JPS6043365B2 - Improved method for producing ring-opened polymers - Google Patents

Description

[Detailed description of the invention] The present invention relates to an improved method for making odoriferous polymers.

More specifically, norbornene derivatives and/or norbornadiene derivatives, or mixtures thereof with cycloolefin compounds copolymerizable with them, are
)■A)■B)■B) An organometallic compound having at least one metal selected from the group consisting of metals of groups IVA and IVB, and (B) "carpene complex of tungsten or molybdenum" (hereinafter "carpene complex") The present invention relates to an improved method for producing a ring polymer, which is characterized by carrying out ring polymerization using a catalytic system obtained from a catalytic converter. Some of the inventors of the present invention have already reported on the method for producing the same monopolymer in Japanese Patent Publication No. 50-2372 Gin and Japanese Patent Application Laid-Open No. 49-6
799 hours, 49-7799 hours, 50-15820 inches,
50-7180 inch, 50-75300 and 5
It was proposed as No. 0-10360α. however,
When producing polymers using the above-mentioned methods, the polymerization activity of these catalyst systems is not always satisfactory. Furthermore, as a result of various searches for obtaining a catalyst system with excellent catalytic activity, the present inventors found that a catalyst system obtained from an organometallic compound and a carpene complex was prepared by combining the above-mentioned norbornene derivative or the derivative with a small amount of a cycloolefin compound. The present invention was achieved based on the discovery that a ring polymer can be obtained in high yield by carrying out ring polymerization.

The catalyst system used in the present invention is characterized by its polymerization activity (
Since the catalyst has a very high activity (catalytic activity), it is possible not only to reduce the amount of catalyst used, but also to increase the production efficiency of the polymerization apparatus.

In addition, since the amount of catalyst used can be small, after the polymerization is completed,
It is relatively easy to remove catalyst residues remaining in the resulting leaky polymer. Furthermore, since the catalyst system used in the present invention has little activity reduction due to the polar groups of the monomers, ring-opening polymerization can be continued for a long time.
Norbornene derivatives used in the present invention are norbornene derivatives having at least one cyano group (nitrile group) or a substituent containing a cyano group (hereinafter referred to as 1).
cyano-based norbornene derivatives), norbornene derivatives having at least one ester group or a substituent containing an ester group (hereinafter referred to as ester-based norbornene derivatives);

Norbornene derivatives J having at least one ether group or a substituent containing an ether group (hereinafter referred to as ether-based norbornene derivatives); 1 Norbornene derivatives J having at least one amide group or a substituent containing an amide group ( 1) Norbornene derivatives having at least one chlorine atom or bromine atom or a substituent containing a chlorine atom or bromine atom (hereinafter referred to as halogenated norbornene derivatives); 1 At least one Norbornene derivatives having an acid anhydride group or a substituent containing an acid anhydride group (hereinafter referred to as acid anhydride-based norbornene derivatives) and 1 having at least one imide group or a substituent containing an imido group. Refers to norbornene derivatives (hereinafter referred to as 1-imide norbornene derivatives). Further, the term "norbornadiene derivative" refers to a norbornadiene derivative having at least one ester group or a hydrocarbon residue containing at most one ester group (hereinafter referred to as a monoester-based norbornadiene derivative).

The general formula of a typical cyano-based norbornene derivative is shown by the following formula [Formula (1)]. [However, W1, X1, Y1 and l may be the same or different, and may be a hydrogen atom, a cyano group (nitrile group), an alkyl group having at most 2 carbon atoms substituted with a cyano group, a cycloalkyl group, or an alkenyl group. and a hydrocarbon group selected from the group consisting of allyl (Ary) group, or an alkyl group having at most 20 carbon atoms, an alkenyl group, a cycloalkyl group, an allyl (AryI) group, and an aralkyl group. Although it is a hydrocarbon group, W1, X1, Y1
and l, at least one is a cyano group or a hydrocarbon group substituted with a cyano group] Typical examples include 5-cyanobicyclo[2,2,1]-heptene-2,5,5 -dicyanobicyclo[2,2,1]-heptene-2,5,6-dicyanobicyclo[2,2,1]
-Heptene-2,5-cyano-5-methyl-bicyclo[
2,2,1]-heptene-2,5-cyano6-methyl-bicyclo[2,2,1]-heptene-2,5-cyano5-ethylbicyclo[2,2,1]-heptene-2
and 5-cyanomethyl-bicyclo[2,2,1]-heptene-2.

Furthermore, another representative example is described in Japanese Patent Laid-Open No. 49-67999. Typical examples of general formulas of ester-based norbornene derivatives include those shown by the above formula (1) and the following formula [formula (■)].

[However, Wl, Xl, yl and Z1 and W2,
X2, Y2 and l are a hydrogen atom, an ester group [the general formula is represented by -COORl or -0C0R1 (however, R1 is a hydrocarbon group having at most 20 carbon atoms)], a hydrocarbon substituted with an ester group Group [general formula is -R2COO
Rl or -R2OCORl [however, R1 is the above-mentioned hydrocarbon group (same as R1), R2 is a divalent hydrocarbon group having at most 2 carbon atoms] or the above-mentioned hydrocarbon group, Wl, Xl, Y1 and l or W2, X2,
At least one of Y2 and Z2 is an ester group or a hydrocarbon group substituted with an ester group;
Other examples are shown by the following formulas [formula (■) and formula (■)].

[However, A is -00C-R3-00C- or -CO
OR4- (wherein R3 and R4 are alkylene groups having at most 20 carbon atoms), W3 and Z3 and W4, X4, Y4 and Z4 may be the same or different, and may be hydrogen atoms or is a hydrocarbon residue or hydrocarbon group substituted with W4,
4, Y4, and Z4, at least one is an ester group or a hydrocarbon group substituted with an ester group] In carrying out the present invention, among the ester-based norbornene derivatives represented by the above general formula, in particular ( 1) Ester based norbornene derivatives shown by the formula are desirable.

A typical example is 5-methoxycarbonyl-bicyclo[2,2,1]-heptene-2,5-methyl-5-
Methoxycarbonyl-bicyclo[2,2,1]-heptene-2,5,6-dimethoxycarbonyl-bicyclo[2
,2,1]-heptene-2 and 5-acetoxybicyclo[2,2,1]-heptene-2.

Moreover, other representative examples are described in Japanese Patent Application Laid-Open No. 49-779.

The general formulas of typical ether-based norbornene derivatives are those shown by formulas (1), (■), and (■) above.

[However, Wl, Xl, Y1 and l and W2,
2, Y2 and l and W3 and l may be the same or different, and may be a hydrogen atom, an ether group, a hydrocarbon group substituted with an ether group [the general formula is -R2ORl- (where R
1 is the same as R1, R2 is a divalent hydrocarbon group having at most 2 carbon atoms] or the hydrocarbon group, W1, X1, Y1 and, Z1 or W2, X2,
At least one of Y2 and Z2 is an ether group or a hydrocarbon group substituted with an ether group, and A is
The general formula is -R3OR4- or -R5O- (where R
3, R4 and R5 may be the same or different, and are a hydrocarbon group having at most 2C@ carbon atoms] Representative examples of the ether-based norbornene derivatives represented by formula (1) is 5-methoxybicyclo [
2,2,1]-heptene-2.

Other representative examples of those represented by formula (1) include those described in Japanese Patent Application Laid-Open No. 718-1983.

Representative examples of the ether norbornene derivatives represented by formulas (■) and (■) can also be shown in the same manner as above.

The general formulas of typical amide norbornene derivatives are shown by the formulas (1), (■), and (■) above.

However, in equations (1), (■), and (■),
W, , X1, Y1 and l or W2, X2, Y2
At least one of Z2 or W3 and Z3 is the amide group or a hydrocarbon group substituted with the amide group.

R1 and R2 may be the same or different and are hydrocarbon groups having at most 20 carbon atoms, and R3 is a divalent hydrocarbon group having at most 2 carbon atoms. A is a hydrocarbon group having a general formula of or (wherein R4, R5 and R6 may be the same or different and have at most 2 carbon atoms, and R7 is an alkylene group having at most 2 carbon atoms) It is a group represented by

Furthermore, in the present invention, in the above formula (1), W1
, X1, Y1 and l, at least one has the general formula! -γ (However, R3 has at most 2C@
An amide norbornene derivative represented by the alkylene group) can also be used as a monomer.

A typical example is N,N-dimethyl-bicyclo [
2,2,1]-heptene-2-carbonamide 5,6
can be given.

Further, another representative example is described in Japanese Patent Application No. 49-61851. The general formulas of typical halogenated norbornene derivatives are those shown by formulas (1) and (■) above.

However, in equations (1) and (■), W1, X1
, Y1 and 1 and W2, X2, Y2 and 1 may be the same, and the number of carbon atoms substituted with a hydrogen atom, a chlorine atom, a bromine atom, or at least one chlorine atom or a bromine atom is at most 2? or a hydrocarbon group having at most 2 carbon atoms, and at least one of W1, X1, Y1 and l or W2, X2, Y2 and l is a chlorine atom, a bromine atom, or a chlorine atom or A hydrocarbon group substituted with a bromine atom.

A typical example is 5-chloroubicyclo[2,2
,1]-heptene-2,5-chloromethyl-bicyclo[
2,2,1]-heptene-2 and 5,6-dichloroubicyclo[2,2,1]-heptene-2.

Other representative examples are described in Japanese Patent Application Laid-Open No. 50-15310 and Japanese Patent Application No. 49-129581. The number of halogen atoms in the derivative is generally at most one. The general formulas of typical acid anhydride norbornene derivatives are shown by the following formulas [formula (■) and formula (■)].

- [However, W5 and Z5 and W6 and X6 may be the same or different, and are hydrogen atoms or hydrocarbon groups having at most no more than one carbon number, and B is a tetravalent hydrocarbon having 4 to 2 carbon atoms. group, D is oxygen, 1 and m are independently 0, 1 or 2, and q is O or 1]
In the above formulas (■) and (■), when q is O, the carbon of the norbornene ring and the acid anhydride-containing group form a monocycle.

Typical examples include 3,6-methylene-1,2,3,
6-tetrahydrosis-phthalic anhydride and 1,4
,5,8-dimethanol 1,2,3,4,4a5,8,8
Examples include a-octahydronaphthalene-2,3-dicarboxylic acid anhydride.

Another representative example is described in Japanese Patent Application Laid-Open No. 50-58200. Examples of the general formulas of typical imide-based norbornene derivatives are those shown by formulas (■) and (■) above.

However, in the formula, D is represented by the general formula N-R1 (wherein R1 is a group containing a hydrocarbon group or an ester group having at most no more than one carbon number).

However, B, l, m and q are the same as in the case of the acid anhydride-based norbornene derivative. The general formula of other imide-based norbornene derivatives is shown by the following formula [formula (■)].

(However, W7, Y7 and l may be the same or different and are hydrogen atoms or hydrocarbon groups having at most 2C@ carbon atoms, and R2 is an alkylene group having 2 to 6 carbon atoms, an alkenylene group, or an arylene group. and n is 0, 1 or 2) Representative examples include N-methyl-3,
6-methylene-1,2,3,6-tetrahydrosis-phthalimide, N-n-butyl-3,6-methylene-1
, 2,3,6-tetrahydrosis-phthalimide and N-butyl-3,6-methylene-1-methyl-1,2
, 3,6-tetrahydrosis-phthalimide.

In addition, general formulas of other imide-based norbornene derivatives and their production methods, N-monosubstituted-3,6-methylene-1,2,3,6-tetrahydrosis-phthalimide compounds of imide-based norbornene derivatives, and N-[ ω
-(5-Norborn-2-enyl)A representative general formula of the alkylmaleimide compound and other imide-based norbornene derivatives is disclosed in JP-A-50-753.
(1) It is described in Publication No. A typical example of the ester-based norbornadiene derivative is represented by the following formula [formula (■)].

[However, X8 and Y8 may be the same or different, and may be a hydrogen atom, a hydrocarbon group having at most no more carbon atoms, or a group having the general formula 1(CH2). ．． COOR'' and one (CFI2
)NOCOR'' (However, R'' and R'' are hydrocarbon groups having at most no more than 100 carbon atoms, m and n are O or 1 to
(an integer of 10), where at least one of X8 and Y8 is an ester group or a group containing an ester group] Typical examples include 2-methoxycarbonyl-bicyclo [2, 2, 1]
-hepter 2,5-diene and 2,3-dimethoxycarbonylbicyclo[2,2,1]-hepter 2,5-
I can give you Jien.

Another representative example is described in the specification of Japanese Patent Application Laid-open No. 50-10360. In addition, the heteropolar group-containing norbornene derivatives used as monomers to produce the ring-opening polymer in the present invention include cyano groups, ester groups, halogen atoms (chlorine atoms and bromine atoms), and ether groups. , a polar group selected from the group consisting of an imide group, an acid anhydride group, and an amide group, and a hydrocarbon group substituted with the polar group as W1, X1, Y1 and j or W2, They are different.

For example, if W1 among W1, X1, Y1, and Z1 is a cyano group, one of Xl, Yl, and l is a different polar group such as an ester group, an ether group, and an amide group, or contains these polar groups. Xl,
Norbornene derivatives in which Yl and Z1 have only a cyano group or a hydrocarbon group containing a cyano group are not applicable (in this case, they are cyano-based norbornene derivatives). In addition, W1, X1, Y1 and Z1 and W2,
X2, Y2 and l are hydrogen atoms or hydrocarbon groups selected from the group consisting of alkyl groups, alkenyl groups, cycloalkyl groups, allyl groups and aralkyl groups having at most 2C@ carbon atoms; Good too. The cycloolefin compounds used for copolymerization with monomers in the present invention are broadly classified into monocyclic monoolefin compounds, nonconjugated cyclic polyene compounds, and polycyclic olefin compounds.

The general formula of monocyclic monoolefin compounds is the following formula [(■)
It is expressed by the following formula. (however, n is an integer of 3 to 20) Typical examples include cyclopentene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, and these monocyclic monoolefin compounds containing an alkyl group having one or more carbon atoms and at most w number of carbon atoms. Examples include monocyclic monoolefinic compounds substituted with a hydrocarbon group selected from the group consisting of Aryl, alkenyl, and Aryl groups.

The general formula of the non-conjugated cyclic polyene compound is represented by the following formulas [Formula (X) and Formula (XI)].

(However, 1 is O or an integer of 1 to 20, and m and n are integers of 2 to 20.) Representative examples include 1,5-cyclooctadiene and 1,5,9-cyclododecatriene.

Furthermore, non-conjugated cyclic polyene compounds represented by the above formulas (X) and (X[) are substituted with one or more of the above hydrocarbon groups and/or halogen atoms (for example, 1-chloro 1,5-
cyclooctadiene and 1-methyl-1,5-cyclooctadiene) can also be used. A polycyclic monoolefin compound is a compound having 2 to 1 ring and 1 to 5 carbon-carbon double bonds, and a representative example thereof is bicyclo[2,2,1]-heptene-2. (norbornene), 5-methyl-bicyclo[2,2,1]-heptene-2,5-vinylbicyclo[2,2,1]-heptene-2,5-ethylidene-bicyclo[2,2,1]-heptene 2,5-isopropenylubicyclo[2,2,1
]-heptene-2, dicyclopentadiene, bicyclo[
2,2,1]-hepter2,5-diene (norbornadiene) and 1,4;5,8-dimethanol 1,2,3,
Examples include 4,4a,5,8, &l-octahydronaphthalene.

Moreover, in carrying out the present invention, the above (X[)
Other than the non-conjugated cyclic polyene compound represented by the formula, cyclic compounds such as those obtained by metathesis polymerization of the cycloolefin compounds represented by the above formulas (■) and (X) can be used. Examples include oligomers (generally having a degree of polymerization of at most 100).

Among the above monomers, some of the J cyano-based norbornene derivatives, ester-based norbornene derivatives, ether-based norbornene derivatives, amide-based norbornene derivatives, halogen-based norbornene derivatives, acid anhydride-based norbornene derivatives, and cycloolefin-based compounds (e.g. , 5-methyl-bicyclo[2,2,1]-heptene-2)J (hereinafter referred to as 1 monomer (4) group) have endo (EndO) type and exo (ExO) type for each substituent. There are two types of isomers, and in the present invention, these isomers may be used after being separated, or may be used as a mixture of isomers without separation.

What about equation (1) for the above quantities? The monomer represented by the formula (■) is generally produced by subjecting a corresponding compound having one divalent bond to cyclopentadiene or dicyclopentadiene to a Diels Alder reaction. A monomer that can be obtained is also obtained.

The monomer represented by formula (■) can be obtained by subjecting the monomer represented by formula (1) to a Diels-Alder reaction with cyclopentadiene or dicyclopentadiene. When obtained as a mixture, these monomers may be used separately or without being separated. Generally, as the number of carbon atoms in the monomer used in the present invention increases, the heat resistance decreases, so it is preferable that the total number of carbon atoms (including carbons in the norbornene ring and polar groups) be at most 4. In particular, a structure having two or fewer fences is preferable.

However, the ester-based norbornadiene derivative preferably has a total hydrocarbon residue of at most 4@, and is particularly preferably 3@ or less. Regarding the acid anhydride-based norbornene derivatives, those in which q is 0 and 1 and m are O or 1 in the formulas (V) and (■) are preferable. Among the monomer (4) group, the monomer represented by the formula (■), and among the imide norbornene derivatives (■)
As the monomers represented by formula and (■) increase, a polymer with excellent heat resistance can be obtained,
On the other hand, the processability of the obtained polymer is not necessarily satisfactory.

From the above, among the monomers (4) group, (1)
Among the monomers represented by the formula and imide-based norbornene derivatives, the polymerization ratio of the monomer represented by the formula (■) is generally at least 1 mol%, preferably 10 mol% or more, particularly 50 mol%. % or more is suitable. In carrying out the present invention, only one type of monomer may be used, or two or more types may be used in combination.

Further, the copolymerization ratio of the cycloolefin compound as a copolymerization component is at most 50 mol%, preferably 45 mol% or less, and particularly preferably 40 mol% or less.

The organometallic compounds used to obtain the catalyst system used in the present invention are IA, ■A, ■B, and ■ of the periodic table.
It is an organometallic compound containing at least one metal among Group B, ■A, and IVB metals, some of which have the general formula shown below. MRn [However, M is IA, ■A, ■B, ■B, I of the periodic table.
A VA or IVB group metal, R is an alkyl group, an alkenyl group, or an allyl group having at most no more than one carbon number.
an organic group selected from the group consisting of aralkyl group, alkyl group, alkoxide group, phenoxy group, and cyclopentadienyl group, or a hydrogen atom or a halogen atom, which may be the same or different, but at least one of them is A hydrogen atom or the above organic group, and n is the highest valence number of the metal or less complex and 1 mole of said organometallic compound and at most 2,
Mention may be made of reactants with 0 mol of water as well as double salts of the two organometallic compounds mentioned above.

Typically, organometallic compounds containing lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, gallium, titanium, zirconium, silicon, germanium and tin are preferred, with particular preference given to lithium, sodium, , magnesium, zinc, aluminum, and tin are preferred, and organoaluminium-based compounds are particularly preferred.

Typical examples of the organoaluminum compounds include triethylaluminum, triisobutylaluminum, trihexylaluminum, diethylaluminum chloride, di-n-butylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum butoxide, and the reaction product of triethylaluminum and water. (reaction ratio 1:0.5 (molar ratio)).
Representative examples of other organoaluminum compounds are
0-2372@ and JP-A Nos. 49-67999, 49-77999, 50-58200, 50-
No. 718(4) and No. 50-7580 of the same publication. Examples of other organoaluminum compounds include aluminum/siloxsalene compounds, aluminum/amide compounds, dialmoxalene compounds, and double salts containing the above organoaluminum compounds. Typical examples of other organometallic compounds are Japanese Patent Application No. 50-112068, No. 50-112534, No. 5
No. 0-116324, No. 50-117664, and No. 50-120317.

Furthermore, the general formula of the carpene complex is shown by the following formulas [Formula (4)] and Formula (B)].

In the above formulas (4) and (B), L is an amine, ether, nitrile, and ketone compound, pyridine, phosphorus-containing compound, arsenic-containing compound, and antimony-containing compound having at most 2C@ carbon atoms, and M is tungsten or molybdenum metal, R and R'' may be the same or different, and are organic groups represented by R1, 0R3, SRl or NRlR2 (provided that R1 and R2 are hydrogen or a group having at most two carbon atoms). is a hydrocarbon group, R3
is hydrogen, a hydrocarbon group with at most 2 carbon atoms, or a quaternary ammonium group), u is 0 or 1, and n
is a positive integer less than or equal to 5.

A typical example of carpene complex is (CO)5WC(0CH
3) CH3, (CO)5WC (0C2H5) (C6H5
), (CO)5WC (0H) (C6H5), (CO)5
WC(SH) [N(C2K,)2], (C6ll5)3
]WC(0CH3)(C6H5), (CO)4[As(
C6H5)3]WC(0C21(5)(C6H5), (
CO)5WC(0C2H5)(C4FI9),(CO)
5WC(0C2H5)N(CH3)2,(CO)5M0
C(0C2H5)(C4H9), (CO)5WC(C6
H5)2, [N ((CH3)4)+[(CO)5M0
C(0-)CH3] and [N(C2H5)4]8[(
Examples include those shown by the chemical formula: CO)5WC (O2C6H5).

A typical example of these is Day. J.A. Caldein (D.J.
．． Cardin) et al., Chemical Review (Chem
icalReviews) Page 545, Volume 72, No. 5
No., (197 reviews). In carrying out the present invention, the organometallic compound for one atomic equivalent of tungsten or molybdenum in the carpene complex is:
Generally, the amount is 0.1 to 100 mol, preferably 0.5 to 50 mol, and particularly preferably 1.0 to 30 mol, from the viewpoint of polymerization activity. In carrying out the present invention, a catalyst system obtained from an organometallic compound and a carpene complex may be used, but it is also possible to use a catalyst system obtained from these and another compound (third component). , a catalyst system with even better catalytic activity can be obtained. Examples of the third component include water, hydrogen peroxide, an oxygen-containing organic compound, a nitrogen-containing organic compound, a halogen-containing organic compound, a phosphorus-containing organic compound, a sulfur-containing organic compound, and a metal-containing organic compound. Representative examples of these third components are disclosed in Japanese Patent Application Laid-open No. 5
It is described in the specification of No. 1-63(1). The organometallic compound, the carpene complex, and the third component may be used alone or in combination of two or more.
When a third component is used in the present invention, the ratio of the third component to one atomic equivalent of tungsten or molybdenum metal in the carpene complex is generally at most 100 moles, and from the standpoint of polymerization activity, it is 50 moles or less. is preferable, and 3 mol or less is particularly preferable.

Further, although the catalyst system used in the present invention varies depending on the type of catalyst, the proportion of carpene complex used is 0.001 to 100 mol as the tungsten or molybdenum metal per 1000 mol of the monomer. The atomic equivalent is 0.005 to 50 in terms of polymerization activity and catalyst removal.
An atomic equivalent is preferable, and an atomic equivalent of 0.01 to .10 is particularly preferable.

The above-mentioned organometallic compound, carpene complex, and third component may be added to the polymerization system without any pretreatment, but some or all of them may be crushed or co-pulverized in advance, or one solvent It may be used after performing a pretreatment such as a method of thermal formation by heating in the presence of the compound.

The present invention involves carrying out ring-opening monopolymerization or ring-opening copolymerization of a monomer or a monomer and a cycloolefin compound in the presence of the above catalyst system in the absence of an inert organic solvent.
Although that purpose can be achieved, the ring-opening polymerization may also be carried out in an inert organic solvent.

Examples of inert organic solvents include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and ethers.

When carrying out the present invention in an inert organic solvent, these inert organic solvents may be used alone or as a mixture of two or more. When ring-opening polymerization is carried out in the organic solvent, the proportion of the organic solvent to be used is generally at most 2 parts by volume, and in particular, 1 part by volume or less. preferable. The polymerization temperature is generally -100 to +250°C, particularly -50 to +
180°C is preferred, particularly 0-150°C.

If the polymerization temperature is -100°C or lower, there is no sufficient polymerization activity, so the polymerization rate is very slow, and furthermore, the monomer or the mixture of the monomer and the inert organic solvent may solidify. On the other hand, if the polymerization temperature is 250°C or higher, it is often difficult to sufficiently control the polymerization. Although the target ring-opening polymer of the present invention can be obtained by ring-opening polymerization by the above method, it is also possible to obtain an α-olefin having at most b carbon atoms (for example, ethylene, hexene-1, octene-1, etc.). 1), internal olefins with at most 2 carbon atoms (e.g., hexene-2, octene-2),
Conjugated diolefins having at most 20 carbon atoms or halogen substitution thereof (e.g., butadiene, chloroprene)
, non-conjugated diolefins having at most 2C@ carbon atoms (e.g. 1,4-hexadiene) and JP-A-50-56
No. 494, No. 50-56495, No. 50-56496
The molecular weight of the ring-opened polymer obtained can be adjusted by adding the compounds described in the publications of No. 1 and No. 50-56497 as molecular weight regulators to the ring-opening polymerization system.

The addition ratio of the molecular weight regulator additive to 100 moles of monomer is generally at most 20 moles, preferably 10 moles or less, particularly preferably 2 moles or less.
The present invention may be carried out in a homogeneous system, but may also be carried out in a heterogeneous system.

Moreover, a batch method or a continuous method may be used. Since the catalyst system of the present invention is unstable to oxygen and moisture, it is desirable to operate under an atmosphere of inert gas such as argon and nitrogen. Although the object of the present invention can be achieved by ring-opening polymerization in the absence of an unsaturated polymer, it can also be carried out in the presence of an unsaturated polymer. Unsaturated polymers contain a carbon-carbon double bond, and include butadiene-based rubbers containing butadiene as a main component (for example, butadiene monopolymer rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene). Copolymer rubber); Chloroprene rubber; Isoprene rubber; Natural rubber, ethylene-propylene terpolymer (generally referred to as EPT or EPDM).

; Examples include cycloolefin rubber-like materials. When carrying out the present invention in the presence of the unsaturated polymer, generally the Mooney viscosity thereof is between 10 and 200, and between 20 and 1.
A number of 50 is desirable, and a number of 30 to 130 is particularly preferred.

Further, it is preferable that the carbon-carbon double bond is at least one carbon-carbon double bond per 100 total carbon-carbon bonds, and more preferably one or more carbon-carbon double bonds. The proportion of unsaturated polymer used per 1 part by weight of monomer is generally at most 1 part by weight, preferably 5 parts by weight or less, particularly preferably 3 parts by weight or less.

If the amount is more than 1 part by weight per 1 part by weight of the monomer, it will not be possible to obtain a polymer exhibiting the characteristics of the monomer used in the present invention. When carrying out ring-opening polymerization in the presence of an unsaturated polymer, the unsaturated polymer is generally dissolved or suspended (dispersed) in the monomer or the monomer and the inert organic solvent described below. It is used with

Further, the ring-opening polymerization may be graft polymerization, block polymerization, or a combination of graft and block polymerization. Graft products and block polymers obtained by the above method have excellent impact resistance, and are therefore particularly promising in fields where impact resistance is desired.

After completion of the ring-opening polymerization, the resulting polymer can be recovered by several methods.

As an example of the recovery method, a method for removing the catalyst and recovering the polymer, which is generally used in solution polymerization of isoprene, butadiene, etc., may be applied. Other purification (post-treatment) methods include
72 inches and Japanese Patent Publication No. 49-6799 inches, 50-77 inches
No. 999, No. 49-130500 and No. 50-58
No. 200], No. 50-71800, No. 50-7530
No. 0, 50-10,360 inches, 50-15,310 inches,
It is described in the publications No. 50-1595 and No. 50-16040.

According to the present invention, a ring-opened polymer with excellent properties such as mechanical properties (for example, impact resistance, low-temperature impact resistance, etc.), moldability, and transparency and flexibility, or a ring-opened polymer with good adhesive properties, or Ring-opened polymers useful as ion exchange resins or flocculants can be produced. In addition, since the polymerization activity of the catalyst is very high, the production amount of ring-opening polymer per single catalyst position is high, which not only makes it possible to reduce the amount of catalyst used, but also allows Purification of the ring-opened polymer obtained can be very simple or even omitted. As described above, the ring-opened polymer obtained by the present invention has excellent properties and can be used as is. Graft polymerization of styrene, acrylonitrile, vinyl chloride, methyl methacrylate, etc. to a rubber-like material described below Resin-like products such as grafted products, butadiene-based rubber products, chlorinated polyethylene-based rubber products, acrylic acid ester-based rubber products, ethylene-vinyl acetate copolymer rubber products, chloroprene-based rubber products, etc. Of the rubber-like substances,
One type or two or more types can also be blended.

In addition, light (
UV rays), heat, oxygen and ozone stabilizers, flame retardants, lubricants, fillers, reinforcing agents, impact modifiers (e.g. metal salts of carboxylic acids), colorants, antistatic agents and blowing agents. By incorporating additives such as the following, the effect can be further exhibited. The ring-opening polymer, graft product and/or block polymer obtained by the present invention, and the above-mentioned compound can be used as they are, but compression molding, extrusion molding, and injection molding methods used for general synthetic resins can be used. It can be molded into various shapes such as pellets, films, sheets, vibrators, rods, and containers by applying molding methods such as , blow molding, and the like.

In addition, the above-mentioned ring-opening polymer, grafted product and/or! or block polymers and blends such as styrene, vinyl chloride,
It is also possible to utilize vinyl compounds such as acrylonitrile and methyl methacrylate by graft polymerization, and furthermore, it is also possible to use them by so-called polymer reaction.

c As mentioned above, the ring-opened polymer and the composition thereof obtained by the present invention can be molded into any shape by various molding methods, so they can be used in a wide variety of fields. Examples include containers such as bottles, films and their secondary products (e.g. bags, packaging materials), daily necessities, parts for machinery, parts for electrical appliances and lighting equipment, vibrators, agricultural equipment or their parts. etc. In addition, ring-opening polymers, graft products, and/or block polymers can be used as they are or by polymeric reaction to produce ion exchange resins, flocculants, adhesives, and paints. Copolymers have improved oil resistance and mechanical properties compared to the unsaturated polymers.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, the reduced viscosity was measured using dimethylformamide as a solvent at a concentration of 0.1 da/dl and a temperature of 30°C.

Further, the polymerization activity was expressed with respect to a certain amount (y) of the metal tungsten or molybdenum in the carpene complex used. jExample 1 In a 500ml autoclave completely purged with nitrogen,
The concentration of 0 ml of 1,2-dichloroethane, 150 ml of 5-cyanobicyclo[2,2,1]-heptene-2 (as a monomer, 1.26 mol) and diethylaluminium chloride (as an organometallic compound) was 1.0 ml of a 1.0 mol/l 1,2-chloroethane solution was charged and stirred at room temperature to become homogeneous.

Next, as a carpene complex, 3.0ml of a toluene solution containing phenylethoxycarpenpentacarbonyltungsten [hereinafter referred to as 0 complex (A)j, (CO)5WC(0C2H5)(C6H5)] at a concentration of 0.1 mol/1 was added. added. After raising the temperature of the reaction system to 75°C, at this temperature 6
Polymerization was carried out with stirring for 0 minutes. After completion of polymerization, 2,
6-di-tertiary-butyl-P-cresol to about 1. The polymerization is stopped by adding about 50 mt of a mixed solution of 1.2-dichloroethane and methyl alcohol (about 4:1 by volume) containing 1.2-dichloroethane and methyl alcohol containing 1.2-dichloroethane and methyl alcohol. After the polymer was filtered, the polymer was thoroughly washed with methyl alcohol, and then dried at about 50° C. under reduced pressure for about 2 hours.

As a result, 1179 polymers were obtained. Polymerization activity is 2
It is 120V/y-W・hour. Note that the reduced viscosity of this polymer was 1.19. Examples 2 to 8, Comparative Example 1 Instead of complex (4) used as the carpene complex in Example 1, (CO), WC (CH3) (0C2H5) [
Hereinafter referred to as complex (B)], [N(CH3)4]1[
(CO)5WC(0-)(C6H5)] [Hereafter, 1 complex (
C) J], (CO)4[P (C6H5)3WC
(0CH3)(C6H5) [hereinafter referred to as 1 complex (D)J], (CO)5M0C(0C2H5) (C4H9) [hereinafter referred to as 0 complex (E)], (CO)5WC(0H)(
C6H5) [hereinafter referred to as 1 complex 1/1-゜ゝ1, (F)]], (CO)5WC8-CH2 [hereinafter referred to as 0 complex (G)J], (CO)5WC
Polymerization was carried out in the same manner as in Example 1, except that (SH) [N(C2H5)2] [hereinafter referred to as 1 complex (H)] and tungsten hexachloride (WCl6) were used in the amounts shown in Table 1. I did it.

The results are shown in Table 1. 1y/y-M.time (M: tungsten or molybdenum) Examples 9 to 15 Polymerization was carried out in the same manner as in Example 1, except that 150y of each of the monomers shown in Table 2 was used.

The results are shown in Table 2. Example 16 Copolymerization was carried out in the same manner as in Example 1, except that 5-cyanobicyclo[2,2,1]-heptene-2 was used in a mixture of 100f and 50g of cyclopentene.

As a result, a 128f polymer was obtained. Infrared absorption spectrum analysis and magnetic resonance spectrum analysis of this polymer revealed that 5-cyanobicyclo[2,2,
1]-Heptene-2 and cyclopentene was recognized as a copolymer.

The copolymerization ratio of cyclopentene in this copolymer was 41 mol%. Examples 17 to 21 Polymerization was carried out in the same manner as in Example 1, except that the organoaluminum compounds or reaction products thereof shown in Table 3 were used (however, the concentrations of the organoaluminum compounds used were the same as in Example 1). the same number of moles).

The results are shown in Table 3. 1y/y-W・time 22 mol of triethylaluminum and 1 mol of water Reaction product 3 Reaction product of equimolar of trimethylsilanol and triethylaluminum 4 Reaction product of equimolar of diethylamine and triethylaluminum Examples 22~
Copolymerization was carried out in the same manner as in Example 1, except that 70y of each of the monomers shown in Table 4 were used for 245-cyanobicyclo[2,2,1]-heptene-2.

The results are shown in Table 4. 1y/y-W・time 25-cyano-5-methyl-bicyclo[2,2,1]-
Heptene-235-methoxymethyl-bicyclo[2,2
,1]-heptene-245-chloromethyl-bicyclo[
2,2,1]-heptene-2 Example 25, 26 After adding diethylaluminum chloride, the fifth
1.0% of the molecular weight regulator shown in the table for each monomer.
Polymerization was carried out in the same manner as in Example 1, except that mol% was added.

The results are shown in Table 5. 1y/y-W・Time Example 27 Dried cis-1,4-polybutadiene [manufactured by Japan Synthetic Rubber Co., Ltd., trade name JSRBR-01, Mooney viscosity (ML
l+4100℃) 4\Sis-1,4 content 97.5%]2
0.0y was charged into a 1' glass autoclave purged with nitrogen, and 500ml of 1,2-dichloroethane was added and stirred to completely dissolve.

Claims (1)

[Claims] 1 Nitrile group, ester group, ether group, amide group,
A norbornene derivative having at least one polar group selected from the group consisting of a chlorine atom, a bromine atom, an acid anhydride group, and an imide group, or a hydrocarbon residue containing the polar group and having at most 20 carbon atoms, and at least At least one compound selected from the group consisting of norbornadiene derivatives having one ester group or a hydrocarbon residue having at most 20 carbon atoms containing an ester group, or said compound and at least 50 mol% of a cycloolefin system. A mixture of compounds is prepared in the absence or presence of an unsaturated polymer containing carbon-carbon double bonds (A
) I A, IIA, IIB, IIIB, IVA and I of the periodic table
A ring-opening polymer characterized in that it undergoes ring-opening polymerization using an organometallic compound having at least one metal selected from the group consisting of group VB metals and (B) a catalyst system obtained from a carbene complex of tungsten or molybdenum. Improved manufacturing methods.