JPH04178448A - Production of polymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent physical characteristics at high temperature and excellent balance of physical properties by bringing a specific polymer into contact with a polyolefin in the presence of a specific cationic polymerization initiator. CONSTITUTION:(A) A polymer containing at least one constituent unit derived from a nonconjugated diene or an aromatic vinyl compound is brought into contact with (B) a polyolefin in the presence of (C) a cationic polymerization initiator comprising a halogen-containing metallic compound and a hydrocarbon compound containing two or more chlorines at >=100 deg.C. An organoaluminum chloride is used as the halogen-containing metallic compound. An aliphatic hydrocarbon containing two or more chlorines is used as the hydrocarbon compound. The contact is preferably carried out in a solvent such as benzene or hexane at 100-200 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a composition comprising two or more polymers,
More specifically, it is possible to produce a polymer composition having improved physical properties over each starting polymer. The present invention relates to a method for producing a polymer composition.

TECHNICAL BACKGROUND OF THE INVENTION In recent years, attempts have been made widely to mix two or more types of polymers to produce a composition that combines the inherent advantages of those polymers.

However, in compositions obtained by simply mixing two or more types of polymers, the polymers are often not sufficiently mixed with each other and are not compatible with each other. Things tend not to be obtained.

In Japanese Patent Application No. 2-56006, the applicant of the present application previously reported that a cationic polymerization initiator was added to a homogeneous solution of a specific cyclic olefin copolymer and a rubber-like substance having double bonds to cause a reaction. It was disclosed that by doing so, it is possible to obtain a uniformly mixed composition that has an excellent balance between rigidity and impact resistance. Based on this knowledge, the inventors
Furthermore, as a result of research into compositions obtained by combining various different polymers, the following findings were obtained.

That is, when a crystalline polymer or the like is used as one of the polymers, the reaction may not proceed sufficiently at high temperatures where the polymer is dissolved in a solvent, and the composition may not necessarily have the desired well-balanced physical properties. It doesn't necessarily mean you will get it.

As a result of further intensive research based on the above-mentioned findings, the present inventors have discovered a method for producing a polymer composition with excellent balance of physical properties even at high temperatures, which will be described in detail below.

Purpose of the Invention The purpose of the method for producing a polymer composition according to the present invention is to provide a method for producing a polymer composition with excellent physical properties from two or more types of polymers, and more specifically, The object of the present invention is to provide a method for producing a polymer composition that allows production of a polymer composition with excellent balance of physical properties even at high temperatures.

Summary of the Invention The method for producing a polymer composition according to the present invention comprises [A](i
) a nonconjugated diene, or (ii) a polymer containing at least one structural unit derived from an aromatic vinyl compound, and [B copolyolefin are brought into contact in the presence of a cationic polymerization initiator to form a polymer composition. The cationic polymerization initiator is composed of (a) a halogen-containing metal compound and (b) a hydrocarbon compound containing two or more chlorine atoms, and the contact is carried out at a temperature of 100'C or more. It is characterized by being carried out in

DETAILED DESCRIPTION OF THE INVENTION A method for producing a polymer composition according to the present invention will be described below.

In the method for producing a polymer composition according to the present invention, [A]
(i) A non-conjugated diene or (ii) A polymer containing at least one structural unit derived from an aromatic vinyl compound and [B] a polyolefin are brought into contact in the presence of a specific cationic polymerization initiator. Producing a polymer composition.

First, regarding such a polymer [A], [Al1(
i) A polymer containing a structural unit derived from a non-conjugated diene, [A2] (ii) A polymer containing a structural unit derived from an aromatic vinyl compound will be described below.

(i) used in such polymer [A1]
Examples of non-conjugated dienes include the following compounds.

1.4-hexadiene, 1.6-octadiene, 4-methyl, 4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 5-ethyl-1,4 -hexadiene, 2-methyl-1,5-hexadiene, 4-methyl-1,5-hexadiene, 5-
Methyl-1,5-hexadiene, 5-methyl-1,4-
heptadiene, 6-methyl-1,4-hebutadiene, 5
-ethyl-1,4-hebutadiene, 6-nityl-1,4
-hebutadiene, 5-methyl-1,5-hebutadiene,
6-methyl-1,5-hebutadiene, 5-ethyl-1,
5-heptadiene, 6-nityl-1,5-hebutadiene, 6-methyl-1,4-octadiene, 7-methyl-1
, 4-octadiene, 6-methyl-1,5-octadiene, 7-methyl-1,5-octadiene, 6-methyl-
1,6-octadiene, 7-methyl-1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl- 1,4-nonadiene, 7-ethyl-
1,4-nonadiene, 8-ethyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,
5-nonadiene, 7-ethyl-1,5-nonadiene, ethyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 7-ethyl-1,6- Nonadiene, 8-ethyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 8-methyl-
1,7-nonadiene, 7-ethyl-1, founonadiene, 8-ethyl-1,7-nonadiene, 4-methyl-1,
4-decadiene, 5-methyl-1,4-decadiene, 8
-ethyl-1,4-decadiene, 8-ethyl-1,4-
Decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 8-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6- Decadiene, 8-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene, methyl-1,
7-Zocadiene, 8-ethyl-1,7-decadiene, 8
-ethyl-1,7-decadiene, 8-methyl-1,8-
Decadiene, 9-methyl-1, total decadiene, 8-ethyl-1, decadiene, chain non-conjugated diene cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene,
5-ethylidene-2-norbornene, 5-methylene-2
-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 4.9.5.8-dimethanol-3a, 4.
4a.

5, 8.8a, 9.9a-cyclic non-conjugated diene with octahydro-IH-benzoindene, 2.3-diisopropylidene-5-norbornene, 2-
Examples include ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.

Among these, 1,4-hexadiene, 1,6-octadiene, 7-methyl-1,6-octadiene and cyclic non-conjugated dienes, especially dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl −
2-norbornene and 5-methylene-2-norbornene are preferably used.

The polymer [Al1] used in the present invention is preferably a copolymer of (i) a nonconjugated diene as described above and (iii) an α-olefin as described below.

Such (ii) olefins have 2 to 2 carbon atoms.
0 α-olefins or cyclic olefins can be mentioned.

Specifically, α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, ■-pentene, 1
-hexene, 3-methyl-1-butene, 4-methyl-1
-Pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, l-nonene, 1-decene, 1-undecene, l-dodecene, 1-tetradecene, 1-hexadecene, l-octadecene, 1- Mention may be made of eicosene, vinylcyclohexene or mixtures thereof.

The polymer [Al1] can be obtained by copolymerizing the above-mentioned (i) non-conjugated diene and α-olefin by a conventionally known polymerization method.

Examples of such polymers [AI] are shown below.

A polymer containing a structural unit derived from one type of α-olefin [Al1 includes ethylene/diene copolymer, propylene/diene copolymer, 1-butene/diene copolymer, 1-pentyne/diene copolymer, Polymer, 4-methyl-1-pentene/diene copolymer, l-hexene/diene copolymer, 1-octene/diene copolymer, l-decene/diene copolymer, I-dodecene/diene copolymer Union,
Examples include I-eicosene/diene copolymer.

Polymers [AI] containing structural units derived from two types of α-olefins include ethylene, propylene,
Diene copolymer, ethylene/1-butene/diene copolymer, ethylene/1-pentene/diene copolymer, ethylene/4-methyl-1-pentene/diene copolymer, ethylene/1-hexene/diene copolymer Polymer, ethylene 1-
Decene/diene copolymer, ethylene/1-eicosene/
Diene copolymer, propylene/l-butene/diene copolymer, propylene/1-pentene/diene copolymer, propylene/4-methyl-1-pentene/diene copolymer, propylene/1-hexene/diene copolymer Polymer, propylene/l-decene/diene copolymer, propylene/3-
Methyl-1-butene/diene copolymer, propylene/vinylcyclohexene/diene copolymer, 1-butene/l
-Pentene/diene copolymer, 1-butene/4-methyl-1-pentene/diene copolymer, ]-butene/]-hexene/diene copolymer, 1-butene/1-decene/diene copolymer , 1-butene/l-eicosene/diene copolymer, 4-methyl-1-pentene/1-pentene/diene copolymer, 4-methyl-]-pentene/1-hexene/diene copolymer, 4- Methyl-1-pentene 1-
Decene/diene copolymer, 4-methyl-1-pentene/
Examples include 1-eicosene/diene copolymer.

Furthermore, mention copolymers containing three or more types of α-olefins, such as ethylene/propylene/l-butene/diene copolymer and propylene/1-butene/4-methyl-1-pentene/diene copolymer. I can do it.

(ii) When the olefin is a cyclic olefin, a cyclic olefin represented by the following formula [I] or [II] can be used. In addition, such cyclic olefins can also be used in combination of two or more types.

General formula % Formula % [] (In the formula, n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R1 to RI m and R', Rb are each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R"-R" may be bonded to each other to form a monocyclic or polycyclic ring, and (It may have a ring or polycyclic ring or a double bond, and R'' and R'' may also be combined to form an alkylidene group, or LtRI7 and RI8 may be combined to form an alkylidene group).

- Formula ■: (In the formula [I[], r is an integer of 0 or 1 or more, and S
and t is 0.1 or 2, and R] to R1s are each independently an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an alkoxy group. and R' (or R''
) and R'' (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.) However, the above formula In [1], n is 0 or 1, preferably 0. Further, m is 0 or a positive integer, preferably 0-3.

And q is O or 1.

In the above formula [II], r is 0 or an integer of 1 or more, preferably an integer of 0 to 3.

and R1 to R'' and R1 and R1' (formula [I
]), or R1-R15 (formula [■]) each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, examples of halogen atoms include fluorine atoms, chlorine atoms,
Mention may be made of bromine and iodine atoms. In addition, examples of the hydrocarbon group' include, each independently, an alkyl group usually having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms, and specific examples of the alkyl group include , methyl group, ethyl group, isopropyl group, isobutyl group, and amyl group. Specific examples of the cycloalkyl group include cyclohexyl group, cyclopropyl group, cyclobutyl group, and cyclopentyl group.

Furthermore, in the above formula [I[], R' (or R') and R
9 (or R7) may be bonded via an alkylene group having 1 to 3 carbon atoms, or may be bonded directly without any group.

In addition, in the above formula [I], when q or 0, the ring represented using q forms a five-membered ring.

Furthermore, in the above formula [1], R15 to RIs may be bonded to each other (together) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond. You can. Examples of such a monocyclic or polycyclic ring include the monocyclic or polycyclic rings listed below. moreover,
These rings may have a substituent such as a methyl group.

In addition, in the above formula, the carbon atoms shown with ■ and 2 represent carbon atoms of an alicyclic structure to which the groups represented by R+5 to R18 in formula [1] are bonded.

Furthermore, RlS and R16 or R17 and R18 may form an alkylidene group. Such ``alkylidene group'' usually includes an alkylidene group having 2 to 4 carbon atoms, and specific examples thereof include ethylidene group, propylidene group, isopropylidene group, and isobutylidene group. .

The cyclic olefin represented by the above formula [I] or [II] can be easily produced by condensing a cyclopentadiene and a corresponding olefin or cyclic olefin by a Diels-Alder reaction. .

Specifically, the cyclic olefin represented by the formula [I] or [I[] includes, for example, bicyclo[2,2,
1] Hept-2-ene derivative, tetracyclo[4,4,
0,12・S, l 7. l1)]-3-dodecene derivative, hexacyclo[6,6,1,13'',1''・+3. Q
2.7°o L 14]-4-heptadecene derivative, octacyclot8. s, o, 12. e, +4.7
．． 1) 1.1-91) 1) @, Q l a, Q 1
2.17], -5-tococene derivative, pentacyclo[6
, 6,1,1''', 027.0' 14]-4-hexadecene derivative, heptacyclo[8,7,0,12', 147. 1
+1) 7゜018,0+2・+61-5-eicosene derivative, heptacyclo[8,8,0,121,147,1
"°18°03s, OI2'7]-5-heneicosene derivative, tricyclo[4,3,0,125]-3-decene derivative, tricyclo[4,4,0,125]-3-undecene derivative, pentacyclo[ 6,5,1,l 36.027.09・
131-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo[
7, 4, 0, 12・5. 9.12.01)41]-3
-pentadecene derivative, heptacyclo[8,7,0,13,6,1)0,+7.
1) 2・15°o 2.7. o1). +5) -4
-eicosene derivative, nonacyclo[lQ, 9.1.1
4.7. ll:1.20.1I6-1)゜03・@,
Q2. +6. Q 12.21. Q14.1]
-5-bentacocene derivative, pentacyclo[8,4,0,12・5.9・12.08
・131-3-hexadecene derivative, heptacyclo[8,8,0,14・7.1) 1 item 1
)2.16°03・1. o 12.17]-5-heneicosene derivative, Tsukacyclo[lo, to, 1.1
5.8. t 14.21.1) 1) 9°02nd 04
．． 9.013・22. □ +5.2G]-5-hexadecene derivative, 5-phenyl-bicyclo[2,2,1]hept-2-ene 5-methyl-5-phenyl-bicyclo[2', 2.
1 ] Hebdo-2-ene, 5-benzyl-bicyclo[2,2,1]hept-2-ene, 5-tolyl-bicyclo[2,2,1]hept-2-ene, 5-(ethylphenyl) -bicyclo[2,2,1]hept-2-ene, 5-(isopropylphenyl)-bicyclo[2,21]
Hept-2-ene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, 1,4-methane-1,4,4a, 5,10,1oa-hexahydroanthracene, cyclopentadiene- Acenaphthylene adduct, 5-(α
-naphthyl)-bicyclo[2,2,1]hept-2-ene, 5-(anthracenyl)-bicyclo[2,2,13hept-2-ene, and the like.

More specific examples of such compounds are shown below.

Bicyclo[2,2,1]hept-2-ene derivatives such as Nato.

Shih3 Nato's Tetracyclo[4,4,0,1",+7"]
-]3-dodecene derivative; with hexacyclo[5,6,1,1L6.1)O,1
3,02,7°o 9. +4]-4-heptadecene derivatives: octacyf O[8,8,0,1"°I, 14
．． 7, l1). 181) LI@, 01・#
, Q ILI? ] -]5-tococene derivative 1"
Pentacyclo[6,6,1,1",027,0" with lco-4-hexadecene
°14]-4-hexadecene derivative: Nato's hebutacyclo-5-eicosene derivative or hebutacyclo-5-heneicosene derivative: Nato's tricyclo[4,3,0,1'']-]3-decene derivative, etc. A tricyclo[4,4,0,125]-3-undecene derivative of

Nato's Pentacyclo [6, 5, 1, B', 0" 7
．． 0''']-]4-Pentadecene derivatives and other diene compounds: Nato's pentacyclo[7,4,0,12,S, IQ,
12.01. H]-3-pentadecene derivative.

t,; and'(to D"j9 cyclo[8, 7, 0, 1st, 1
"l', I" 15°o2.7. 4-eicosene derivative.

-5-bentacocene and nonacyclo[10,9,1,+4.7,1+3
．． 20, 1)5. +1°Q3. fi, Q2. to
, Q12.2+, Q14. l ] -] Pentasif O[8,4,0,1'' such as 5-bentacocene derivatives
, 1'°12. □L H co-3-hexadecene derivative; -5-heneicosenatonohebutacyclo[8,8,Q, l L 1. l
Il, Il, l 131g, Q 2.1. Q
12. +? ]-5-heneicosene derivative.

Nato's Nonankuro [10, 10, 1, 1s, s, 1+
42+, 1) LH, 02nd.

04.1.01ff,! 2. QI5・20 ]-]s-
Mention may be made of hexacosene derivatives and also '. (Hereinafter, blank space) A copolymer of such a cyclic olefin and (i) a nonconjugated diene can be produced by a conventionally known polymerization method.

This copolymer may contain structural units derived from ethylene.

The above polymer [Al1 may be a random copolymer or a block copolymer.

In the polymer [Al1] used in the present invention, a small amount (
(i) The structural unit derived from a non-conjugated diene contained in one type is 0.05 to 10 mol%, preferably 0.1
It is desirable that the content be 7 mol%. In addition, the polymer 1
On the 4th day, the iodine value (g-iodine/100g copolymer) is preferably 4, which is 0.1-50, preferably 0.5-40.

Next, [A2] (ii) A polymer containing a structural unit derived from an aromatic vinyl compound will be described.

Specific examples of the aromatic vinyl compound (ii) include styrene, substituted styrene, and vinylnaphthalene compounds.

Examples of the substituted styrene include 0-methylstyrene, m-methylstyrene, p-methylstyrene, 0-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 0-bromstyrene, m-bromstyrene, p-bromstyrene, Examples include styrene, 0-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and the like.

Moreover, as a vinylnaphthalene compound, for example, 1
Examples include -vinylnaphthalene, 2-vinylnaphthalene, and l-vinyl-4-methylnaphthalene.

Among these, styrene and methylstyrene are preferably used. These aromatic vinyl compounds can be used alone or in combination.

The polymer [A2] used in the present invention includes the above-mentioned (ii) aromatic vinyl compound and the above-mentioned carbon number 2 to 2.
Preferably, it is a copolymer with 0 α-olefin.

Such a polymer [A2] can be obtained by copolymerizing (ii) an aromatic vinyl compound and an α-olefin using a conventionally known polymerization method.

Specific examples of such polymer [A2] are shown below.

As the polymer [A2] containing a structural unit derived from one type of α-olefin, ethylene/aromatic vinyl compound copolymer, propylene/
Aromatic vinyl compound copolymer, 1-butene, aromatic vinyl compound copolymer, 1-pentene/aromatic vinyl compound copolymer, 4-methyl-1-pentene/aromatic vinyl compound copolymer, ■- Two examples include eicosene/aromatic vinyl compound copolymers.

As the polymer [A2] containing structural units derived from two types of α-olefins, ethylene, propylene,
Aromatic vinyl compound copolymer, ethylene/1-butene/
Aromatic vinyl compound copolymer, ethylene/1-pentene/aromatic vinyl compound copolymer, ethylene/4-methyl-1-pentene/aromatic vinyl compound copolymer, aromatic vinyl compound copolymer, ethylene・1-hexene/aromatic vinyl compound copolymer, ethylene/1-decene/aromatic vinyl compound copolymer, ethylene/1-eicosene/aromatic vinyl compound copolymer, propylene/1-butene/aromatic vinyl Compound copolymer, propylene/1-pentene/aromatic vinyl compound copolymer, propylene/4
-Methyl-1-pentene/aromatic vinyl compound copolymer, -aromatic vinyl compound copolymer, propylene/1-hexene/aromatic vinyl compound copolymer, propylene/1
-Decene/aromatic vinyl compound copolymer, propylene/
3-Methyl-1-butene/aromatic vinyl compound copolymer, propylene/vinylcyclohexene/aromatic vinyl compound copolymer, 1-butene/l-pentene/aromatic vinyl compound copolymer, l-butene/4 -Methyl-1=pentene/aromatic vinyl compound copolymer, -aromatic vinyl compound copolymer, 1-butene/1-hexene/aromatic vinyl compound copolymer, l-butene/1-decene/aromatic Vinyl compound copolymer, 1-butene/■-eicosene/aromatic vinyl compound copolymer, 4-methyl-1-pentene/l-pentene/aromatic vinyl compound copolymer, 4-methyl-1-pentene/ 1-hexene/aromatic vinyl compound copolymer, 4-methyl-1-pentene/l-decene/
Examples include aromatic vinyl compound copolymers, 4-methyl-1-pentene/1-eicosene/aromatic vinyl compound copolymers, and the like.

As the polymer [A2] containing structural units derived from three types of α-olefins, ethylene, propylene,
I-butene/aromatic vinyl compound copolymer, propylene/1-butene/4-methyl-1-pentene/aromatic vinyl compound copolymer, etc. may be mentioned.

These copolymers may be random copolymers or block copolymers.

In addition, although the polymer [A2] containing structural units derived from up to three types of α-olefins is exemplified above, it goes without saying that the α-olefins may contain four or more types. .

In such a polymer [Ag3, at least one structural unit derived from (ii) an aromatic vinyl compound is contained in an amount of 0.1 to 20 mol%, preferably 0.2 to 20 mol%.
It is desirable that it be 10 mol%.

The polymer [A] containing a structural unit derived from a non-conjugated diene as described above or the crystalline polyolefin [Ag3] containing an aromatic vinyl compound was measured in decalin at 135°C. The intrinsic viscosity [η] is 0.1 to 10 di/g, preferably 1 to 7
cti/g is desirable.

Next, the polyolefin [B] used in the present invention will be explained.

As such polyolefin [B], for example,
It may be a polyolefin obtained by polymerizing or copolymerizing (ii) the olefin, such as the above-mentioned α-olefin having 2 to 20 carbon atoms or a cyclic olefin, alone or in combination.

For example, polyolefins [B] containing structural units derived from α-olefins are as follows: ■ As α-olefin homopolymers, polyethylene,
polypropylene, polyl-butene, bojan-pentene,
Examples include poly-4-methyl-1-pentene and poly-l-eicosene.

■ α-olefin binary copolymers include ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/l-pentene copolymer, and ethylene/4-methyl-1-pentene copolymer. , copolymer, ethylene bow-
Hexene copolymer, ethylene/1-decene copolymer, ethylene/1-eicosene copolymer, propylene bow-butene copolymer, propylene/l-pentene copolymer, propylene/4-methyl-1-pentene copolymer Polymer, copolymer, propylene/1-hexene copolymer, propylene/1
-decene copolymer, propylene/3-methyl-butene copolymer, propylene/vinylcyclohexene copolymer, l-butene/l-pentene copolymer, 1-butene/4
-Methyl-1-pentene copolymer, copolymer, 1-butene/1-hexene copolymer, l-butene/needesene copolymer, 1-butene/1-eicosene copolymer, 4-methyl-1 -Pentene/1-pentene copolymer, 4-methyl-1-pentene/1-hexene copolymer, 4-methyl-1-pentene/1-decene copolymer, 4-methyl-1
-pentene/1-eicosene copolymer and the like.

■ Examples of α-olefin ternary or higher copolymers include ethylene/propylene/l-butene copolymers, propylene/l-butene copolymers,
Examples include 1-butene/4-methyl-1-pentene copolymer.

These copolymers may be random copolymers or block copolymers.

When producing an α-olefin polyolefin, other copolymerizable unsaturated monomers may be used in addition to the above α-olefin as necessary, as long as the object of the present invention is not impaired. Examples of the unsaturated monomer, which may be optionally copolymerized, include the aforementioned non-conjugated dienes, aromatic vinyl compounds, and cyclic olefins. Such non-conjugated dienes, aromatic vinyl compounds, and cyclic olefins can be used alone or in combination.

In the polyolefin [B] used in the present invention, the polyolefin containing a structural unit derived from a cyclic olefin includes ethylene and a cyclic olefin represented by the above-mentioned general formula [I] or [II] alone or in combination. and (co)polymerization.

When producing a cyclic olefin-based polyolefin, in addition to ethylene and cyclic olefin, other copolymerizable unsaturated monomers may be used as necessary, as long as the object of the present invention is not impaired. Even if the unsaturated monomer is optionally copolymerized, the unsaturated monomer may have, for example, the above-mentioned carbon number or 3 to 3 carbon atoms.
20 α-olefins, nonconjugated dienes, and aromatic vinyl compounds can be mentioned. These α-olefins, nonconjugated dienes, and aromatic vinyl compounds can be used alone or in combination.

It is preferable that the amount of structural units derived from such optionally used unsaturated monomers is less than equimolar to the units composed of ethylene in the polyolefin [B] to be produced.

A cyclic olefin-based polyolefin can be produced, for example, by polymerizing ethylene and a cyclic olefin in a hydrocarbon medium in the presence of a catalyst formed from a hydrocarbon-soluble vanadium compound and a nitrogen-containing organoaluminum compound. I can do it. Such a polymerization method itself is already known, and is disclosed in Japanese Patent Application Laid-Open No. 168708/1983.
No. 61-120816, JP-A-61-120816, JP-A-61-120816
-1) Publication No. 5912, Japanese Unexamined Patent Publication No. 61-1) Publication No. 5916, Japanese Patent Application No. 95905, Japanese Patent Application No. 61-95
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in JP-A No. 906, JP-A No. 61-271308, JP-A No. 61-272216, etc.

In such a cyclic olefin polyolefin, the structural unit derived from the cyclic olefin represented by the above formula [I] or [II] is represented by the following formula [III] or [I
It is thought that it forms a repeating unit with a structure represented by V].

(In the formula [I[[], m, nSq, R1-R1m and R1, Rb are the same as defined in the above formula [I].) (In the formula [IV], r, s, t and Rl to RI 6 is the same as the definition in the above formula [I[].) In the cyclic olefin polyolefin used in the present invention, the structural unit derived from ethylene is usually 40 to 85 mol%, preferably 50 to 75 mol%. and (ii)
The structural unit derived from a cyclic olefin usually has 60 to 1
It is desirable that the amount is 5 mol%, preferably 50 to 25 mol%.

The cyclic olefin polyolefin [B] has an iodine value (
g-iodine/100 g copolymer) is preferably 0.5 to 50, preferably 1 to 40, and therefore preferably contains a structural unit derived from a non-conjugated diene.

In the above-mentioned cyclic olefin polyolefin [B], the optional structural units include 0.05 to 10 mol%, preferably 0.1 to 7 mol%, aromatic In the case of vinyl compounds, 0.1 to 20 mol%
, preferably 0.2 to 10 mol %.

Furthermore, in the present invention, a cyclic olefin-based ring-opening polymer can also be used as the polyolefin [B].

Such a cyclic olefin-based ring-opening polymer may be obtained by ring-opening polymerization of the same or different cyclic olefin monomers represented by the above-mentioned general formula [I] or [II] in the above-mentioned cyclic olefin-based polyolefin. The resulting cyclic olefin ring-opened polymer, ring-opened copolymer, or hydrogenated product thereof can be used. To explain such cyclic olefin ring-opening polymers, ring-opening copolymers, and hydrogenated products thereof using the cyclic olefin represented by the formula [I] as an example, they react as described below. Ring opening (
It is thought that it constitutes a co)polymer and a hydrogenated product thereof.

Specific examples include ring-opened copolymers of tetracyclododecene and norbornene and derivatives thereof, and hydrogenated products thereof.

No. Ring-opening ↓ When producing a hydrogenated cyclic olefin-based ring-opening polymer,
In addition to the above-mentioned cyclic olefins [I] and [I[], other copolymerizable unsaturated monomer components may be used as necessary, as long as the object of the present invention is not impaired. Examples of the unsaturated monomer that may be optionally copolymerized include a cyclic olefin represented by the following formula [V].

(In the formula, R"-R' is hydrogen, a hydrocarbon group, or)\rogen, and each may be the same or different. m is an integer of 4 or more, and R1 to R' are repeated multiple times. (When repeated, these may be the same or different.) As the cyclic olefin represented by the above formula [V],
For example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, methylcyclopentene, methylcycloheptene, methylcyclooctene, methylcyclononene, methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, 3 , 4-dimethylcyclohexene, 3-methylcyclohexene, 2-
(2-Methylbutyl 1-cyclohexene, trimethylcyclodecene, 2.3.3a, 7a-tetrahydro-
4,7-methano-IH-indene, 3a, 5.6.7
Examples include a-tetrahydro-4,7-methano-IH-indene.

Such other cyclic olefins can be used alone or in combination, and are usually used in an amount of 0 to 50 mol%.

In order to produce a cyclic olefin-based ring-opening polymer, the cyclic olefin represented by the above-mentioned formula [I] or [I[] and, if necessary, the cyclic olefin represented by the above-mentioned formula [V] are used. Then, ring-opening polymerization can be carried out by a conventional ring-opening polymerization method. At this time, examples of polymerization catalysts include ruthenium, rhodium, palladium, osmium,
A system consisting of a reducing agent such as a halide, nitrate, or acetylacetone compound such as iridium, platinum, molybdenum, or tungsten, and an organic tin compound or alcohol;
Alternatively, a system consisting of a halide of titanium, vanadium, zirconium, tungsten, or molybdenum or an acetylacetone compound and an organic aluminum can be used.

The molecular weight of the ring-opening polymer produced can be adjusted by adding an olefin or the like during ring-opening polymerization.

When the ring-opened polymer obtained as described above is hydrogenated, it can be carried out according to a conventional hydrogenation method. As such a hydrogenation catalyst, those normally used when hydrogenating olefin compounds can be used. Specifically, examples of the heterogeneous catalyst include nickel, palladium, platinum, etc., or solid catalysts in which these metals are supported on carbon, silica, diatomaceous earth, alumina, titanium oxide, and the like. More specifically, examples include nickel/silica, nickel/diatomaceous earth, palladium/carbon, palladium/silica, palladium/diatomaceous earth, and palladium/alumina.

In addition, homogeneous catalysts include those consisting of metals from group Ⅰ of the periodic table, such as compounds containing Ni and Co, and organometallic compounds from groups 1 to ① of the periodic table, specifically, nickel naphthenate/ Examples include triethylaluminum, cobalt octenoate/n-butyllylium, nickel acetylacetonate/triethylaluminum, and Rh compounds.

Hydrogenation of ring-opened polymers can be carried out in 1-1 times depending on the type of catalyst.
Under a hydrogen pressure of 50 atm, from 0 to 180°C, preferably at 20
It is carried out at a temperature of ~100°C.

The hydrogenation rate can be adjusted by adjusting hydrogen pressure, reaction temperature, reaction time, catalyst concentration, etc.

The intrinsic viscosity [η] of the cyclic olefin ring-opening polymer obtained in this way, measured in decalin at 135°C, is usually 0.05 to 10 dl/g, preferably 0.08 to 5 dl/g.
dl/g. Softening temperature (TMA) is 70°C
The above temperature is preferably 90 to 200°C. Further, the iodine value is preferably 0.1 to 50, preferably 0.5 to 40.

In the present invention, a part of the cyclic olefin polyolefin as described above may be modified with an unsaturated carboxylic acid such as maleic anhydride. Such modified products include the above-mentioned cyclic olefin polyolefin,
It can be produced by reacting unsaturated carboxylic acids, their anhydrides, and derivatives such as alkyl esters of unsaturated carboxylic acids. In this case, the content of structural units derived from the modifier in the modified cyclic olefin polyolefin is usually 0.5 to 10
It is mole%.

Such a cyclic olefin-based polyolefin modified product is
It can also be produced by blending a modifier with a cyclic olefin polyolefin to achieve a desired modification rate and performing graft polymerization, or by preparing a modified product with a high modification rate in advance, and then combining this modified product with an unmodified one. It can also be produced by mixing with a cyclic olefin polyolefin.

Next, a method for producing a polymer composition according to the present invention will be explained.

In the present invention, a polymer [A] containing at least one structural unit derived from (i) a non-conjugated diene or an aromatic vinyl compound as described above, and a polyolefin [B]
A polymer composition is produced by contacting these in the presence of a cationic polymerization initiator.

Such a cationic polymerization initiator consists of (a) a halogen-containing metal compound, and (b) a hydrocarbon compound containing two or more chlorines.

As such (a) halogen-containing metal compound, B
e, Mg, Zn, Cd, Hg, B, Ah Ga, Ti,
Zr, Sn, , P, Sb, Nb5Bi, Ta5
U, Re.

Examples include halides of Fe, and among these, halides of B, AI, Ti, and 5nSFe are particularly preferred.

Specifically, boron trifluoride (BF, ), boron trifluoride/diethyl ether complex (BF, ○(C2H6)2)
, boron trifluoride-phenol complex (BF30-HO
C, Hg), an organoaluminum compound represented by the general formula R, A IX 3-n (X is chlorine, bromine, iodine, or fluorine, n is a value satisfying 0≦n<3, R represents an alkyl group), titanium tetrachloride (Tic 14), tin tetrachloride (S
nC14), iron trichloride (FeCl=), and the like.

Among the halides of B, Al, Ti, Sn, and Fe, halogen-containing metal compounds of At are particularly preferred,
Particularly preferred are organoaluminum compounds represented by the formula R, AlX2-.

Specifically, aluminum trichloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, methylaluminum sesquichloride, propylaluminum dichloride, propylaluminum sesquichloride, isobutylaluminum dichloride, isobutylaluminum sesquichloride,
Examples include hexylaluminum dichloride, hexylaluminum sesquichloride, ethylaluminum dichloride, and ethylaluminum sesquipromide. Although organoaluminum chloride is preferably used, it may be used in combination with other organoaluminum compounds as long as the resulting composition is expressed as R, AlX3-.

Further, in the present invention, as (b) a hydrocarbon compound containing two or more chlorines, the following compounds can be mentioned.

As aliphatic dichloro compounds, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1,2-dichloro-2-methylpropane, 1,
3-dichloro-2-methylpropane, 1,2-dichloro-2,2-dimethylpropane, l,3-dichloro-2,
2-dimethylpropane, 1,3-dichloropropene, 2
, 3-dichloropropene, 1.3-dichloro-2-methylpropene, 1.2-dichlorobutane, 1.3-dichlorobutane, 1,4-dichlorobutane, 1.2-dichloro-2-methylbutane, 2. 2-dichlorobutane, 2.3
-dichlorobutane, 2,3-dichloro-2-methylbutane, 2,3-dichloro-2,3-dimethylbutane, 1,
2-dichlorobutene, 1,3-dichloro-2-butene,
1,4-dichloro-2-butene, 1,2-dichloropentane, 1,3-dichloropentane, 1,4-dichloropentane, 5-dichloropentane, 2,2-dichloropentane, 2,3-dichloro Pentane, 2,4-dichloropentane, 3,3-dichloropentane, 2,3-dichloro-2-methylpentane, 2,3-dichloro-2,3
-dimethylpentane, 2,4-dichloro-2-methylpentane, 2,4-dichloro-2,4-dimethylpentane, 3,3-dichloropentane, 1,2-dichlorohexane, 1,3-dichlorohexane, ■ , 4-dichlorohexane, 1.5-dichlorohexane, 2.2-dichlorohexane, 2.3-dichlorohexane, 2,4-dichlorohexane, 2.5-dichlorohexane, 3,3-dichlorohexane, 3. 4-dichlorohexane, 4,4-dichlorohexane, 2.3-dichloro-2-methylhexane, 2.4-dichloro-2-methylhexane, 2.5-dichloro-2-methylhexane, 3,4-dichloro -3-
Methylhexane, 2,3-dichloro-2,3-dimethylhexane, 2,4-dichloro-2,4-dimethylhexane, 2,5-dichloro-2,5-dimethylhexane,
3.4-dichloro-3,4-dimethylhexane, 1,2
-dichlorooctane, 1,3-dichlorooctane, 1.
4-dichlorooctane, 1.5-dichlorooctane, 1
, 6-dichlorooctane, 1,7-dichlorooctane,
1,8-dichlorooctane, 1,2-dichloro-2-methyloctane, 1,3-dichloro-3-methyloctane, 1,4-dichloro-4-methyloctane, 1,5-dichloro-5-methyloctane , 1,6-dichloro-6-
Methyloctane, 1.7-dichloro-7-methyloctane, 2.2-dichlorooctane, 2,3-dichlorooctane, 2.4-dichlorooctane, 2.5-dichlorooctane, 2.6-dichlorooctane, 2 , 7-dichlorooctane, 3.3-dichlorooctane, 3,4-dichlorooctane, 3.5-dichlorooctane, 3,6-dichlorooctane, 4.4-dichlorooctane, 4.5-dichlorooctane, 2. 3-dichloro-2-methyloctane, 2.4-dichloro-2-methyloctane, 2.5-
Dichloro-2-methyloctane, 2,6-dichloro-2
-Methyloctane, 2.7-dichloro-2-methyloctane, 3.4-dichloro-3-methyloctane, 3.5
-dichloro-3-methyloctane, 3,6-dichloro-
3-methyloctane, 4.5-dichloro-4-methyloctane, 2.3-dichloro-2,3-dimethyloctane, 2,4-dichloro-2,4-dimethyloctane, 2.
5-dichloro-2,5-dimethyloctane, 2,6-dichloro-2,6-dimethyloctane, 2,7-dichloro-2,7-dimethyloctane, 3,4-dichloro-3,
4-dimethyloctane, 3,5-dichloro-3,5-dimethyloctane, 3,6-dichloro-3,6-dimethyloctane, 4,5-dichloro-4,5-dimethyloctane, 1,2-dichlorodecane , 1,3-dichlorodecane, 1,4-dichlorodecane, l,5-dichlorodecane,
1,6-dichlorodecane, 1,7-dichlorodecane, 1
．． 8-dichlorodecane, 1,9-dichlorodecane, 1.
to-dichlorodecane, 2.2-dichlorodecane, 2
．． 3-dichlorodecane, 2.4-dichlorodecane, 2.
5-dichlorodecane, 2,6-dichlorodecane, 2,7
-dichlorodecane, 2,8-dichlorodecane, 2,9-
Dichlorodecane, 3.3-dichlorodecane, 3.4-dichlorodecane, 3,5-dichlorodecane, 3,6-dichlorodecane, 3.7-dichlorodecane, 3.8-dichlorodecane, 4,4- Dichlorodecane, 4,5-dichlorodecane, 4,6-dichlorodecane, 4,7-dichlorodecane, 5,6-dichlorodecane, 1,2-dichloro-
2-methyldecane, 1,3-dichloro-3-methyldecane, 1,4-dichloro-4-methyldecane, 1,5-dichloro-5-methyldecane, 1,6-dichloro-6-methyldecane, 1,7-dichloro- 7-methyldecane, 1
．． Dichloro-8-methyldecane, 1,9-dichloro-
9-Methyldecane, 2.3-dichloro-2-methyldecane, 2.4-dichloro-2-methyldecane, 2.5-dichloro-2-methyldecane, 2.6-dichloro-2-methyldecane, 2.7-dichloro- 2-methyldecane, 2
．． 8-Dichloro-2-methyldecane, 2.9-dichloro-2-methyldecane, 3,4-dichloro-3-methyldecane, 3,5-dichloro-3-methyldecane, 3.6-
Dichloro-3-methyldecane, 3,7-dichloro-3-
Methyldecane, 3,8-dichloro-3-methyldecane,
4.5-dichloro-4-methyldecane, 4,6-dichloro-4-methyldecane, 4.7-dichloro-4-methyldecane, 5.6-dichloro-5-methyldecane, 2,3
-dichloro-2゜3-dimethyldecane, 2,4-dichloro-2,4-dimethyldecane, 2,5-dichloro-2,
5-dimethyldecane, 2.6-dichloro-2,6-dimethyldecane, 2,7-dichloro-2,7-dimethyldecane, 2. 2. total dimethyldecane, 2,9-
Dichloro-2,9-dimethyldecane, 3.4-dichloro-3,4-dimethyldecane, 3.5-cyclo3.5
-dimethyldecane, 3,6-dichloro-3,6-dimethyldecane, 3,7-dichloro-3,7-dimethyldecane, 3,8-dichloro-3, 4゜5-
Dichloro-4,5-dimethyldecane, 4,6-cyclo4,6-dimethyldecane, 4,7-dichloro-4,7
-dimethyldecane, 5,6-dichloro-5,6-dimethyldecane, and the like.

Examples of aliphatic cyclic dichloro compounds include 1,2-dichlorocyclopentane, 1,3-dichlorocyclopentane,
1,2-dichlorocyclopentene, 3,5-dichlorocyclopentene, 1,2-dichlorocyclohexane, 1.
3-dichlorocyclohexane, 1,4-dichlorocyclohexane, 1,2-dichlorocyclohexene, 3.6-
Dichloro, rocyclohexene, chlorinated products of ethylene/α-olefin copolymers, such as ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/1
Examples include chlorinated products such as -hexene copolymer and ethylene/4-methyl-1-pentene copolymer.

Examples of aromatic dichloro compounds include 1,2-bis(chloromethyl)benzene, 1,3-bis(chloromethyl)benzene, and 1,4-bis(chloromethyl)benzene.

Among these, aliphatic hydrocarbon compounds containing two or more chlorines are preferably used.

The cationic polymerization initiator used in the present invention consists of (a) a halogen-containing metal compound as described above, and (b) a hydrocarbon compound containing two or more chlorines. In the initiator, (b) a hydrocarbon compound containing two or more chlorines has a molar ratio of 0.00 to (a) halogen-containing metal compound in terms of chlorine molar ratio in (b). It is desirable that it be present in an amount of 1 to 10 O, preferably 0.1 to 3.

In the present invention, polymer [A] and polyolefin [B] are combined in the presence of a cationic polymerization initiator as described above.
make contact with The contacting method includes a method in which the mixture is heated and melted using an extruder, Brabender, kneader, etc., and then a cationic polymerization initiator is added and brought into contact with the polymer [A] and the polyolefin [B] using a solvent. ]
There is a method of mixing them in a solution state and then adding a cationic polymerization initiator and bringing them into contact with each other, and the latter method is preferably used.

When contact is carried out by the latter method, any solvent may be used as long as it does not inhibit cationic polymerization of carbon-carbon double bonds. Specifically, aromatic compounds such as benzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and nitrobenzene, and compounds having 5 to 18 carbon atoms such as n-hexane, heptane, and decane.
Saturated aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, l-sumethylcyclohexane and methylethylcyclohexane, saturated alicyclic hydrocarbons such as decalin, and their halides such as methylene chloride and chloroform. ,Carbon tetrachloride,
Examples include dichloroethane and trichloroethane.

These solvents can be used alone or in combination. Furthermore, the solvents that can be used in the present invention are not limited to these solvents.

When bringing the above components into contact, the physical properties of the resulting composition may change depending on the type of solvent used. For example, if a polar solvent such as a halide solvent is used, the crosslinking reaction tends to proceed relatively quickly. It is in.

In contacting, the contact temperature is preferably 150° C. or more and 300° C. or less when the contact is carried out in a heated molten state, and preferably 100° C. or more and 200° C. or less when the contact is carried out in a solution state.

In the present invention, the crosslinking reaction sufficiently proceeds even when the contact is carried out at a temperature of 100°C or higher, which is dramatically superior to the conventional method in which the contact reaction can only be carried out at a temperature of several tens of degrees Celsius. Therefore, crosslinking contact in the molten state is possible, and the range of applications of the crosslinking reaction can be greatly expanded.

The amount of the cationic polymerization initiator to be used is determined by the content of the structural unit derived from the non-conjugated diene or aromatic vinyl compound in the polymer [A] and polyolefin [B], the contact temperature,
Depending on the solvent used, contact time, etc., it is usually the sum of polymer [A] and polyolefin [B]! 10
The amount is 0.1 to 300 mmol, preferably 0.1 to 200 mmol, per 0 g.

In addition, the pressure during contact treatment can be selected as appropriate.
Atmospheric pressure to about 10Kg/al, preferably atmospheric pressure to about 5K
It is preferable to carry out the test under conditions of g/cd.

After the contact is completed, the resulting contact material is first washed with alkaline water and methanol to remove the used cationic polymerization initiator, and then dried under reduced pressure to obtain a first cyclic olefin polymer composition. . The composition ratio of the first composition obtained is:
This is the same as the ratio of the amounts of each raw material copolymer used for contact.

The above-mentioned contact can be carried out by any of the batch, semi-continuous, and continuous methods.

The polymer composition obtained as described above is different from a simple mixture of the polymer [A] and the polyolefin copolymer [B], in that the double bonds in the polymer [A] are cross-linked and the cross-linked It is presumed that the polymer [A] and the molecular chains in the polyolefin [B] are intricately intertwined and have a three-dimensional structure.

In such a composition, while maintaining the inherent properties of the polymer [A] or polyolefin [B], it also has properties as a polymer alloy.

In the polymer composition as described above, the polymer [A
] or 100 parts by weight, polyolefin [B] is 1
It is preferably present in an amount of 0 to 900 parts by weight.

The above polymer composition may contain heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. I can do it. The blending amount can be selected as appropriate. Such stabilizers include, for example, tetrakis[methylene-3(3,5-di-t-butyl-4
-Hydroxyphenyl)propionate comethane, β-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionic acid alkyl ester, phenolic antioxidants such as 2,2'-oxamidopis[ethyl-3(3,di-t-butyl-4-hydroxyphenyl)propionate], zinc stearate, calcium stearate, 1
Fatty acid metal salts such as calcium 2-hydroxystearate, polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, etc. I can give an example.

These can be used alone or in combination; for example, tetrakis[methylene-
Examples include a combination of 3(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, zinc stearate and glycerin monostearate.

Furthermore, the olefin polymer according to the present invention includes silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, Basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass peas, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, Fillers such as molybdenum sulfide, holon fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

Effects of the Invention The present invention is a method for producing a polymer composition with excellent physical properties by bringing a specific polymer [A] into contact with a polyolefin in the presence of a specific cationic polymerization initiator. It has the characteristic that it can be manufactured at a higher temperature than the above.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

The methods for measuring and evaluating various physical property values are shown below.

(1) Melt flow index (MFR): Measured at 260°C in accordance with ASTM-D785.

(2) Tensile elongation at break: ASTM-
Measured according to D638.

(3) Evaluation of dispersion state: Evaluated by scanning electron microscope observation.

Polymerization Example 1 [Synthesis of cyclic olefin random copolymer] Ethylene and tetracyclo[4,4,0,12517'']- were continuously synthesized using a 21-volume glass polymerization vessel equipped with a stirring blade.
] A copolymerization reaction with 3-dodecene structural formula (hereinafter abbreviated as TCD-3) was carried out by the following method.

A cyclohexane solution containing TCD-3 monomer is added from the top of the polymerization vessel to a concentration of TCD-3 in the polymerization vessel of 60 g/
I, and as a catalyst ■○(○C2H5)C
The cyclohexane solution of No. 12 was mixed with a vanadium concentration of 0.6 mmol/I! in the polymerization vessel. , ethylaluminum sesquichloride CAI (C,, H5), 5C1,5) in cyclohexane at an aluminum concentration of 4.8 mlJ in the polymerization vessel.
The polymerization solution in the polymerization vessel is continuously fed into the polymerization vessel from the bottom of the polymerization vessel so that the ratio is mol/I.
The samples were extracted continuously so that the average residence time was 0.5 hours. Further, from the top of the polymerization vessel, ethylene was supplied at a rate of 2Of/hour, hydrogen at a rate of 0.5Of/hour, and nitrogen at a rate of 10.77Of/hour.

The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

A copolymerization reaction was carried out under the above reaction conditions to obtain a polymerization reaction mixture containing an ethylene/TCD-3 random copolymer. The polymerization reaction was stopped by adding a small amount of isopropyl alcohol to the polymerization liquid extracted from the lower part of the polymerization vessel. Next, the polymerization solution was poured into a household mixer containing about three times as much ascent as the polymerization solution while rotating the mixer, and the resulting copolymer was precipitated. The precipitated copolymer was collected by filtration, and the polymer concentration was approximately 50 g/I! The copolymer was dispersed in acetone so as to have the following properties, and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment, the copolymer was collected by filtration and dried under reduced pressure at 120°C for 24 hours.

In the ethylene/TCD-3 random copolymer obtained as above, the ethylene content of the copolymer measured by C-NMR analysis was 62 mol%, and the intrinsic viscosity [η] measured in decalin at 135°C was 0.46 cU/g, and the softening temperature (TMA) was 148°C.

Polymerization Example 2 A random copolymerization reaction of ethylene, TCD-3, and 5-ethylidene-2-) was carried out under the same conditions and method as in Polymerization Example 1 using the monomers and hydrogen shown in Table 1. This was done using the supplied amount.

Table 1 shows the physical properties of the cyclic olefin copolymers obtained in Polymerization Examples 1 and 2.

Polymerization Example 3 (Synthesis of propylene-ethylene copolymer (P/S copolymer)) Volume 1 with stirring blades. ! Add 1) of n-decane and 5rnl of styrene to a 1-liter glass polymerization vessel, add 10 mmol of triisobutylaluminum after nitrogen substitution, and 3.33 mmol of p-1 methyl ruylate, and add 2507 ml of propylene.
/hour, hydrogen was supplied at a rate of 201/hour, and the temperature was raised to 60°C.

After raising the temperature, 0.2 mmol of the titanium catalyst component prepared by the method described in Example 1 of Japanese Patent Publication No. 63-54004 was added, and at the same time as the addition, styrene was started dropwise, and 8- was added dropwise over 30 minutes. .

At the same time as the addition of styrene was completed, isobutyl alcohol was added to stop the reaction.

The polymerization solution was transferred to a glass filter under a nitrogen atmosphere and filtered. Filter side edge, n- containing 5% isobutyl alcohol
The polymer was washed three times with 500 ml of decane and dried under reduced pressure. The obtained polymer will be referred to as Polymer 3.

The polymer yield was 120 g, the styrene content was 0.5 mol% as measured by 'H-NMR, the MFR was 20 g/10 min as measured at 230°C and a load of 2 kg, and the press sheet was measured by X-ray diffraction method (prepared at 230°C). ) has a crystallinity of 50%
Met.

Polymerization Example 4 (Synthesis of propylene/4(5)-methyl-1,4-hexadiene copolymer (P/MHD copolymer)) N-decane was placed in a 1.51-volume glass polymerization vessel equipped with a stirring blade. 1)
．． A 4/1 mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene was added with 100% nitrogen gas, and after the atmosphere was replaced with nitrogen, propylene was added at 2501/hr and hydrogen was added at 1/hr.
The temperature was raised to 60°C.

After raising the temperature, add 10 mmol of triethylaluminum, 2 mmol of cyclohexylmethyldimethoxysilane, JP-A-5
1 mmol of the titanium catalyst component prepared by the method described in Example 1 of Publication No. 8-83006 was added, and the reaction was carried out for 60 minutes.

The reaction was stopped by adding isobutyl alcohol.

The polymerization solution was transferred to a glass filter under a nitrogen atmosphere and filtered. Filter side edge, n- containing 5% isobutyl alcohol
The polymer was washed three times with 500 rIL of decane and dried under reduced pressure. The obtained polymer is referred to as Polymer 4.

Polymer yield was 76 g, MHD determined by C-NMR.
The content is 4.3 mol%, the crystallinity of Blessy 1' (prepared at 230°C) is 40%, measured by X-ray diffraction method. there were.

Polymerization Example 5 Synthesis of chlorinated ethylene-propylene copolymer (EPR) EPR (
Manufactured by Mitsui Petrochemical Industries, Ltd.: Tafmar P-0680)
400 g was collected and the polymer concentration was 80 g/I! 51 ml of carbon tetrachloride was added to the solution, and the polymer was dissolved under reflux while blowing nitrogen.

After confirming that the polymer was completely dissolved, the nitrogen supply was stopped and chlorine gas was supplied at a rate of 301/hour.

After 2 hours of reaction, the supply of chlorine gas was stopped, and the dissolved chlorine gas was removed by replacing the reactor with nitrogen. After cooling, the reaction solution was precipitated in methanol and dried under reduced pressure. The obtained polymer will be referred to as Polymer 5.

Elemental analysis shows that the chlorine content in the polymer is 3.2% by weight.
Met. The measured VFR at 260° C. and 12 kg load was 0.9 g/10 minutes.

Example 1 In a glass 1.57 separable flask, [A] acid component was propylene/styrene copolymer (polymer 3) 36
g, [B] EPT as acid component (Mitsui Petrochemical Industries, Ltd.)
: EPT #3070) 24 g, n-decane 1) was added as a solvent, and 1) was added without stirring under a nitrogen atmosphere.
It was uniformly dissolved at 50°C.

Next, while stirring the above polymer solution at 150°C, 2.5 mmol of ethylaluminum sesquichloride was added,
Thereafter, 1.25 mmol of 1,4-dichlorocyclohexane was added dropwise over 10 seconds. After dropping, the viscosity of the solution increased as the reaction proceeded. After reacting for 10 minutes, the reactant was added to 5 p of methanol while stirring, and the polymer was taken out and dried.

The obtained polymer was press-molded at 230° C., test pieces were prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 2.

Comparative Example 1 In Example 1, ethylaluminum sesquichloride,
A similar operation was performed except that 1,4-dichloroisochlorohexane was not used.

The results are shown in Table 2.

Comparative Example 2 The same operation as in Example 1 was carried out except that chlorocyclohexane was used instead of 1.4-dichlorocyclohexane.

The results are shown in Table 2.

Example 2 The same operation as in Example 1 was performed except that chlorinated EPR (polymer 5) was used as the [B] acid component and 1,4-dichlorocyclohexane was not used.

The results are shown in Table 2.

Example 3 In Example 1, [A] acid component is propylene/MHD
The same operation was performed except that a copolymer (polymer 4) was used.

The results are shown in Table 2.

Example 4 The same operation as in Example 1 was carried out except that the [A] acid component was used as the polymer 1 obtained in Polymerization Example 1, and the decalin solvent was used.

The results are shown in Table 2.

Example 5 The same operation as in Example 1 was carried out except that Polymer 2 obtained in Polymerization Example 2 was used instead of the acid component [A].

The results are shown in Table 2.

Example 6 SUS[1,5I! In an autoclave, 30 g of pellets of Polymer 1 obtained in Polymerization Example 1 as [A] acid component,
[30 g of propylene/MHD copolymer (polymer 3) as component B, and cyclohexane II as solvent! was added and uniformly dissolved at 150°C under a nitrogen atmosphere without stirring.

Next, while stirring the above polymer solution at 150°C, 1 mmol of ethylaluminum sesquichloride was added, and then 05 mmol of 1,4-dichlorocyclohexane was added at 10 mmol.
It dripped in seconds. After reacting for 10 minutes, the reaction product was cooled to 50'C, added to methanol 5A' with stirring, and the polymer was taken out and dried.

The obtained polymer was press-molded at 230''C, test pieces were prepared by the method described above, and the physical properties were evaluated.

The results are shown in Table 2.

Comparative Example 3 In Example 6, ethylaluminum sesquichloride,
A similar operation was performed except that 1,4-dichlorocyclohexane was not used.

The results are shown in Table 2.

Claims (4)

[Claims] (1) [A] A polymer containing at least one structural unit derived from (i) a nonconjugated diene or (ii) an aromatic vinyl compound, and [B] a polyolefin in the presence of a cationic polymerization initiator. A method for producing a polymer composition by contacting with a cationic polymerization initiator, wherein the cationic polymerization initiator comprises (a) a halogen-containing metal compound, and (b) a hydrocarbon compound containing two or more chlorines, and the contacting A method for producing a polymer composition, characterized in that the above steps are carried out at a temperature of 100°C or higher. (2) The method for producing a polymer composition according to claim (1), characterized in that a chlorinated organic aluminum is used as the halogen-containing metal compound (a). (3) The polymer according to claim (1), wherein an aliphatic hydrocarbon compound containing two or more chlorines is used as the hydrocarbon compound containing two or more chlorines (b). Method for manufacturing the composition. (4) The method for producing a polymer composition according to claim (1), wherein the contact is carried out in a solvent.