JPH02180910A - Production of cycloolefin polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer of a narrow MW distribution in good efficiency by polymerizing a cycloolefin optionally having an unsaturated bond outside the ring in the presence of a catalyst comprising a combination of a transition metal compound with an aluminooxane. CONSTITUTION:The purpose polymer is obtained by polymerizing a cycloolefin optionally having an unsaturated bond outside the ring in the presence of a catalyst comprising a transition metal compound (a) and an aluminooxane (b). The compound (a) is one containing a metal selected from among group IV b, V b and VI b elements of the periodic table, among which a titanium or zirconium compound is desirable because of its high activity. A desirable form of this compound is one having a halogen atom, one having a halogen atom and a hydrocarbon group or one having an alkoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a cyclic olefin or a homopolymer of a cyclic olefin having an extracyclic unsaturated bond.

Specifically, by using a catalyst that combines a specific transition metal compound and a specific organic aluminum, a cyclic olefin or a cyclic olefin with an unsaturated bond outside the ring can be efficiently polymerized to produce a polymer with a narrow molecular weight distribution. Relating to a method of manufacturing.

(Prior Art) Conventionally, as a method for producing a cyclic olefin polymer, a method using a titanium-based catalyst consisting of a titanium compound and an organoaluminum compound, and a vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound are well known.

However, when these catalyst systems are used, the reactivity of the cyclic olefin is poor, and when a large amount of cyclic olefin is used, the catalyst activity is impaired, and side reactions such as ring-opening polymerization reactions and isomerization reactions are likely to occur. There are drawbacks. In particular, vanadium-based catalysts have the disadvantage of extremely low polymerization activity compared to titanium-based catalysts.

In addition, as a method for producing a cyclic olefin polymer having an extracyclic unsaturated bond, Kennedy
Method by cationic polymerization by et al. Journal of Macromolecule Science Chemistry Edition Al
(3) 345 (1967) [J, Macromo
l, Sci, (chem,) Al (3) 345
(1967)], Method using palladium compounds as catalysts Journal of Polymer Science B4541 (
1966) [J, Polym.

Sci, B4541 (1966)]
USI) 3494897 is fried.

Among these methods, the production method using cationic polymerization is very low temperature (-5
It has the disadvantage that it is necessary to carry out the polymerization at a temperature (below 0°C) and that the yield is also low. On the other hand, the method of using a palladium compound as a catalyst has the drawbacks that the monomer forms a complex with the catalyst and becomes stable, the polymerization activity is low, and a ring-opening reaction also occurs.

In addition, in the polymerization method of olefins, a method using a catalyst consisting of a transition metal compound and aluminoxane as a new highly active polymerization catalyst is described in JP-A-61-221206 and Journal of Polymer Science Chemistry Edition (23) 2151-2164 ( 1985)
[J, Polym, Sci Chem, Ed.
(23) 2151-2164 (1985)], only the copolymerization of α-olefins and cyclic olefins is described, but cyclic olefins or single cyclic olefins having an extracyclic unsaturated bond are described. No information is given regarding the method for producing the polymer.

(Problems to be Solved by the Invention) When producing a cyclic olefin or a homopolymer of a cyclic olefin having an extracyclic unsaturated bond, side reactions such as ring-opening reactions, isomerization reactions, and crosslinking are likely to occur. There were problems such as low polymerization activity and low yield. Therefore, there is a strong demand for a catalyst system and a method for producing a polymer that has excellent polymerization activity and allows the polymerization reaction to proceed selectively at either the extracyclic or intracyclic unsaturated bonds without causing side reactions. The present inventors, based on the above-mentioned state of the prior art in the field of producing cyclic olefins or cyclic olefin polymers having an unsaturated bond on the outside of the ring, As a result of investigating a method for producing a polymer in which the polymerization reaction of cyclic olefins proceeds preferentially at either the endocyclic or extracyclic unsaturated bonds, has excellent polymerization activity, and has a narrow molecular weight distribution, we found that transition metal compounds We have discovered that the above object can be achieved by polymerizing a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond alone in the presence of a catalyst consisting of a specific aluminoxane, and have thus arrived at the present invention. .

(Means for Solving the Problems) (1) The present invention involves polymerizing a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond in the presence of a catalyst consisting of (a) a transition metal compound and (b) aluminoxane. The present invention relates to a method for producing a cyclic olefin polymer characterized by the following.

(2) The transition metal compound in (1) above is IVb of the periodic table.
The group consisting of Vb group, Vb group, and Vb group.

(3) The extracyclic unsaturated bond in (1) above is a vinyl group or a vinylidene group.

The present invention will be explained in detail below.

The transition metal compound (a) as a catalyst component used in the method of the present invention is a transition metal compound selected from the group consisting of Group 1'/b, Group Vb, and Group Vb of the periodic table,
Examples include compounds such as titanium, zirconium, hafnium, vanadium, and chromium. Among these transition metal compounds, titanium or zirconium compounds are preferred because of their high activity. A preferred form of the transition metal compound is a compound having a halogen atom, a compound having a halogen atom and a hydrocarbon group, a compound having a hydrocarbon group, or a compound having an alkoxy group.

Specific examples of the halogen atom include fluorine, chlorine, and iodine atoms. Specifically, the hydrocarbon group includes alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, 5ec-butyl group, tert-butyl group, and isobutyl group, isopropenyl group, and 1-butenyl group. Alkenyl groups with radicals Cycloalkagenyl groups such as cyclopentagenyl groups, methylcyclopentagenyl groups, tetramethylcyclopentagenyl groups, indenyl groups, tetrahydroindenyl groups, aralkyl groups such as benzyl groups, neophyl groups, etc. Examples include groups. Specific examples of the alkoxy group include alkylalkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, 5ec-butoxy group, and tert-butoxy group, and cyclohexanoxy group. For example, an alkoxy group including a cyclic compound such as a group or a menthoxy group can be exemplified.

Furthermore, specific transition metal compounds include titanium tetrachloride, titanium trichloride, bis(cyclopentadienyl)dimethyltitanium, bis(cyclopentajenyl)diethyltitanium, bis(cyclopentajenyl)diisopropyl Titanium, bis(methylcyclopentagenyl)dimethyltitanium, bis(cyclopentagenyl)methyltitanium monochloride, bis(cyclopentagenyl)ethyltitanium monochloride, bis(cyclopentagenyl)isopropyltitanium monochloride, bis (cyclopentagenyl)methyltitanium monopromide, bis(cyclopentagenyl)methyltitanium monochloride, bis(cyclopentagenyl)methyltitanium monochloride, bis(indenyl)methyltitanium monochloride, bis(indenyl)methyl Titanium monoplumide, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl) titanium dichloride, bis(cyclopentagenyl)
Titanium dichloride, bis(cyclopentagenyl) titanium dichloride, bis(indenyl) titanium dichloride, bis(indenyl) titanium dichloride, tyrene bis(indenyl) titanium dichloride, ethylene bis(indenyl) titanium, tetramethoxytitanium, tetraethoxytitanium, Titanium compounds such as tetra-n, propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-5ec-butoxytitanium, tetra-tert-butoxytitanium, tetramentoxytitanium. Zirconium tetrachloride, bis(cyclopentagenyl)dimethylzirconium, bis(cyclopentagenyl)diethylzirconium, bis(cyclopentagenyl)diisopropylzirconium, bis(methylcyclopentagenyl)dimethylzirconium, bis(cyclopentagenyl)dimethylzirconium ) Methylzirconium monochloride, bis(cyclopentagenyl)ethylzirconium monochloride, bis(cyclopentagenyl)isopropylzirconium monochloride, bis(cyclopentagenyl)methylzirconium monopromide, bis(cyclopentagenyl) ) Methylzirconium monochloride, bis(cyclopentagenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium cyfloride, bis(cyclopentagenyl)zirconium dibromide, bis(cyclopentagenyl)zirconium monochloride hydride , bis(indenyl)zirconium dichloride, bis(indenyl)zirconium dibromide, ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium dibromide, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraiso Propoxyzirconium, tetra-n-butoxyzirconium, tetraisobutoxyzirconium, tetra-5ec-butoxyzirconium, tetra-tert-butoxyzirconium,
Zirconium compounds such as tetramentoxyzirconium. Hafnium tetrachloride, bis(cyclopentagenyl)
Dimethyl hafnium, bis(cyclopentagenyl) methyl hafnium monochloride, bis(cyclopentagenyl) ethyl hafnium monochloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dichloride, bis(cyclo pentagenyl) hafnium monochloride halide, bis(indenyl) hafnium dichloride, ethylene bis(
hafnium compounds such as indenyl) hafnium dichloride, tetraethoxy hafnium, tetra-n-propoxy hafnium, tetraisopropoxy hafnium, tetra-n-butoxy hafnium, tetra-tert-butoxy hafnium, and tetramentoxy hafnium. Examples include vanadium compounds such as bis(cyclopentagenyl)vanadium dichloride and bis(cyclopentagenyl)vanadium monochloride.

In the present invention, examples of the aluminoxane (b) used as a catalyst component include organoaluminum compounds represented by the formula - (wherein R represents a hydrocarbon group and n represents an integer of 1 or more). I can do it. Regarding the aluminoxane, R is a straight or branched hydrocarbon group such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, and particularly preferred is a methyl group. n is an integer of 1 or more, preferably 5 or more, particularly preferably 10-100.

The method for producing the aluminoxane includes the following method.

(1) A compound containing adsorbed water, a compound containing crystal water, such as copper sulfate hydrate, aluminum sulfate hydrate, etc., is suspended in an organic solvent, and trialkyl aluminum is added thereto and reacted. Method.

(2) A method in which water is directly added to trialkylaluminium in an organic solvent to cause the reaction.

Among these methods, method (1) is preferred. Note that the aluminoxane may contain a small amount of organometallic component.

Specifically, the cyclic olefins supplied to the polymerization reaction using the catalyst of the present invention include monocycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, and cyclododecene, norbornene, 5, methyl-2-norbornene, 5-ethyl-2-norbornene, 5-inbutyl-2-norbornene, 5,6-dimethyl-2, bicycloalkenes such as norbornene, 2.3.3a, 7a-tetrahydro-4,
Tricycloalkenes such as 7-methano-1n-indene, 3a,5,6,7a-tetrahydro-4,7-methano-IH-indene, 1,4,5.8-dimethano-1,2
, 3,4,4a,5,8.8a-octahydronaphthalene, as well as 2-methyl-1,4,5,8-dimethano-
1,2,3,4,4a,5,8.8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1
,2,3,4,4a,5,8.8a-octahydronaphthalene,2-propyl-1,4,5,8-dimethano-1
,2,3,4,4a,5,8.8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethanol-1
,2,3,4,4a,5,8,8a-octahydronaphthalene,2-stialyl-1,4,5.8-dimethano-
1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8, 8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,
8-dimethano-1,2,3,4,4a,5,8.8a-
Octahydronaphthalene, 2-chloro-1,4,5,8
-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-
Dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-
Dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dichloro-1,4,5,
8,8-dimethano-1,2,3,4,4a,5,8,8
Tetracycloalkenes such as a-octahydronaphthalene, hexacyclo[6,6,1,13・6,110・1
3,02,7. Q9,14] heptadecene-4, pentacyclo[8,8,12.9,14.7,111.18.
Q, Q3・8,012・171 Henikosen-5, Octacyclo[8,8,12,9,14,7J11,18,
113,16,0,03,8゜012J7] Tokosen-
Cyclic monoenes such as polycycloalkenes such as 5, 5-
Vinyl-2-norbornene, vinylcyclohentene, vinylcyclohentene, 4-vinyl-1-cyclohexene, lytin-2-norbornene, 5-methylidene-2-norbornene, dicyclopentadiene, dicyclopentajenylheptene, Alkylidene tetrahydroindene, 3
Examples include cyclic polyenes such as a,4,7,7a-tetrahydroindene. (R1 and R2 are hydrogen alkyl groups,
Indicates halogen, and each may be the same or different. ) The cyclic olefin used in the polymerization reaction system in the present invention consists of only one type of cyclic olefin.

In the process of the invention, the polymerization reaction is usually carried out in a hydrocarbon medium. Examples of hydrocarbon media include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, and gasoline, kerosene, and light oil. In addition to petroleum fractions, raw material olefins also serve as hydrocarbon media. Among these, aromatic hydrocarbons are preferred.

In the present invention, the polymerization method is not particularly limited and may be selected from commonly used polymerization formats such as suspension polymerization and solution polymerization. The temperature during the polymerization reaction is usually -50 to 23
0°C, preferably -30 to 200°C, more preferably 0°C to 150°C.

In the present invention, the amount of transition metal compound used in the liquid phase polymerization reaction system is usually 10-8 as the concentration of metal atoms.
It ranges from 10@-1 to 10@-1 gram atoms/l, preferably from 10@-7 to 10@-2 gram atoms/liter.

The amount of aluminoxane to be used is usually in the range of 10-6 to 10-1 gram atom/l, preferably 10-5 to 5X10-2 gram atom/l, and the concentration of aluminum atoms is in the range of 10-6 to 10-1 gram atom/l, and The ratio of aluminum atoms to transition metal atoms in the reaction system is usually 2 to 10.
7, preferably in the range of 10 to 106. After the polymerization reaction is completed, a cyclic olefin polymer can be obtained by pouring the mixture into a methanol/hydrochloric acid mixed solvent.

(Effects of the Invention) According to the present invention, it is possible to obtain a cyclic olefin polymer having excellent polymerization activity, no side reactions, and polymerization proceeding through an addition reaction without ring opening and having a relatively narrow molecular weight distribution.

Furthermore, when a cyclic olefin having a vinyl group is used, the reaction proceeds by addition reaction of the endocyclic olefin. The resulting polymer has unreacted vinyl groups, which can be chemically modified by halogenation, epoxidation, alcoholization, hydroformylation, and the like.

Examples of the present invention will be shown below.

(Examples) Example 1 (1) [Preparation of aluminoxane] Aluminoxane was prepared as follows under a nitrogen stream. C in a 300ml flask that was sufficiently purged with nitrogen.
Suspend 4 g of uSO4.5H and 67 ml of toluene, drop 24 ml of trimethylaluminum diluted with 150 ml of toluene at a temperature of -30 to -20°C, and stir at 0°C for 6 hours after the dropwise addition is complete. After that, the temperature was gradually raised and the reaction was carried out at 40°C for 12 hours. Subsequently, solid-liquid separation was performed once, and the separated liquid was used for polymerization as aluminoxane.

(2) [Polymerization] 35 ml of toluene, 2 mmol of methylaluminoxane obtained in (1) above, and 0.1 mmol of bis(cyclopentadienyl)zirconium dichloride were added to a 100 ml glass pressure flask purged with nitrogen. Next, 5
- Add 5 ml of vinyl-2-norbornene and heat at 80°C for 2 hours.
The polymerization reaction was carried out for 4 hours. After the reaction was completed, the reaction product was poured into methanol-hydrochloric acid to stop the reaction, and the resulting polymer was filtered and dried. The obtained poly(5-vinyl-2-
norbornene) was 0.91 g.

3070, 1630, 980 from IR spectrum
, absorption of vinyl groups was confirmed at 900 cm'. Also,
It was confirmed that the absorption of the endocyclic double bond between 710 and 720 cm' was almost completely eliminated. From IH-NMR spectrum analysis, 4.8-5.2 ppm, 5.5-
Absorption originating from the proton of the vinyl group at 6.2 ppm was observed, but almost no absorption originating from the sharp proton of the endocyclic double bond at 6.0 ppm was observed. From the above, it has become clear that the reaction in this catalyst system proceeds as an addition reaction of the endocyclic double bond.

Comparative Example 1 A polymerization reaction was carried out in the same manner as in Example 1-(2) except that 0.4 mmol of triethylaluminum was used instead of methylaluminoxane. I couldn't.

Example 2 In Example 1-(2), 0.1 mmol of tetraisopropoxytitanium was used instead of bis(cyclopentadienyl)zirconium dichloride, and the reaction temperature was 40
A polymerization reaction was carried out in the same manner as in Example 1-(2) except that the temperature was °C. As a result, poly(5, vinyl) was obtained.

2-norbornene) was 0.15 g. IR,H-
It was confirmed by NMR that the reaction proceeded as an addition reaction of the intracyclic double bond, and that the vinyl group remained largely uninvolved in the reaction.

Example 3 Same as Example 1-(2) except that 0.1 mmol of titanium tetrachloride was used instead of bis(cyclopentadienyl)zirconium dichloride and the reaction temperature was 40°C. A polymerization reaction was carried out in the same manner. the result,
The obtained poly(5-vinyl-2-norbornene) was 0.
It was 18g. It was confirmed from IR, 'H-NMR that the reaction proceeded as an addition reaction of the intracyclic double bond, and that the vinyl group mostly remained without participating in the reaction.

Example 4 In Example 1-(2), 5-ethylidene-2,norbornene was used instead of 5-vinyl-2-norbornene.
The polymerization reaction was carried out in the same manner as in Example (2) except that ml was used. As a result, the obtained poly(5-ethylidene-
2-norbornene) was 1.41 g. IR,”H
-NMR confirmed that the reaction proceeded only by the addition reaction of the endocyclic double bond.

Example 5 A polymerization reaction was carried out in the same manner as in Example 1-(2), except that 5 ml of norbornene was used instead of 5-vinyl-2-norbornene. the result,
The amount of polynorbornene obtained was 0.51 g.

It was confirmed from IR and 1H-NMR that the reaction proceeded as an addition reaction of the intracyclic double bond and that the ring did not open.

Example 6 In Example 1-(2), 0.1 mmol of tetraisopropoxytitanium and 5-vinyl-
Example 1 except that 5 ml of norbornene was used instead of 2-norbornene and the polymerization reaction was carried out at a reaction temperature of 40°C.
-A polymerization reaction was carried out in the same manner as in (2). As a result, the amount of poly(norbornene) obtained was 0.3 g. IR.

``H-NMR confirmed that the reaction proceeded as an addition reaction of the intracyclic double bond and that the ring did not open.

Comparative Example 2 In Example 1-(2), 0.1 mmol of tetraisopropoxytitanium was used instead of bis(cyclopentadienyl)zirconium dichloride, and 0.4 mmol of triethylaluminum was used instead of methylaluminoxane.
Example 1-(2) except for the reaction temperature of 40°C.
A polymerization reaction was carried out in the same manner as above, but no polymer was obtained.

Comparative Example 3 In Example 1-(2), 0.1 mmol of titanium tetrachloride was used instead of bis(cyclopentadienyl)zirconium dichloride, 0.4 mmol of triethylaluminum was used instead of methylaluminoxane, and the reaction temperature was 40°. A polymerization reaction was carried out in the same manner as in Example 1-(2), except that C was used for the reaction. As a result, the obtained poly(5
-vinyl-2-norbornene) was 0.01 g. Furthermore, it was confirmed by IR and ``H-NMR that a ring-opening reaction was occurring.Also, there were few vinyl groups remaining, and it is thought that side reactions were occurring.

Patent applicant: Daicel Chemical Industries, Ltd. Procedural amendment (voluntary) 1. Case description 1985 Otsu 3-3 Go 12 E; F-1 Patent u filed on 112427 (3) No suffix 2, Name of invention Postal code Address Name Name wo90 1 Teppocho, Sakai City, Osaka Prefecture [ 290) Da, Isel 1, Representative of Higaku Kogyo Co., Ltd. Contents of Supplement 5, Supplement Ⅰ of the detailed description of the invention in the specification subject to the amendment by Akabe Kojima (1) Second line from the bottom of page 8 of the specification: ``・... (indenyl) titanium,..." τ "... (indenyl) titanium dibromide.

Correct by 1σ.

(2) Page 14, line 15 of the specification “Rusiklohenten.

vinyl cyclobegden of °　” °　” [Luciclopentene.

Vinyl cyclohepden... Correct.

(3) Chemical rod 1 construction formula on page 8 bottom of the specification [ Correct. (Margin below)

Claims (3)

[Claims] (1) A method for producing a cyclic olefin polymer, which comprises polymerizing a cyclic olefin or a cyclic olefin having an extracyclic unsaturated bond in the presence of a catalyst consisting of (a) a transition metal compound and (b) aluminoxane. (2) Transition metal compounds include groups IVb, Vb and
A method for producing a cyclic olefin polymer according to claim 1 selected from the group consisting of Group VIb. (3) The method for producing a cyclic olefin polymer according to claim 1 or 2, wherein the exocyclic unsaturated bond is a vinyl group or a vinylidene group.