DE1925114B2 - Process for the production of a sulfur-vulcanizable polymer from ethylene and at least one other α-alkylene and its use for the production of shaped bodies - Google Patents

Description

The invention relates to a method for producing a sulfur-vulcanizable polymer from Ethylene, at least one other α-alkylene and at least one polyunsaturated compound, wherein a mixture of these monomers is brought into contact with a catalyst in a liquid distribution medium which is composed of an aluminum halogen compound, a transition metal compound and an organomagnesium compound.

The process mentioned is known from Dutch patent application 6613606 where as an organomagnesium compound a diaryl magnesium, preferably diphenyl magnesium, is used. A disadvantage of this process is that the polymerization agent must not contain any oxygen, water or other polar compounds. Another disadvantage is that the diaryl magnesium compound tends to give rise to colored polymerization products Cause.

According to the invention, an alkyl or cycloalkyl magnesium derivative is now used as the organomagnesium compound used, where one of the hydrocarbon groups by an alkoxy group, a chlorine, bromine or Iodine atom or a hydroxyl group can be replaced and the ratio of magnesium to the transition metal between 0.1 and 200 or between AIu- "' The minium and magnesium compound is between 0.5 and 30.

The catalyst used is very effective and has excellent solubility in the polymerization agent. The magnesium compounds in question fall

ι <· namely ais colorless, clear solutions. An advantage of the magnesium compounds which can be used according to the invention consists in the fact that one relatively larger Amounts of such a polar compound, e.g. B. diethyl ether, introduce into the polymerization agent

π can. With the aid of the catalyst used according to the invention, easily homogeneous polymers can be produced from ethylene, at least one other α-alkylene and at least one polyunsaturated compound which do not contain gel and which are easy to use

: ii way with sulfur to vulcanizates with excellent Properties are to be processed. Next is the initial activity of the catalyst according to the invention greater than when using a diaryl magnesium as an organomagnesium compound, which is

r. nem continuous process with a short dwell time of Advantage is. Further advantages of the invention are discussed later.

Examples of the magnesium compound which can be used according to the invention are dialkyl magnesium with the

The same or different alkyl groups with 1 to 12 carbon atoms and preferably 2 to 4 carbon atoms, e.g. B. Diethylmagnesium, Dipropylmagnesium, Dibutylmagnesium, Didecyl magnesium and didodecyl magnesium; Dicycloalkylmagnesium with the same or

ι. different cycloalkyl groups with 3 to 12 carbon atoms, and preferably 5 to 6 carbon atoms. Furthermore, the magnesium compound can be both an alkyl and contain a cycloalkyl group. In the compounds mentioned above, one of the hydrocarbons

Ki hydrogen groups through an alkoxy group, e.g. Legs Ethoxy, isopropoxy, butoxy or decoxy group, furthermore by a halogen atom, e.g. B. a chlorine, Bromine or iodine atom or be replaced by a hydroxyl group. For this purpose, connections come into

ii fertilize like ethyl magnesium chloride, ethyl magnesium bromide, Propyl magnesium hydroxide, butyl decoxymagnesium, dodecylbutoxymagnesium, butylisopropoxy magnesium, isobutylbutoxymagnesium and cyclohexylbutoxymagnesium. Especially with the last

~> <i th category of magnesium compounds advantageous polar compounds such as ethers, e.g. B. diethyl ether, dibutyl ether or tetrahydrofuran im Use excess so that the magnesium bond is very simple and without the necessary

can be produced by ether-free conditions can. Diethylmagnesium, dibutylmagnesium, butylisopropoxymagnesium are preferred and butyl decoxymagnesium. Mixtures of magnesium compounds can also be used

mi become.

Furthermore, activators can optionally also be used for the catalyst system, for. B. an alkanol, an alkenol, an alkanolate, an alkenolate, a carboxylic acid, an ester or a salt of the same

ivi ben, an aldehyde, a ketone, ozone, oxygen and / or water.

An aluminum trihalide, z. B. aluminum trichloride or

Aluminum tribromide, or an organoaluminum halide Find application. Mixtures of aluminum compounds can also be used. Suitable Organoaluminum halides contain, on average, a minimum of 1 per aluminum atom, however a maximum of 2 halogen atoms and at least one directly bonded to aluminum with a carbon atom Hydrocarbon radical. This hydrocarbon radical can be an alkyl, cycloalkyl, alkaryl, aryl or be an aralkyl group. Examples are diethyl aluminum chloride, Monoethyl aluminum chloride, diisobutyl aluminum chloride, Diisobutyl aluminum bromide, aluminum ethyl sesquichloride, and monohexyl aluminum dichloride.

A compound is preferably used as a compound of a transition metal, in particular a chloride of a metal of groups 4 to 6 inclusive of the periodic table according to Mendelejeff, in particular a compound of trivalent or tetravalent titanium or vanadium which is soluble in the polymerization agent. Examples of such compounds are TiBr., TU ₄ , VCl ₄ , VBr ,, VOCl ₃ and VCl ₅ , ZrCl ₄ , MoCl ₅ , MoCl ₄ , MoCl ₃ , WCl ₆ and in particular TiCl ₄ and / or TiCl ₃ . Optionally, one or more halogen atoms can be replaced by an alkoxy group or a chelate radical, so that, for. B. tetrabutoxytitanium or vanadium acetylacetonate come into consideration.

The ratio between the aluminum compound and the compound of a transition metal can vary within a wide range, e.g. B. between 2: 1 and 100: 1 and preferably between 5: 1 and 45: 1. The order of addition the catalyst components can be chosen as desired. It is preferred not to leave the transition metal compound first react with the aluminum halogen compound. The catalyst components are - after dissolving in a distribution agent continuous implementation of the process is preferably fed directly to the reaction zone. Man preferably leaves the catalyst for some time after mixing the catalyst components, e.g. B. some Seconds to less than 10 minutes, preferably below 0 ° C, e.g. B. at -40 ° C, mature.

The molar ratio between the magnesium compound and the transition metal compound can vary within the specified range. In general, as this ratio increases, the catalyst activity initially increases, then reaches a maximum value and then decreases again. The ratio at which the activity reaches its maximum value is generally reduced as the aluminum: transition metal ratio also becomes smaller. The magnesium / transition metal ratio is preferably between 0.3 and 50, in particular between V ₂ and 10.

Suitable a-alkylenes which can be used as monomers in addition to ethylene are the a- alkylenes with a maximum of 9 carbon atoms, e.g. B. propylene, butene-1, pentene-1, hexene-1, octene-1, the branched isomers thereof, e.g. B. 4-methylpentene-1, styrene, α-methylstyrene, vinyl chloride or acrylic acid, and mixtures of the above compounds. Propylene and / or 1-butene are extremely suitable.

Any customary compound can serve as the polyunsaturated compound; it contains minimal two C = C bonds and can be both aliphatic and alicyclic. The aliphatic, multiply un-

Saturated compounds generally contain 3 to 20 carbon atoms, both conjugated and can give non-conjugated double bonds. Examples are: 1,3-butadiene, isoprene, 2,3-dimethylbutadiene-1,3, 2-ethylbutadiene-1,3, piperylene, myrcene, allene, 1,2-butadiene, 1,4,9-decatrienes, 1,4-hexadiene, 1,5-hexadiene and 4-methylhexadiene-1,4. the alicyclic polyunsaturated compounds, which may contain a bridging group, can be both monocyclic and polycyclic and, if desired, contain one or more halogen atoms. It can in general, for. B. the alkyinorbornadienes can be used; also the alkylidene norbornenes, especially the 5-alkylidene norbornene-2, in which the alkylidene group I to 20 and preferably Contains 1 to 8 carbon atoms; the alkenylnorbornenes, especially the 5-alkenylnorbornenes-2, their alkenyl groups Contains 3 to 20 and preferably 3 to 10 carbon atoms, e.g. B. 5- (2'-methyl-2'-butenyl) -norbornen-2 and 5- (3'-methyl-2'-butenyl) -norbornen-2; Dicyclopentadiene and the polyunsaturated compounds of bicyclo- (2.2.1) -heptane, bicyclo- (2.2.2) -octane, bicyclo- (3.2.1) -octane and dicyclo- (3.2.2) -nonane, wherein at least one of the rings is unsaturated. There are also compounds such as 4,7,8,9-tetrahydroindene and isopropylidene tetrahydroindene. In particular, dicyclopentadiene, 5-methylene or 5-ethylidene norbornene-2 or hexadiene-1,4 used. Mixtures of the abovementioned compounds can also be used.

In general, only small amounts of these polyunsaturated compounds, e.g. B. 0.5 up to 10% by weight, to be incorporated into the amorphous polymer in order to nevertheless achieve good vulcanization reach; but larger quantities can also be processed.

The polymerization reaction usually takes place at a temperature between -40 and 80 ° C, preferably at 10 to 50 ° C instead. The pressure will usually be 1 to 50 at, but it can also be higher or lower pressures. A continuous process has the advantage, but it is a semi-continuous or batch process is also possible, if appropriate in one or more stages.

Any liquid which is inert with respect to the catalyst can be used as the distribution medium behaves, e.g. B. one or more saturated, aliphatic hydrocarbons, such as butane, pentane, hexane, heptane, Pentamethylheptane or petroleum fractions; further aromatic hydrocarbons, e.g. B. benzene or toluene, or halogenated aliphatic or aromatic hydrocarbons, e.g. B. tetrachlorethylene. It can preferably be carried out at such temperature and pressure conditions that a or more monomers, especially α-alkylene, z. B. propylene, is liquid and can be added in such an amount that it is used as a distribution agent serves. Another means of distribution is then superfluous. The inventive method can in one gas- and liquid-filled polymerization reactor take place; A whole with is preferred here Liquid filled reactor.

The molecular weight of the polymers is indicated by the specific viscosity; this viscosity is measured on a solution of 0.1 g of polymer in 100 cm ^{3 of} decalin at 135 ° C. The molecular weight can usually be determined by using so-called

Chain regulators, ζ. B. acetylene, zinc alkylene and alkyl halides and are preferably influenced by the use of hydrogen. Very little Amounts of hydrogen have a sufficient influence on the molecular weight and are still soluble in the polymerization agent.

From the reaction mixture formed during the polymerization, optionally after deactivation of the catalyst with z. B. water, alcohol or an acid, the polymer, optionally with addition of water, steam or methanol, are distilled off.

The polymer obtained according to the invention usually contains between 20 and 75% by weight of ethylene, 24 up to 79% by weight of one or more other α-alkylenes and at least 0.5% by weight of mono- or polyunsaturated compounds. For special purposes can the polymer in larger amounts, e.g. B. contain up to 30 wt .-%, a polyunsaturated compound.

The customary chemicals can be added to the polymers formed in this way, e.g. B. zinc oxide, Stearic acid, sulfur, antioxidants, organic accelerators, e.g. B. tetramethylthiuram disulfide, so-called "tackifiers" dyes and pigments. If necessary, at least some can this means, e.g. B. one or more antioxidants, already during the polymerization process be added. They can be added as such, but they are preferably added beforehand in the Liquid or liquids which are used as a dispersing agent in the polymerization, or mixed in one or more of the liquid or liquefied monomers. It can during the polymerization also reinforcing fillers such as chalk, kaolin and carbon black and the so-called extender oils are mixed into the polymer.

After vulcanization, the polymers result in a product that is characterized by its excellent properties very suitable for car tires. Mixing of the polymers according to the invention with other, slightly unsaturated Rubbers, e.g. B. butyl rubber and / or with highly unsaturated rubbers, e.g. B. Butadiene styrene rubbers produce products with excellent mechanical properties after vulcanization. The polymers can also be used in the manufacture of bicycle tires, conveyor belts, Footwear, flooring and waterproofing strips are applied.

The polymers formed according to the invention can easily be added by heating Vulcanize sulfur at a temperature of 100 to 250 ° C, preferably 140 to 170 ° C. It can If necessary, the vulcanization recipes customary for butyl rubber can be used. aside from that Free radical sources such as peroxides can also be used, but this is not a requirement.

The polymers according to the invention can be supplied in the form of crumbs, films, strands or balls will.

The following examples are intended to provide a more detailed explanation.

example 1

In a double-walled one with a stirrer, a thermometer, a gas inlet and gas outlet pipe equipped metal reactor are introduced 0.9 liters of benzene. Then be 100 mmol of butadiene-1,3 introduced and also ethylene and propylene in a molar ratio of 60:40 initiated; this introduction of ethylene and propylene is continued during the polymerization. leads. The catalyst components dissolved in benzene are then diethylaluminum chloride and titanium tetrachloride and dibutylmagnesium added, in amounts of 6.0 or 0.1 and 2.0 mmol. That Ultimately, the volume is 1 liter. The polymer

The ionization temperature is kept at 30.degree. C., and the The polymerization pressure is 0.7 at. The polymerization process is ended after two hours, after which time 84 g of polymer are obtained. This polymer contains 26% by weight propylene and is 0.13 mgeq / g

r> unsaturated. The specific viscosity is 3.3.

Example 2

In a long-term test, the same catalyst components are used in the same con-

'"centrations worked with heptane as a distribution medium. The ratio of ethylene to propylene is 30:70. The pressure is 1 at. The middle one Dwell time is 30 minutes. 110 mmol of butadiene are added per liter of distribution agent. Per liter of po-

^Ji lymerisationsmittel accumulates an amount of 9.6 g of polymer which contains 39 wt .-% propylene and is 0.47 mgeq / g unsaturated. The specific viscosity is 1.7.

'"Example 3

Example 2 is repeated, but now using a catalyst composition from 1 mmol diethylaluminum chloride, 0.25 mmol / 1 Din.-Butylmagnesium and 0.025 mmol / 1 titanium tetra- '' chloride. Instead of butadiene, an amount of 30 mmol / l dicyclopentadiene is now added. Per liter of polymerisation agent 27 g of polymer are obtained which, in addition to ethylene, also contain 49% by weight of propylene and 3.8 Contains wt .-% dicyclopentadiene. Use of diethyl magnesium instead of di-n.-butyl magnesium yields roughly the same result.

Example 4

j- After repeating experiment 3, where instead of 30 mmol / 1 dicyclopentadiene now 20 mmol / 1 5-ethylidene norbornene-2 are used, becomes a Yield of 30 g of polymer obtained which contains 0.7% by weight of 5-ethylidene norbornene. The in

- "Magnesium compound used in this example contains more than two molecules of dibutyl ether per atom of magnesium.

Example 5

■ • j A mixture of ethylene, propylene and 5-ethylidene norbornene-2 was polymerized continuously at a temperature of 25 ° C and a pressure of 1 atm. The following were fed into the reactor per hour:

bo a) 200 ml of heptane, in which 1 mmol of dibutylmagnesium and 40 mmol of 5-ethylidene-norbornene-2 were dissolved,

b) 900 ml of heptane, in which the reaction product of 4 mmol of diethylaluminum chloride with

to 1 mmol of decanol was dissolved, and

c) a solution of 0.1 mmol of TiCl ₄ in 900 ml of heptane.

In addition, the reactor was using 66 liters per hour

gaseous ethylene and 154 liters of gaseous propylene /.leitleit. The mean residence time in the reactor was M) minutes.

HM g of part polymer were obtained per hour.

Example 6

A mixture of ethylene, propylene and dicyclopentadiene was polymerized continuously at a temperature of 25 ° C. and a pressure of 1 atm. The following were fed into the reactor per hour:

a) a solution of 0.5 mmol of dibutyl magnesium and 60 mmol of dicyclopentadiene in 200 ml of heptane,

b) 900 ml of heptane, in which the reaction product of 2 mmol of diethylaluminum chloride mil

"> 0.5 mmol of decanol was dissolved, and

c) a solution of 0.045 mmol TiCl ₄ in 900 m heptane.

In addition, 55 liters of ethylene and liters of propylene per hour were introduced into the reactor.
The yield of terpolymer was 54 g per hour.

Claims (6)

Patent claims: L Process for the production of a sulfur vulcanizable polymer from ethylene, at least another α-alkylene and at least one polyunsaturated compound, being a mixture of these monomers in a liquid Distribution agent is brought into contact with a catalyst which is composed of an aluminum halogen compound, composed of a compound of a transition metal and an organomagnesium compound, characterized in that that an alkyl or cycloalkyl magnesium derivative is used as the organomagnesium compound is, where one of the hydrocarbon groups by an alkoxy group, a chlorine, Bromine or iodine atom or a hydroxyl group can be replaced and the ratio of magnesium to the transition metal between 0.1 and 200 or between aluminum and magnesium compounds is between 0.5 and 30. 2. The method according to claim 1, characterized in that the magnesium derivative is a dialkyl or dicycloalkylmagnesium is used. 3. The method according to claim 2, characterized in that diethyl magnesium is used will. 4. The method according to claim 2, characterized in that dibutyl magnesium is used will. 5. The method according to any one of claims 1 to 4, characterized in that the ratio Magnesium and transition metal compound is between 0.5 and 100. 6. Use of the unsaturated polymers prepared according to the preceding claims for the production of moldings by vulcanizing agents a sulfur-containing vulcanizing agent.