JPH0422921B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention utilizes a catalyst system comprising a vanadium compound soluble in the polymerization medium and an organoaluminum compound in which at least one hydrocarbon group is directly bonded to the metal atom via a carbon atom, in which 25 to 85 wt. , 15 to 75% by weight of at least one other 1-alkene, and optionally up to 20% by weight of polyunsaturated compounds. This type of method has been known for a long time;
It has already been industrialized on a large scale. On the other hand, the most preferred catalyst systems contain vanadium compounds and alkyl aluminum halides that are soluble in the polymerization medium. However, such catalyst systems have the disadvantage of low activity. In other words, the catalyst cost per unit of polymer weight is quite high and extensive purification is required to remove catalyst residues from the resulting polymer. For these reasons, various attempts have been made for quite some time to find ways to increase polymer yields, and it has been found that the addition of certain materials to the catalyst system increases yields. For example, Dutch Patent Application No. 6410447 proposes the use of various halogenated compounds such as trichloroacetic acid (or its esters), hexachloroacetone, hexachloropropylene or α-trichlorotoluene as promoters. In this case, the use of perchlorocrotonic acid compounds as activators is very effective, as described in Dutch Patent Application No. 6712044. However, the drawback of these compounds is that they have a high chlorine content. A portion of the perchlorocrotonic acid compound conversion remains in the polymer, but is rather difficult to recover by conventional catalyst residue removal methods. Therefore, polymers obtained using these compounds have a high chlorine content. The properties of the product, especially its aging resistance, which is influenced by climate, are adversely affected by high chlorine contents. In addition, high chlorine content polymers have the problem of corrosive processing equipment. Therefore, copolymerization of ethylene with at least one other 1-alkene and optionally a polyunsaturated compound results in a high polymer yield per unit of catalyst weight and a low chlorine content in the polymer product. A method of manufacturing a composite remains desirable. Using a novel activator for the catalyst system, 25~
85% by weight of ethylene, 15-75% by weight of at least 1
other 1-alkenes of the species, and in some cases 20
We have now found a method for copolymers consisting of up to % by weight of polyunsaturated compounds with high polymer yields per unit of catalyst weight, but in many cases the polymers obtained by this method have a low halogen content. . That is, the present invention utilizes a catalyst system comprising a vanadium compound soluble in the polymerization medium and an organoaluminium compound in which at least one hydrocarbon group is directly bonded to the metal atom via a carbon atom.
A method for producing a copolymer consisting of ~85% by weight ethylene, 15-75% by weight of at least one other 1-alkene, and optionally up to 20% by weight of a polyunsaturated compound, comprising: It is characterized in that polymerization is carried out in the presence of a halogen-containing compound represented by the general formula. A halogen-containing compound represented by the following general formula: In the formula, A is a phenyl group which can have one or two substituted halogen atoms or an alkyl group,
or a thienyl group bonded to a carbon atom; has the following structural formula: -C≡N,

【formula】

【formula】

【formula】

A group represented by any one of [Formula],
In the formula, R and R' are both hydrocarbon groups having 1 to 8 carbon atoms, and X is a chlorine atom or a bromine atom. Preference is given to using halogen-containing compounds having one or two halogen atoms, especially chlorine atoms, per molecule. Particularly preferred are alkyl esters and alkoxyalkyl esters of phenyl dichloroacetic acid, diphenyl chloroacetic acid, and (2-thienyl) mono- or di-chloroacetic acid, but compounds with a larger number of halogen atoms can also be used. Particular examples of suitable halogen-containing compounds are as follows. Ethyl chlorophenyl acetate, ethyl dichlorophenyl acetate, propyl chlorophenyl acetate, propyl dichlorophenyl acetate, butyl chlorophenyl acetate, butyl dichlorophenyl acetate,
Ethyl bromophenyl acetate, ethyl dibromophenyl acetate, butyl bromophenyl acetate, butyl dibromophenyl acetate,
Methoxyethyl chlorophenyl acetate, methoxyethyl bromophenyl acetate, methoxyethyl dibromophenyl acetate, ethyl-2
-chloro-3-oxo-3-phenyl-propionate, ethyl 2,2-dichloro-3-oxo-
3-phenylpropionate, butyl 2,2-dibromo-3-oxo-3-phenylpyropionate, methyl chlorodiphenyl acetate, ethyl chlorodiphenyl acetate, ethyl bromodiphenyl acetate, butyl bromodiphenyl acetate . These compounds were described by M. Julia and M.
Baillarged “Bull.Sco.Chim.de France”1959,
It can be obtained by the method described in P850-853. Further examples of suitable halogen-containing compounds are as follows. Monochlorophenylacetonitrile, dichlorophenylacetonitrile, monobromophenylacetonitrile, dibromophenylacetonitrile, cyclobenzoylmononitrile, chlorophenylacetyl chloride, dibromophenylacetyl chloride, dichlorophenyl-N,N-dimethylacetamide, dibromof enyl-N,N-diethylacetamide, (carboethoxyphenyl)phenyldichloromethane,
(carbomethoxyphenyl)phenylbromomethane, ethylchloro(2-thienyl)acetate,
Ethyldichloro(2-thienyl)acetate, Butylbromo(2-thienyl)acetate, Butyldichloro(2-thienyl)acetate, Ethylchloro(2-thienyl)acetonitrile, Butylbromo(2-thienyl)acetonitrile, Ethyldichloro(2-thienyl)acetonitrile , butyldibromo(2-thienyl)acetonitrile, chloro(2-thienyl)acetyl chloride. Suitable examples of organoaluminum compounds include diethylaluminum chloride (DEAC), diisobutylaluminum chloride, monoethylaluminum dichloride (MEAC), and ethylaluminum sesquichloride (AEAC). Mixtures of these compounds can also be used. Further, as the vanadium compound, vanadium oxytrichloride (VOCl ₃ ), vanadium alkoxide [VO(OR) ₃ ], etc. are preferable. Although the molar ratio of organoaluminum compound to vanadium compound can be varied within a wide range,
Generally this molar ratio is between 1:1 and 1500:1. Suitable molar ratios may be selected between 2:1 and 300:1, especially between 3:1 and 50:1. The activating halogen-containing compound has a molar ratio of 0.1:1 to 300:1, preferably 1:1 to vanadium.
It is used in an amount of 1 to 50:1, especially 2:1 to 30:1. In addition to the three components mentioned, other substances may be added to the catalyst if advantageous. As such a substance, a Lewis base may also be used as a catalyst component. However, this substance does not need to be added at all in order to increase the polymer yield per catalyst weight unit. Suitable 1-alkenes which can be used as monomers in addition to ethylene include 1-alkenes having up to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and their branches. isomers such as 4-methylpentene-
1, styrene, α-methylstyrene, and mixtures of these alkenes. Particularly preferred are propylene and/or butene-1. Polyunsaturated compounds which can be used in the present invention and which can desaturate the polymer are well known and may be aliphatic or cycloaliphatic compounds having at least two C═C bonds. The number of carbon atoms of the aliphatic polyunsaturated compounds that can be used is generally 3 to 3.
20, and the double bond may be either a conjugated bond or a non-conjugated bond (which is preferred). Examples include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene 1-3,2
-ethylbutadiene 1-3, piperylene, myrcene, allene, 1,2-butadiene, 1,4,9-
decatriene, 1,4-hexadiene, 1,5-
Hexadiene and 4-methylhexadiene 1-4
There is. The alicyclic polyunsaturated compound may or may not have a bridging group, and is either a monocyclic compound or a polycyclic compound. Among the commonly applicable ones are, for example, norbornadiene and its alkyl derivatives. For example, alkylidene norbornene, especially when the number of carbon atoms in the alkylidene group is 1
~20 preferably 1 to 8 5-alkylidenenorbornene-2, alkenyl group having 2 to 20 carbon atoms,
Preferably 2 to 10 alkenylnorbornene-2, especially 5-alkenylnorbornene-2, such as vinylnorbornene, 5-(2'-methyl-2'-butenyl)-norbornene-2 and 5-(3'-methyl-2)
2'-butenyl)-norbornene-2, dicyclopentadiene and bicyclo-(2,2,1)-heptane, bicyclo-(2,2,2)-octane, bicyclo-(3,2,1)-octane and Bicyclo-(3,
There are polyunsaturated compounds of 2,2)-nonane in which at least one ring is unsaturated. Furthermore, compounds such as 4,7,8,9-tetrahydroindene and isopropylidenetetrahydroindene can also be used. In particular, dicyclopentadiene,
5-methylene or 5-ethylidene norbornene-2, or hexadiene 1-4 is used.
Mixtures of said compounds can also be used. Polyunsaturated compounds may be present in amounts up to 20% by weight, especially 10
It may be present in amounts up to % by weight. In addition to or instead of the above polyunsaturated compounds, e.g. halogen atoms, OH- groups, OR
If desired, unsaturated compounds having one or more functional groups such as - groups, COOH- groups, COOR groups or NH ₂ - groups can be incorporated into the polymer in amounts up to 20% by weight. Generally, such functional monomers have a negative effect on the activity of the polymerization catalyst, but with the activator according to the present invention, even if such monomers are present in the polymerization mixture,
A reasonable polymerization rate can be achieved. The molar ratio of monomers used will vary depending on the desired polymer composition. Since the polymerization rate of the monomers can vary widely, it is not possible to set an effective molar ratio, but in the case of copolymerization of ethylene and propylene, the molar ratio should be selected from approximately 1:1 to 1:5. Bye. When polyunsaturated compounds are included in the polymerization, their molar ratio to ethylene is approximately
It can be selected from between 0.001:1 and 1:1. The polymerization reaction is usually carried out at -40 to 100°C, preferably at 10°C.
Perform at a temperature of ~80 °C. Also, the pressure is 1~
50 atm is typical, but higher or lower pressures can also be used. Preferably, it is carried out continuously, but it is also possible to carry out semi-continuously or batchwise. The residence time during the polymerization reaction can vary from several seconds to several hours. Generally, residence times of several minutes to one hour may be selected. The polymerization reaction is carried out using an inert liquid such as butane,
one or more saturated aliphatic hydrocarbons such as pentane, hexane, heptane, pentamethylpentane or petroleum distillates; aromatic hydrocarbons such as benzene or toluene; or halogenated aliphatics or aromatics such as tetrachloroethylene. Performed in hydrocarbons. Temperature and pressure may be selected such that one or more of the monomers used, particularly the 1-alkene such as propylene, is in liquid form and is present in an amount such that it functions as a resolving agent. In this case no other dispensing agent is required. The method of the present invention can also be carried out in a polymerization reactor filled only with gas or liquid. The molecular weight of the polymers can be adjusted by means of so-called chain regulators such as acetylene, zinc alkyls, alkyl halides, preferably hydrogen. Hydrogen can have a significant effect on molecular weight even in small amounts and is nevertheless soluble in the polymerization medium. The polymer is separated from the polymerization reaction mixture by distillation in a known manner, optionally with the addition of water, steam or methanol, after deactivation of the catalyst, optionally with water, alcohol or acid. It can be recovered. The copolymers obtained by the process of the invention contain from 25 to 85% by weight of ethylene. However, preferred copolymers are those having an ethylene content of 40 to 75% by weight. The method of the invention is particularly advantageously applied to the production of elastomeric copolymers. Such copolymers are suitable for a wide variety of applications, such as the production of hoses, conveyor belts, seals. If desired, the copolymers can be vulcanized using free radial formers such as peroxides or sulfur in known manner. EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not intended to be limited by these Examples. The activating materials used in the following examples were selected from the following group: 1 Ethylchlorophenylacetate 2 Ethyldichlorophenylacetate 3 Butylchlorophenylacetate 4 Butyldichlorophenylacetate 5 Methyldichlorophenylacetate 6 Methoxyethyldichlorophenylacetate 7 Ethyl-2,2-dichloro-3-oxo-3
-Phenylpropionate 8 2,2-dichloro-1,2-diphenylethanal 9 Ethylchloro(2,4-dichlorophenyl)
Acetate 10 Ethylchlorophenylacetate 11 Dichlorophenylacetonitrile 12 Ethylchloro(2-thienyl)acetate 13 Phenyl(4-carboethoxyphenyl)dichloromethane The structural formulas of the above compounds are shown in the attached structural formula table. In addition, only the number of the compound is included in the table described after each example. The meanings of the abbreviations used in each example and each table are as follows. EN Ethylidene norbornene DCPD Dichloropentadiene SEAC Ethylaluminum sesquichloride TCAE Ethyl trichloroacetate PCCE Butyl ester of pechlorocrotonic acid sol.conc. Solution concentration C ₃ -cont. Propylene units of polymer Example 1 Production of ethylene/propylene copolymer 0.5 volume of gasoline was introduced into a glass, double-walled reactor with a volume of 1, equipped with a stirrer, ethylene and propylene feed pipes and gas discharge pipes. Ethylene and propylene were then fed to the reactor at flow rates of 35/hour and 70/hour, respectively. After monomer saturation with gasoline, catalyst components were added in the amounts shown in Table 1. During the polymerization, the concentration in the reactor was maintained at 50°C. After 15 minutes, methanol was added to terminate the polymerization. The polymer was recovered from the solution by evaporating the gasoline. The conditions and results are summarized in Table 1.

[Table] From the above results, it is clear that as the ratio of halogen-containing compound to vanadium increases, the copolymer yield also increases. It is also seen that various ratios of aluminum compound to halogen-containing compound can be used to obtain good polymer yields. Example 2 Continuous production of ethylene/propylene copolymer The polymerization was carried out in a 2.5 steel reactor equipped with a stirrer, a cooling jacket and the necessary feed and discharge pipes. Gasoline was introduced into the reactor at a flow rate of 3/hour. Gaseous ethylene, propylene and hydrogen were introduced into the reactor in the amounts indicated in the table. Gasoline solutions of ethylaluminum sesquichloride, vanadium oxytrichloride, and the activator butyl ester of phenyldichloroacetic acid were all fed to the reactor at a flow rate of 0.6/hour. The concentrations of each of the above gasoline solutions were determined so that the concentration of catalyst components in the reactor was maintained at the values shown in the table. By continuously withdrawing the polymer solution, the content of the reactor is maintained at 0.6, and the temperature and pressure inside the reactor are controlled respectively.
It was maintained at 50°C and 6.5 atm. The solution removed from the reactor was quenched by the addition of methanol and the polymer concentration was determined. Solution concentration is one measure of catalyst system activity. Conditions and results are shown in Table 2
I will summarize it in.

【table】

[Table] From the above results, it can be seen that the lower the vanadium concentration, the higher the yield of the copolymer. Example 3 Preparation of a copolymer of ethylene, propylene and polyunsaturated compounds The polymerization was carried out in a 2.5 steel reactor equipped with a stirrer, a cooling jacket and the necessary feed and discharge pipes. Gasoline was fed to the reactor at a flow rate of 3/hour. Gaseous ethylene and propylene were fed in the amounts indicated in the table. Ethylaluminum sesquichloride was delivered to the reactor at a flow rate of 0.6/hour. The termonomer, ethylidene norbornene and activator were dissolved together in gasoline and the resulting solution was sent to the reactor at a flow rate of 0.6/hour.
The concentrations of each solution were determined so that the monomer and catalyst component concentrations were maintained at the values shown in the table. By continuously withdrawing the polymer solution, the contents of the reactor were kept constant at 0.6/hour, and the temperature and pressure inside the reactor were kept at 50°C and 6.5 atm, respectively.
maintained. The reaction mixture removed from the reactor was quenched by addition of methanol and the polymer concentration was determined. The polymer concentration of the solution is one measure of the activity of the catalyst system. The conditions and results are summarized in Table 3.

[Table] * Not according to the present invention.
We tried using the corresponding bromine compound, but the results were similar. Example 4 In a similar manner to Example 3, at 50°C and
A terpolymer of ethylene, propylene and ethylidene norbornene was prepared at 6.5 atm. The conditions and results are as shown in Table 4. It can be seen that when using the activator of the present invention, reasonable polymer yields can be obtained even at low vanadium concentrations in the reactor.

[Table] Example 5 A terpolymer of ethylene, propylene and ethylidenenorbornene (EN) or dicyclopentadiene (DCPD) was prepared in the same manner as in Example 3.
It was made at 50℃ and 6.5atm. After deactivating the catalyst with methanol, the polymer solution was washed first with dilute hydrochloric acid and then with water, and the polymer was recovered by evaporating the solvent. The halogen content of the obtained polymer was determined. The conditions and results are summarized in Table 5. It is clear that using the activators of the invention products with low halogen content are obtained.

[Table] * Not according to the present invention.
TCAE Trichloroacetic acid ester
PCCE Perchlorocrotonic acid ester Example 6 Vanadium alkoxide [VO
(OR) ₃ ], as well as diethylaluminum chloride (DEAC) and monoethylaluminum chloride (MEAC), similar effects were obtained. Structural formula table

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【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】 [Brief explanation of drawings]

FIG. 1 is a flowchart of the catalyst used for producing the copolymer of the present invention.

Claims (1)

[Claims] 1. Using a catalyst system comprising a vanadium compound soluble in a polymerization medium and an organoaluminium compound in which at least one hydrocarbon group is directly bonded to a metal atom via a carbon atom, A process for the preparation of copolymers consisting of ethylene, 15 to 75% by weight of at least one other 1-alkene, and optionally up to 20% of polyunsaturated compounds having the general formula : [In the formula, A is a phenyl group which can have one or two substituted halogen atoms or an alkyl group,
or a thienyl group bonded to a carbon atom; is a group represented by any one of the following structural formulas: -C≡N, [Formula] [Formula] [Formula] [Formula], where R and R' both have 1 carbon atom. -8 hydrocarbon groups, and X is a chlorine atom or a bromine atom]. 2. The method according to claim 1, wherein the halogen-containing compound has one or two halogen atoms. 3. The method according to claim 1 or 2, wherein the halogen-containing compound is an alkyl ester or alkyl alkoxy ester of phenyl monochloroacetic acid or phenyl dichloroacetic acid. 4. The method according to claim 1 or 2, wherein the halogen-containing compound is an alkyl ester or alkyl alkoxy ester of benzoyl monochloroacetic acid or benzoyl dichloroacetic acid. 5. The method according to claim 1 or 2, wherein the halogen-containing compound is an alkyl ester or an alkoxyalkyl ester of diphenylmonochloroacetic acid. 6. The method according to claim 1 or 2, wherein the halogen-containing compound is an alkyl ester or alkyl alkoxy ester of thienyl monochloroacetic acid or thienyl dichloroacetic acid. 7. A method according to any one of claims 1 to 6, wherein the catalyst system comprises an alkyl aluminum halide. 8. The method of claim 7, wherein the catalyst system comprises vanadium oxytrichloride and ethylaluminum sesquichloride. 9. Process according to any one of claims 1 to 8, characterized in that the halogen-containing compound is used in an amount such that the molar ratio to vanadiur is from 0.1:1 to 300:1. 10. The method of claim 9, wherein the halogen-containing compound is used in an amount such that the molar ratio to vanadium is from 1:1 to 50:1.