DE1495324A1 - Process for the preparation of multicycloalkane-containing vulcanizable copolymers - Google Patents

Description

Process for the preparation of multioycloalkenes containing vulcanizable copolymers

By polymerizing ethylene, (/ -olefins and polyunsaturated compounds, e.g. diolefins in the presence of organometallic mixed catalysts, terpolymers are known to be obtained, which can be vulcanized with sulfur. The diolefin used can be, for example, dicyclopentadiene or other compounds with double bonds of different reactivity, in particular diolefins with non-conjugated double bonds. What is essential is that one double bond is very reactive and coopolymerizes with the ethylene and the o-olefin via this C = C grouping, while the second double bond is less reactive and is retained for subsequent sulfur vulcanization. In the case of the previously known polyunsaturated compounds, e.g. in the Dicyclopentadiene, there is a risk of crosslinking, especially when a large amount of diolefin is available Double bond content and thus faster vulcanization is to be achieved.

It has now been found that easily vulcanizable elastomeric copolymers of ethylene, o ( -olefins and polyunsaturated compounds in the liquefied monomers or in inert solvents in the presence of organometallic mixed catalysts, on the one hand from compounds of main groups I to III of the periodic table , which contain at least one hydrogen atom or an alkyl group bonded to the metal atom, and on the other hand can advantageously produce from compounds of the metals of the IV. to VI. subgroup of the perlode system, if the polyunsaturated compounds are multicycloalkenes with 2 to 6 rings, the number of ring members 3 to 12 carbon atoms and whose ring units are monocyclic, are used, and the molar ratio of ethylene, ϋζ -olefin and multieyoloalkene 1 to 10 to 1 to 10 to 0.01 to 1, preferably 1 to 5 to 1, 5 to 0, 01 to 0.05, is

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Suitable multicycloalkenes for the production of which no protection is claimed are e.g. di-, tri- and tetracyclopropenyl, Di-, tri-, tetra-cyclopentenyl and their double bond isomers with isolated double bonds, also di-, tri- and tetracyclohexenyls, di-, tri- and tetracyclooctenyls and multicycloalkenes with cycloalkenes different ring size.

Such compounds can be z. B. produce as follows: Through Addition of hydrogen chloride to cyclopentadiene results in high yields of 3-chloro-cyclopentene- (l). This can be done by dehalogenating Dimerization, e.g. with magnesium, easily produced dicyclopenten- (2) -yl will. The addition of 3-chloro-cyclopentene- (1) to cyclopentadiene results in correspondingly chloro-dicyclopentenyl, from which with magnesium Tetracyclopentenyl can be obtained. By converting 3-chloro ' -cyclopenten-U) with chlorodicyclopentenyl can obtain tr | cyclopentenyl will. Similarly, multicycloalkenes z. B. produce with cyclohexenyl and cyclooctenyl. So z. B. from 3-chloro-cyclopentene- (l) with cyclooctadiene- (1,3) the l-cyclopenten- (2 ') - yl-4- -chlor-cycloocten- (2) and the corresponding 1,2-addition product with ;: allylic chlorine. By dehalogenating dimerization, e.g. B. with iron, the bis-cyclopenten- (2 ') - yl-dicycloocten- (2) -yl (I) be won. Analogously one obtains Π. , ·

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Finally, by dehalogenating dixnerization more appropriate Mixtures e.g. IV, V or VI can be obtained: /;

VI

Suitable α-olefins are, for. B. propylene, α-butylene, α-pentene, α-hexene and a-heptene. The monomers used for the copolymerization, Ethylene, a-olefin and polycycloalkene, are in a molar ratio ' 1 to 10 to 1 to 10 to 0.01 to 1, preferably 1 to 5 to 1 to 5 from 0.01 to 0.05.

The polymerization takes place with the help of organometallic mixed catalysts made from compounds of the metals from I. to ΙΠ. Main group of the periodic table containing at least one hydrogen atom or an alkyl group bonded to the metal atom, and compounds of metals from IV. to VI. Subgroup of the periodic table, before * '

preferably of vanadium.

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As compounds of I. to ΠΙ. Main group of the periodic table, which contain at least one H atom, amyl sodium, butyllithium, diethyl zinc, but especially aluminum compounds, such as Trialkyl aluminum, triaryl and triaralkyl aluminum compounds, such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum,: Triphenyl aluminum, tri- (ethylphenyl) aluminum, and mixtures thereof, and also dialkyl aluminum monohalides, such as. B. Diethyl -aluminium monochloride and the monoalkyl aluminum dihalides, such as B. monoethyl aluminum dichloride, monoethyl aluminum dibrömid. Can also be used with particular advantage as alkyl-aluminum -sesquichlorid designated mixtures of equimolecular amounts of dialkyl aluminum monochlorides and alkyl aluminum dichlorides, such as z. B. ethyl aluminum sesquichloride. In addition, dialkyl aluminum hydrides, such as B. diethyl aluminum monohydride, diisobutyl aluminum monohydride, etc. are suitable.

Suitable compounds of metals from IV. To VI. Subgroups of the periodic table are titanium tetrachloride and chloro-titanic acid esters, such as. B. dichlorotitanic acid diethyiester / Ti (OC ₂ H ₅ J ₂ Cl ^, but in particular also vanadium compounds such as vanadium trichloride, vanadium tetrachloride, vanadium oxytrichloride, vanadium esters such as vanadium triacetate / V (C ₂ H ₃ O ) J and vanadium triacetylacetonate / V (C ₅ H ₇ O ₂ ) ^.

The copolymerization can be carried out in the liquefied monomers, optionally under pressure; it is advantageous to work in the presence of inert diluents, for example in hydrocarbons or hydrocarbon mixtures such as butane, pentane, hexane, cyclohexane, isopropylcyclohexane, gasoline fractions such as petroleum ether, benzene, toluene, xylene, etc., which are liquid under the polymerization conditions or in s chlorinated hydrocarbons such as B. chlorobenzene and mixtures thereof. Particularly suitable are mixtures of aliphatic and cycloaliphatic hydrocarbons, for example, proved to Hexane ■ ~ \ and isopropylcyclohexane.

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The copolymerization proceeds advantageously between -30 and + 60 ° C., in particular between -20 and + 35 ° C. It works without the use of Print at sufficient speed, but can also be done under pressure are executed.

The reaction proceeds particularly smoothly if mixed catalysts jj uses which are soluble or colloidal in the solvents used are distributed. The reaction products which are obtained by bringing together vanadium compounds, such as vanadium tetrachloride, vanadium oxytrichloride and vanadium esters, with organometallic compounds of aluminum, such as e.g. B. triethyl aluminum, Triisobutyl aluminum, trihexyl aluminum, diethyl aluminum monochloride or ethyl aluminum sesquichloride, in an inert diluent.

By adding compounds from the group of ethers, thioethers, amines and phosphines, for example diethyl ether, anisole, tetrahydrofuran, di-n-butyl sulfide, triethylamine and triphenylphosphine, the catalyst activity can be further controlled if desired. The molar ratio of the organoaluminum compound to the vanadium compounds is 50: 1, advantageously 12: 1, in particular 10: 1. The air and moisture sensitive catalysts must be kept under a protective gas such as nitrogen or argon. The solvents must not contain any water or oxygen. Once the poly merization 'a desired level has been reached, breaks through (J ₀ adding alcohols or ketones from. The work-up of the polymerisation ^ sats can be done in a conventional manner, for example by _> precipitation with alcohols or ketones or by evaporation of the diluent.

^ The new copolymers are amorphous, almost colorless and soluble in hydrocarbons. What is surprising is that with a small number

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'of double bonds that are already introduced by low proportions of polycycloalkene, sufficient crosslinking is achieved during vulcanization. A content of only 1 to 2 double bonds per 1000 carbon atoms is sufficient for vulcanization, whereby the vulcanizate properties of a vulcanizate of a copolymer of ethylene « _(!

Propylene and dicyclopentadiene, which have 4 to 5 double bonds per |! Contains 1000 C atoms. The minimal incorporation of e.g. tetracyclopentenyl into the ethylene-α-olefin chain makes the new process particularly economical. :

The new copolymers in the continuous process. The new copolymers are oil-extendable without the properties requiring below that lend comparable level drop. With regard to aging resistance and ozone resistance, the new copolymers or their Vulcanized materials are superior to natural rubber. Because of these advantageous properties, the claimed vulcanizates are suitable, inter alia. for the manufacture of motor vehicle tires and for cable sheathing.

example 1

Tetracyclopentenyl is prepared as follows: 531 g (5.2 mol) of chlorocyclopenten-d) are initially taken, cooled to -5 ° C., 0.8 g of anhydrous zinc chloride is added at this temperature and added dropwise while stirring while maintaining the temperature from -5 ^e C within 35 minutes 345 g (5.2 mol) of cyclopentadiene. The reaction mixture turns blue-black. The reaction is allowed to continue for 2 hours, initially at 0 ° C., then at room temperature. The reaction mixture is then stirred into ice water, the color disappearing. The organic phase is taken up in ether and the aqueous phase is extracted several times with ether. The combined ether solutions are dried over calcium chloride and, after the drying agent has been filtered off, evaporated in a water jet vacuum.

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Vacuum distillation of the residue gives 560 g (64.5% of theory) of crude chlorodicyclopentenyl at 55 to 80 ° C. and 2 to 3 torr.

In the redistillation, the product (540 g) goes at 55 to 59 * C and 20-

2 torr about, n £ - 1.5143

f. The tetracyclopenteny | JL is obtained from the chloro-di-cyclopentenyl

as follows:

In a mixture of 600 ml dry ether, 300 ml tetrahydrofuran (dried over lithium aluminum hydride) and 35.5 g of magnesium turnings are gradually added dropwise, first of all, 30 to 50 g of chlorodicyclopentenyl. When the reaction is in progress, τη adds to the remainder of a total of 473.5 g of chloro-dicyclopentenyl added and keeps the Reaction for 3 to 4 hours with stirring at reflux temperature. To Stirring overnight at room temperature, the reaction mixture is introduced into water and decomposed with dilute sulfuric acid to the weakly acidic reaction. The organic phase is separated the aqueous extracted with ether. After drying over calcium chloride, the combined ether solutions are evaporated and the residue is distilled under nitrogen in vacuo.

At 170 to 180 "C and 3 Torr, the main amount of 291.5 g is obtained (77.8% of theory) as a yellowish oil. In the redistillation over A little sodium under nitrogen is obtained at 140 to 155 ° C / 3 Torr, 273.3 g as the main fraction. It represents a still faintly yellowish ' colored liquid, which is redistilled again over a little sodium under nitrogen for analysis. Kp_ 150 to 153'C, colorless oil. niy »1.5322.

The continuous polymerization of ethylene, propylene and tetracyclopentenyl is carried out in a molar ratio of 1: 1: 0.02 as follows:

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The apparatus consists of a reaction vessel (3 liter capacity), which is provided with a stirrer, three graded dropping funnels and gas inlet and outlet devices. The reaction vessel is

connected to two vessels connected in series; in the first . , Vessel occurs, the stopping of the polymerization, the second serves as a reservoir. AUe three vessels are connected to one another by an overflow. .

After 1.5 liters of η-hexane have been poured into the reaction vessel, ■

the apparatus and the solvent are first cleaned with pure ..... dry nitrogen and then flushed with an ethylene-propylene mixture in a molar ratio of 1: 3. Located in the three drip funnels 1.74 ml of vanadium oxytrichloride, dissolved in one liter of η-hexane, 16.8 ml of ethyl aluminum sesquichloride, dissolved in one liter of n-hexane

dissolves, and 20.8 g of tetracyclopentenyl, dissolved in 2.5 liters of η-hexane. These three solutions are uniformly dripped into the reaction vessel over the course of four hours with stirring, with ethylene at the same time and propylene are introduced in a molar ratio of 1: 1. The amount of gas entering the dried olefins is monitored by a manometer and the amount of exhaust gas is monitored by means of a gas meter. 25 liters per hour Ethylene and propylene are offered. The amount of catalyst is 0.5 mmol Vanadium oxytrichloride per liter and hour and 6.0 mmol of ethyl aluminum -sesquichloride per liter per hour. The residence time is 30 minutes; it is regulated via a tap between the reactor and stopper. After the polymerization reaction for the first ten minutes has started and the temperature has risen to 30 * C, this will be Temperature with the help of a thermostat over the entire reaction time

held for 4 hours. to ^β "^ ■

The reaction is started in the 2nd vessel by continuously adding dropwise 200 ml of n-butanol "to which 0.2 ml of stabilizer have been added, while stirring" stopped. In the third vessel, the polymer solution is washed with 0.5 liters of water. After separating the phases, the hexane solution is 2 liters

ORIGINAL INSPECTED

° to OO

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Acetone added. The precipitated polymer is then stirred with acetone overnight. After drying in vacuo at 50 ^° C., 148 g of a pale yellowish colored, rubbery polymer are obtained. It has the reduced specific viscosity (HSV) of 1.22 (measured in 0.1% solution in p-xylene at 110 ° C.). The XJIU analysis shows 45 percent by weight propylene, no crystalline polyethylene and no isotactic polypropylene. Double bonds are Not recognizable in the UR; the cis double bonds are covered by the bands of the ethylene that has been polymerized in. After subtracting the blank value, the iodine number is 3.9, which corresponds to a little more than 2 double bonds per 1000 carbon atoms.

The vulcanization of this copolymer succeeds with the usual sulfur recipe. The property profile of the vulcanizate obtained is in the order of magnitude of a vulcanizate with a copolymer is obtained from ethylene, propylene and dicyclopentadiene, and is even superior to the comparative product in some values.

Example 2

The copolymerization is carried out in the apparatus described in Example 1 of ethylene, propylene and tetracyclopentenyl in a molar ratio of 1: 2: 0.03 made as follows:

The "reaction vessel is charged with 1.5 liters of isopropylcyclohexane The apparatus and the solvents are then rinsed with pure, dry nitrogen Then, the solvent is a mixture of ethylene / propylene in the molar ratio 1:.. 5 saturated and cooled to -2O ⁰ C The following solutions are in the three drip funnels:

1) 104.8 ml of 4% benzene vanadium tri-acetylacetone solution in one liter of n-hexane,

2) 17.5 ml of diethyl aluminum monochloride in one liter of n-hexane,

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3) 31.2 g of tetracyclopentenyl in one liter of η-hexane.

These 3 solutions are added dropwise uniformly with stirring into the reaction vessel over the course of 4 hours. Be at the same time Ethylene and propylene introduced in a molar ratio of 1: 2; 25 liters of ethylene and 50 liters of propylene are offered per hour. By external cooling, the temperature in the reactor is kept at -20 ° C. and the residence time is set to 15 minutes.

After working up and drying, 191 g fall slightly yellowish colored, rubber-like polymer with the following values:

RSV 1.38; 47 percent by weight propylene, no crystalline homopolyethylene, no isotactic polypropylene, iodine number after subtracting the blank value 2.4.

The vulcanization is carried out with the following recipe:

100 parts by weight of copolymer

6 "zinc oxide.

1.5 "tetram ethylthiuram disulfide

1.5 "sulfur

■ '

After 50 minutes at 160 ° C., a vulcanizate is obtained which is similar in its properties to a copolymer of ethylene, propylene and dicyclopentadiene vulcanized with the same formulation.

Example 3

^ Di- / cyclopenten- (l) -yl- (3 j7 is after Ber.d. Akad.Wise.SSSR 85, ^ 107 '

- »(1952), CA. 47, 7448 (1953) obtained from S-chloro-cyclopenten-d). ^;

The continuous copolymerization of ethylene, propylene and

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Dicyclopentenyl is used in a molar ratio of 1: 2: 0.01 in the in the apparatus described in Examples 1 and 2 carried out as follows:

Are used 1 g of dicyclopentenyl 0.5 mmol VOCl and 10.0 mmol of ethyl-aluminum sesquichloride and ^r over the entire reaction time of 4 hours per liter of hexane per hour. The residence time is 30 minutes, the reaction temperature 29 to 30 ^e C and the supply of ethylene and propylene 25 and 50 liters per hour. After the work-up described in Example 1, 160 g of pale yellowish colored polymer are obtained.

_a RSV 1.25, 57 percent by weight propylene, no crystalline polyethylene, no isotactic polypropylene. After subtracting the blank value, the iodine number is 2.5.

The vulcanization takes place with the following reaction:

100 parts by weight of polymer 5 "zinc oxide

1.5 "sulfur

1.5 "zinc diethyl dithiocarbamate (Vulkazit LDA)

After 30 minutes at 150 ° C., a highly elastic vulcanizate is obtained. Example 4

The discontinuous polymerization with ethylene, propylene and dicyclopentenyl in a molar ratio of 1: 2: 0.1 is carried out in tetrachlorethylene with 50 mmol of ethyl aluminum sesquichloride and 15 mmol of vanadium oxytrichloride. 1 100 ml of dry tetrachlorethylene are first saturated with dry nitrogen, then with ethylene / propylene in a molar ratio of 1: 2. The two catalyst components and the dicyclopentenyl are dissolved in tetrachlorethylene, the volumes of these three solutions are 100 ml each. With vigorous stirring and introduction of 25 liters of ethylene and 50 liters of propylene per hour, the ethyl aluminum sesquichloride \ solutions and the dicyclooentenyl solution within three minutes

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at the same time admitted. The VOCl solution is then added within 5 minutes.

The reaction temperature rises to 45 ° C. in a few minutes and is maintained by external cooling for the entire reaction time of one hour. After working up, 50 g of rubbery polymer are obtained. RSV 1.90, 49 weight percent propylene. The polymer is free of homopolyethylene and isotactic polypropylene and contains about three C ■ C double bonds per 1000 C atoms. the
Vulcanization with the recipe mentioned in Example 3 results in a highly elastic product. .

ORIGINAL INSPECTED

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Claims (1)

April 22, 1968 Claim Process for the preparation of easily vulcanizable elastomeric copolymers from ethylene, cK -olefins and polyunsaturated compounds in the liquefied monomers or in inert solvents in the presence of organometallic mixed catalysts, on the one hand from compounds of Z. to HI. Main group of the periodic table, which contain at least one hydrogen atom or an alkyl group bonded to the metal atom, and on the other hand from compounds of the metals of IV. To VI. Subgroup of the periodic table, characterized in that the polyunsaturated compounds used are multicycloalkenes with 2 to 6 cyoles, the number of ring members is 3 to 12 carbon atoms and the ring units are monocyclic, and the molar ratio of ethylene, o ( -olefin and multicyoloalkene 1 up to 10 to 1 to 10 to 0.01 to 1, preferably 1 to 5 to 1 to 5 to 0.01 to 0.05. Meue documents {Art 7 1 1 Abe. 2 No. I Sate 3 of the alteration gas. ν. 4.9. 19G 909815/1072 ORIGINAL INSPECTED