DE1224044B - Process for the production of polycyclopentadienes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C08d

C08f

German class: 39 c-25/05

Number: 1224 044

File number: B 69913IV d / 39 c

Filing date: December 8, 1962

Opening day: September 1, 1966

It is known that cyclopentadiene polymerizes slowly at room temperature and somewhat at elevated temperature faster to low-molecular-weight polycyclopentadiene, which has a degree of polymerization below 10. It it is also known to accelerate the polymerization with Friedel-Crafts catalysts. One obtains but only polycyclopentadiene with a molecular weight of up to 7000, from which no moldings or Foils can be produced.

It is also known to use cyclopentadiene catalysts from organometallic Compounds of metals from I. to III. Group and compounds of the transition metals of IV. To VIII. Group of the Periodic Table of the Elements, especially those containing titanium compounds as Heavy metal components contain to polymerize. However, one gets in strongly fluctuating Yields of highly crosslinked polycyclopentadiene. This known method is also not guided Polymerization and is also cumbersome because a two-component catalyst is required. In addition, the compounds of the transition metals of groups IV to VIII must be carried out carefully cumbersome cleaning operations are separated from the polymers, as they are their resistance to aging badly affect and partly discolor them.

It has now been found that polycyclopentadienes can be obtained by polymerizing cyclopentadiene and / or of cyclopentadiene derivatives which carry indifferent substituents, using a Can produce halogen-containing organoaluminum compound as the only catalyst with advantage, by using a catalyst in which the atomic ratio of aluminum to halogen is 1: 1.1 up to 1: 2.

As halogen-containing organoaluminum compounds are suitable, for. B. alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl and / or aralkyl aluminum halides, especially chlorides, bromides and iodides. Examples are methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, isooctyl, buten-2-yl, cyclohexyl, cyclohexen-3-yl, phenyl and Benzyl aluminum dichloride and dibromide, and methyl, ethyl, butyl, cyclohexyl and phenyl aluminum sesquichloride, sesquibromide and sesquiodide. In the case of the halogen-containing organoaluminum compounds mentioned, the atomic ratio of aluminum to halogen is in any case 1: 1.1 to 1: 2. Instead of the halogen-containing organoaluminum compounds mentioned, mixtures of aluminum tri-processes for the production of
Polycyclopentadienes

Applicant:

Aniline & Soda Factory in Baden
Aktiengesellschaft, Ludwigshafen / Rhein

Named as inventor:

Dr. Adolf Steinhofer, Ludwigshafen / Rhine;

Dr. Herbert Müller, Frankenthal (Palatinate)

Halide and halogen-free organoaluminum compounds are used as catalysts, since it is known that these components easily form halogenated organoaluminum compounds of the type mentioned above. In the process according to the invention, halogen-containing organoaluminum compounds are preferably used as halogen-containing alkylaluminum compounds, especially those which have straight-chain or branched alkyl groups with 1 to 10 carbon atoms, especially with 1 to 4 carbon atoms. In the process, the higher the halogen content of the catalysts, the higher the throughputs and the higher molecular weight polycyclopentadienes. Conversely, the lower the halogen content of the catalysts, the lower the rate of polymerization and the lower the degree of polymerization. In this way it is in hand, and this is a particular advantage of the process, that the molecular weight in the polymerization can be regulated simply by the choice of the catalyst composition. It is easy to produce polycyclopentadienes whose intrinsic viscosity is above [η] = 0.3 up to 3 cm ³ / g and higher. The molecular weights of the resulting polymers can also be influenced by the catalyst concentration and the reaction temperature. Low catalyst concentration and low temperature generally result in high molecular weights, while high catalyst concentration and high temperature result in lower molecular weights. Although higher and lower temperatures are possible, but we generally operates in a temperature range from -100 to +200 ⁰ C, and preferably temperatures of from -80 to ⁰ C. H-IOO For economic reasons, it is expedient that

609 658/415

3 4

Reaction with as little catalyst as possible to produce substances such as sulfur, oxygen or hydrogen, to lead. Sufficient reaction rates are achieved with the double bonds still present one reaches z. B. even at catalyst concentrations polymers react to form shaped structures, such as of 0.01 percent by weight of catalyst, based on household items and foils, can be processed. The used cyclopentadiene. However, the usual stabilizers for polymers can also be used even smaller or larger amounts of catalyst are added to polyolefins in the usual amounts, be turned. In general, the catalyst concentration is the other 1,3-dienes, such as butadiene, isoprene, and the pipe concentration between 0.001 and 1 percent by weight, rylene and cyclohexadiene, using halogen based on the amount of cyclopentadiene. containing organoaluminum catalysts in waste

In the process, cyclopentadiene is preferred as a mono-essence of transition metals of IV. To VIII, meres. In addition, groups with other monomers, such as isobutylene cyclopentadiene derivatives, which carry one or more 2-methylbutene- (l), mixed substituents at low temperatures, which are indifferent to the polymerized, but are also catalysts at higher temperatures, are also suitable as monomers. Such substituents are e.g. B. cannot be homopolymerized, it is superfluous or polyvalent hydrocarbon radicals, such as 15 surprising that cyclopentadienes homopolymerized according to the present the ethoxy and iso-butoxy groups. can be copolymerized.
Substituents with acidic hydrogen atoms, such as The parts of hydroxyl and carboxyl groups mentioned in the following examples, are unsuitable because they are parts by weight. The carbon used in it reacts with the catalysts. In particular, hydrogen solvents are practically free from the following suitable cyclopentadiene derivatives, such as oxygen and water,
named: l-methylcyclopentadiene (2,4), 3,4-dimethoxycyclopentadiene (2,4) and indene. example 1

In the process, you can in substance or in

Polymerize the solution. Suitable solvents are 25 to a solution of 240 parts of cyclopentadiene in

especially hydrocarbons, such as heptane, cyclo- 1500 parts of toluene, a solution of 1.03 parts

hexane, benzene, toluene, xylene or petroleum fractions len aluminum triethyl and 0.73 parts aluminum

with a boiling range from 100 to 300 ° C, halogen chloride in 50 parts of toluene. One stirs vigorously and

hydrocarbons, such as chlorobenzene, chloroform, cools down to 20 to 25 ^° C. After 15 minutes it begins

Trichlorethylene, and ether, e.g. B. diethyl ether, Pro- 30 colorless reaction mixture to become viscous. To

pylbutylether, tetrahydrofuran and glycol dimethyl 2 hours is the catalyst by adding

ether. Mixtures of these parts of a mixture of equal parts of acetone can of course also be used

like solvents can be used. Destroyed as a solution and methanol and the polymer with a

Medium are aromatic hydrocarbons, in excess of the acetone-methanol mixture.

special one that falls through one or more alkyl 35. A stabilizer is added to the polymer

groups are substituted, such as toluene and xylenes, pre- 1 percent by weight di-tert-butyl-p-cresol and dries

drawn. under reduced pressure at 6O ⁰ C. This gives

In the process, the pressure can be varied within 230 parts of white, powdery polycyclopentadiene, within wide limits. It is polymerized at 50 ° C in benzene, the intrinsic viscosity [η] = 0.5 cyclopentadiene at a relatively high temperature, 40 has. It can become transparent at 180 ° C. B. tough plates or tear-resistant foils are pressed: at 5 to 10 atmospheres, to work. In general, polymerizing is carried out at atmospheric pressure for economy. B is ρ ie 1 2
pressure.

A solution of 40 parts of indene in 200 parts of organoaluminum compound to the given toluene is mixed with a solution of 3 parts of ethylalufall monomers diluted with solvent in 27 parts of benzene. The giving. A lively polymer reaction mixture then sets in immediately at room temperature, during which heat is developed and the reaction temperature is stirred. One then adds 1 part of acetone and 2 parts of the mixture becoming increasingly viscous. However, 5 "methanol can be added and the polymer is precipitated with an excess of methanol, also advantageously the monomer to the catalyst. After drying, under add, since in this case the temperature at the reduced pressure gives 19 parts of polyindene, merization easily can be kept constant, which melts at about 250 ° C.
After the reaction has ended, the catalyst is in

generally by adding small amounts of protons
active substances such as water, alcohols or acids. Before adding such decomposers, it is often advantageous to add substances to a solution of 1.3 parts of ethylaluminum disintegrant which have groups with sesquichloride added dropwise to 900 parts of benzene with free electron pairs, such as ketones, amines, 20 ° C. within 15 minutes 240 Share cyclo-ammonia, ethers, esters, sulfides and sulfoxides. Since 60 pentadiene with stirring. After one hour the catalysts used are sensitive to air and moisture polymerizate by pouring in the reaction mixture, all operations are expediently precipitated in 2000 parts of acetone. The precipitated polymer, with the best possible exclusion of oxygen, is made by adding 1 percent by weight of di-tertiary and water. butyl-p-cresol stabilized and under reduced

The process generally gives 65 prints dried at 60.degree. 230 parts are obtained

uncrosslinked polycyclopentadienes, the thermoplastic colorless, uncrosslinked, elastic polycyclopentadiene,

or have rubber-elastic properties. that at 50 ° C in benzene the intrinsic viscosity [η] = 1.54

They can be implemented as such or after implementation with has.

Example 4

To a solution containing each 0,203 parts of aluminum in the form of a reaction product from varying amounts of aluminum triethyl and aluminum chloride in 1400 parts of toluene, are added at 1O ⁰ C with good stirring rapidly each 210 parts of cyclopentadiene. As a result of the polymerization which occurs immediately, the reaction mixture warms up despite external cooling with ice water. The mixture is left to polymerize for a total of 1 hour and then worked up as described in Example 1. The molar ratio of aluminum triethyl and aluminum chloride, the temperature rise of the reaction mixture during the polymerization, the yield of polycyclopentadiene and the intrinsic viscosity [η] of the polycyclopentadiene obtained are shown in the table below.

AlR ₃ · AlCl ₃ tempera yield M. ver
search 1.9: 1.1 increase in speed
° C in
share 0.66 a 1.8: 1.2 13th 120 0.82 b 1.7: 1.3 30th 160 0.82 C. 1.5: 1.5 40 198 1.3 d 1.7: 1.3 60 210 1.6 e 60 210

Example 5

A solution of 1.03 part of aluminum triethyl and 0.8 part of aluminum chloride in 50 parts of xylene is added to a solution, cooled to -10 ° C., of 570 parts of cyclopentadiene in 2000 parts of technical grade xylene, with vigorous stirring. Despite intensive cooling with a coolant having a temperature of - 15 ⁰ C, the temperature of the reaction mixture rises rapidly to 2O ⁰ C. To complete the conversion is stirred for 2 hours at 15 ° C and then, operates as indicated in Example 1 , on. 560 parts of polycyclopentadiene with a molecular weight of 410,000 are obtained.

Claims (1)

Claim: Process for the preparation of polycyclopentadienes by polymerizing cyclopentadiene and / or cyclopentadiene derivatives bearing indifferent substituents using a halogen-containing organoaluminum compound as the only catalyst, thereby characterized in that a catalyst is used in which the atomic ratio from aluminum to halogen is 1: 1.1 to 1: 2. Considered publications:
Chemical Abstracts, vol. 56, column 3609. 609 658/415 8.66 © Bundesdruckerei Berlin