agents to be polymerized can also be added to the catalyst solution using an excess of the complexing agent 1,3-diene. In addition, in addition to the diene polymer components A and B, aluminum halides can also be used as catalyst components, such as in excellent catalyst yields, generally aluminum chloride / aluminum bromide and aluminum in the form of a more or less viscous iodide solution. The catalyst yields are about 1000 den. up to 100,000 moles of polymerized 1,3-diene per mole of nickel — the amount of catalyst used can be compound. Before the reaction is worked up, it can be varied within wide limits. In general, the catalyst can easily be used, for example between 0.01 and 10 percent by weight, based on the amount of catalysts, by adding a strong base such as ammonia. But you can also add 1,3-diene, preferably working with 0.1 to 1 Ge of water to the reaction mixture, a part of the weight percent catalyst. Extract the molar ratio of nickel to 60 catalyst. "The polymers can be combined to boron fluoride can also be varied within wide limits then easily separated from the solvents. It is generally possible.

between 1: 1 and 1: 1000, preferably between, depending on the catalysts used, are obtained

1: 2 and 1:50. The polymers which may be oily or elastomeric in addition to boron fluoride. You can

complexing agents used and / or the aluminum 65 z. B. instead of natural rubber or as valuable

Minium halide is preferably used in 0.1 to full additives to rubber. Except-

Ten times the molar merg; n, based on the boron fluoride, which can, according to the new process, e.g. B. from Bu-

to. tadiene, linear, practically unbranched polymers

5 6

which have the character of viscous oils can be obtained from the oil by extracting them five times and having viscosities between about 500 and 5000 cP, with each 500 parts of acetone 35 parts of a polymer measured in a falling ball viscometer. Separated at sats, which have a content of a poly-50 ⁰ C in benzene having the oily butadiene polymers merisiertem styrene of 10.5 percent by weight, an intrinsic viscosity of 0.05 to 1, and S products The acetone insoluble polymer has a Styrolmit an intrinsic viscosity of 0.08 to 0.5 cm ^s / g are content of 5.2 percent by weight,
of special interest. The polymers are marked with _R. . . .
many organic solvents, e.g. B. aliphatic e ι s ρ ι e
and aromatic hydrocarbons, halogen, one is made from 200 parts of benzene, 0.2 parts of nickel hydrocarbons and ethers, in any ratio io carbonyl and 1.1 parts of boron trifluoride dihydrate a miscible. They almost exclusively contain 1,4-structure catalyst solution, in which one has at 50 ° C. within the door, the portion with a cis-1,4 structure introducing 50 parts of butadiene- (1,3) over half an hour , weighs. The vinyl group content in the polymerizate is allowed to react for a further 30 minutes, the decomposition is about 0.5 to 3%, and this corresponds to the fact that the catalyst has an average degree of polymerisation due to the introduction of gaseous Ammodie polymers and evaporates after separation have insoluble from about 20 to 200, the vinyl end components from the solvent at normal pressure. For group calculable share. You can e.g. For example, for reduced pressure, the product can also be used to coat fertilizers. 1.5 parts of phenylbutene- (2) are separated off. as

The parts of residue mentioned in the following examples give 42 parts of little colored poly-

are parts by weight. 20 butadiene oil, which at 50 ° C in benzene has the limiting viscosity

. tat [η] = 0.18. It has 23% trans-1,4- and

B e 1 s ρ 1 e 1 1 to 73% cis-1,4 structure. 4% of its double bonds

In a stirred vessel under nitrogen at 50 ° C are present in vinyl groups.

in 1000 parts of benzene 1.8 parts of gaseous boron fluoride _R. -ic

and 0.4 parts of triphenylphosphine-nickel-tricarbonyl 25 e 1 s ρ 1 e

solved. Then, within 3 hours, a mixture is removed by heating for 3 hours

320 parts of gaseous butadiene (1.3) and holds the 200 parts of benzene, 0.6 parts of Raney nickel and 6 parts

Temperature of the reaction mixture at 50 ° C. Man len aluminum chloride to 80 ° C and adding

allows 3 parts of boron fluoride diethyl etherate to react at this temperature for 3 hours, a catalyst

yaw, 2000 parts of methanol are added and the suspension suspension is separated.

separated polymer from. After drying under 36 parts of this catalyst suspension, in

305 parts of colorless 900 parts of dissolved benzene are obtained under reduced pressure. One leads into the solution

Polybutadiene oil, 'which at 20 ° C has a viscosity of 30 to 35 ° C 110 parts of gaseous butadiene. The Re-

190OcP. Its cryoscopically determined mid-action mixture is kept for 15 hours at 25 ° C and

leres molecular weight is 2130. It has about 73 ° / ₀ 35 it then pours in 3000 parts of a mixture of equal

cis-1,4 structure and about 26% trans-1,4 structure. small proportions of methanol and acetone. You get

. ·, ~ 103 parts of rubber-elastic polybutadiene, which is used in

B e 1 s ρ 1 e 1 2 50 ⁰ C in benzene has the intrinsic viscosity [η] = 2.14. It

In a stirred vessel under nitrogen at 50 ° C, 90% cis-1,4-structure and 6% trans-1,4-

in 1000 parts of benzene 0.2 part of nickel tetracarbonyl 40 structure. 4% of its double bonds are in

and 2 parts of boron trifluoride diethyl etherate dissolved and an- vinyl groups.

closing with cooling within 3 ^x / ₂ hours Example 6
605 parts of butadiene (1,3) initiated. One still leaves

After reacting for 10 hours at room temperature, a mixture of 0.26 parts of nickel carbonyl and saturates

then the reaction mixture with gaseous Ammo 45 1.5 parts of aluminum chloride is for 1 hour at

different Ka 50 to 55 ⁰ C stirred, cooled to room temperature and then the niak excluding separates

catalyst residues are removed by centrifugation. After evaporation and then with a part of boron fluoride diethyl etherate

of the solvent is obtained from the clear polyset. The solution is passed within 2 hours

merisate solution 597 parts of water-white oil, which at 20 ⁰ C at 35 ° C 160 parts of gaseous butadiene and holds the

has a viscosity of 1410 cP. 50 reaction mixture then for a further 15 hours

If the same amount of room temperature is used instead of benzene. You work up in the usual way

dry technical xylene mixture, this gives 154 parts of rubber-elastic polymer at and

approximately the same reaction rate with the same as that in benzene at 50 ° C., the intrinsic viscosity [η] = 1.08

Yield a polybutadiene oil which has the viscous at 20 ° C. It has 70% cis-1,4- and 28% trans-

sity is 2960 cP. 55 1,4 structure. 2% of its double bonds are in

. . , Vinyl groups.

Example3

In a solution of 0.2 parts of nickel tetracarbonyl

and 4 parts of boron trifluoride diethyl etherate in 1000 parts In a stirred vessel under nitrogen len benzene is passed at 50 ° C for 2 minutes buta- 60 155 parts of liquid butadiene and introduced as catalydiene, 80 parts of styrene are added and then passed under sator 1.3 parts of the complex BF ₃ · 2 CH ₃ OH and cooling at 50 ⁰ C within 3 ¹ ^ hours a further solution of 0.13 part of nickel carbonyl in 2 parts of 340 parts of butadiene. Benzene is allowed to be added for a further 30 minutes. The system is depressurized by after-reacting and the polymer is precipitated by adding evaporative cooling to a temperature of −6 to −5 ° C. of 2000 parts of methanol. After drying 65 held. The solution turns within 5 Minuunter reduced pressure one obtains 360 parts of a yellow th and 75 minutes hochviskos.Nun adds colorless oil which at 2O ⁰ C, the viscosity of 617 cps up to 2 parts of acetone and 300 parts of benzene and removes the boron fluoride complex by stirring

8 parts calcium hydroxide. The sludge is centrifuged off and excess butadiene and the solvent are evaporated off under reduced pressure. 65 parts of a rubber-like polymer which has an intrinsic viscosity [η] = 1.1 are obtained. From the result of Ultrarotanalyse, the product 97 7o cis-, 2 ° / ₀ ° trans- and l / _0-vinyl double bonds.

Example 8

In a solution of 0.25 part of nickel carbonyl and 1.3 parts of the complex BF ₃ · 2 CH ₃ OH in 900 parts of benzene, gaseous butadiene is introduced in a stirred vessel under nitrogen at 50 ° C. in proportion to its consumption. The weight gain is 635 parts within 6 hours. The butadiene feed is now interrupted and the reaction is allowed to continue for 3 hours at 50 ° C., the catalyst is decomposed by adding 10 parts of calcium hydroxide, stirring is continued for 3 hours at room temperature and the precipitate formed is then separated off by centrifugation. After the solvent has been distilled off, 612 parts of a practically colorless oil remain, which has a viscosity of 1870 cP at 20 ° C.

Claims (1)

Claim: Process for the preparation of diene polymers by polymerizing 1,3-dienes in the presence of catalysts made from nickel and boron halogen compounds, characterized in that that you can make a catalyst A. a compound containing nickel in a zero-valent state, B. boron fluoride or an addition complex of boron fluoride and optionally C. an aluminum halide used and in the absence of organometallic compounds of the metals of the I. to III. so main group of the periodic table of the elements polymerized. 709 650/403 9.67 © Bundesdruckerei Berlin