JP2002220440A - Cyclic olefin ring-opening polymer and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic olefin ring-opening polymer having large elastic recovery, moderate elastic modulus and excellent transparency and heat resistance. SOLUTION: The polymer, wherein a straight chain having 2 or more carbon atoms and a hydrocarbon ring are alternately arranged, has a ratio of the chain having 3 or more carbon atoms based on the all chains of 5-95 wt.%, a ratio of a double bond based on the all C-C bonds in the chain of 50% or less, a weight average molecular weight expressed in terms of polystyrene by gel permeation chromatography of 1,000-1,000,000 and a chloroform insolubles of 0.1 wt.% or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyclic olefin ring-opening polymer which gives a molded article having a large elastic recovery and a method for producing the same.

[0002]

2. Description of the Related Art Films and sheets obtained by extrusion or inflation molding of olefin polymers such as polyethylene, polypropylene, polybutene, ethylene-propylene copolymer and ethylene-vinyl acetate copolymer include buffer sheets and tapes. It is widely used as packaging materials such as, and as consumer materials such as trays and cups. However, these films and sheets have problems such as insufficient elastic recovery, too high elastic modulus, poor adhesion to metal or other resins or rubber, and low transparency. there were. JP-A-5-97933 describes that an α-olefin / cyclic olefin addition copolymer having a specific composition ratio is excellent in elastic recovery and has an appropriate elastic modulus. However, since this copolymer contains a crystal component, transparency is still insufficient, and there is a problem in heat resistance.

On the other hand, a hydrogenated ring-opened polymer of a norbornene monomer represented by the following formula [1] has heat resistance, transparency,
It is attracting attention as a resin excellent in low water absorption.

[0004]

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Wherein R ¹ , R ² , R ³ and R
⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Or represents a substituent containing a halogen atom, a silicon atom, one atom of oxygen atom and nitrogen atom, R ¹ and R
^3, or may be R ² and R ⁴ are bonded to each other to form another ring. n is 0, 1 or 2. This resin has a structure in which hydrocarbon rings and straight chains are alternately arranged, and the straight chains have a short carbon number of two. That is, the norbornene-based monomer is formed into a polymer by ring-opening polymerization into a linear structural unit having 2 carbon atoms represented by the following formula [2] and a hydrocarbon ring structural unit represented by the following formula [4]. But does not form a linear chain having a size equal to or larger than a linear structural unit having 3 carbon atoms represented by the following formula [3].

[0006]

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(A bond formed by a solid line and a broken line between carbon and carbon represents a single bond or a double bond. Each R is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Or a substituent containing any one of a halogen atom, a silicon atom, an oxygen atom, and a nitrogen atom.
It is a symbol meaning two when it is a single bond and one when it is a double bond. )

[0008]

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(The meaning of each symbol is the same as in equation [2].)

[0010]

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(A represents a hydrocarbon ring, preferably 4 to
It is an 8-membered ring, more preferably a 5- to 6-membered ring, and may be a polycyclic ring having one or two to five additional rings. In some cases, a molded product of a norbornene-based ring-opened polymer hydride has a large rigidity and an excessively high elastic modulus, and an elastic recovery is too small to be used as a film or a sheet in some cases. Examples of lowering the elastic modulus of this polymer include ring-opening copolymerization of cyclopentene and dicyclopentadiene described in US Pat. Nos. 4,002,815 and 4,025,708. Polymer having a longer straight chain connecting hydrocarbon rings. However, as described in these publications, those polymers are difficult to hydrogenate because they contain a large amount of insoluble components (gel components),
It was inferior in transparency and heat resistance.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cyclic olefin-based ring-opened polymer having a large elastic recovery, an appropriate elastic modulus, and excellent transparency and heat resistance, and a process for producing the same. Is to do.

[0013]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a polymer having two or more carbon atoms and a hydrocarbon ring alternately arranged. When the ratio of the straight chain having 3 or more carbon atoms to the total straight chain is 5 to 95% by weight, and the ratio of the number of double bonds to the total number of carbon-carbon bonds in the straight chain is 50% or less, A cyclic olefin-based ring-opening polymer containing no coalescing has a large elastic recovery property,
It has been found that the polymer has an appropriate elastic modulus and is excellent in transparency and heat resistance. The present invention has been completed based on this finding. Thus, according to the present invention, (1) a polymer in which a straight chain having 2 or more carbon atoms and a hydrocarbon ring are alternately arranged, and the ratio of the straight chain having 3 or more carbon atoms to the total straight chain is 5 to 5. 95% by weight, the ratio of the number of double bonds to the total number of carbon-carbon bonds in the linear chain is 50% or less, and the weight average molecular weight in terms of polystyrene by gel permeation chromatography is 1,000 to 1,000. , 00
0, a cyclic olefin-based ring-opening polymer having a chloroform-insoluble content of 0.1% by weight or less, (2) a cyclic olefin-based monomer which forms a straight chain having 2 carbon atoms by a ring-opening reaction, A ring-opening polymerization of a cyclic olefin-based monomer forming a straight chain having 3 or more carbon atoms by a ring reaction using a carbene compound containing a transition metal belonging to Groups 4 to 9 of the periodic table; A step of obtaining a polymer in which linear and hydrocarbon rings are alternately arranged, and hydrogenating the carbon-carbon double bond in the polymer to obtain the total number of carbon-carbon bonds in the linear chain. A method for producing a cyclic olefin-based ring-opened polymer having a step of reducing the proportion to 50% or less, and (3) the above (1).
And a cyclic olefin-based ring-opening polymer composition having the cyclic olefin-based ring-opening polymer and the antioxidant described above.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin ring-opening polymer of the present invention is a polymer in which a straight chain having 2 or more carbon atoms and a hydrocarbon ring are alternately arranged, and has 3 carbon atoms with respect to the total straight chain. The proportion of the above straight chain is 5 to 95% by weight, and
The ratio of the number of double bonds to the number of carbon bonds is 50% or less, and the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent is 1,000.
A cyclic olefin ring-opened polymer having a chloroform-insoluble content (gel) of 0.1% or less. The cyclic olefin-based ring-opening polymer of the present invention contains an appropriate amount of a straight chain connecting a hydrocarbon ring and a straight chain having 3 or more carbon atoms in addition to a straight chain having 2 carbon atoms as described above. Therefore, the obtained molded article has an appropriate elastic modulus and a large elastic recovery rate. In addition, the polymer of the present invention has excellent transparency and heat resistance because it has few double bonds and few gels in addition to the inherent properties of the cyclic olefin ring-opened polymer.

The hydrocarbon ring as one component of the cyclic olefin ring-opening polymer of the present invention has preferably 4 to 8, more preferably 5 to 6 carbon atoms. If the carbon number of the hydrocarbon ring is too small, the polymer may be decomposed at a high temperature, and if it is too large, the elastic recovery may not be exhibited. The hydrocarbon ring may be a polycyclic ring having one or two to five additional rings, such as a ring-opening polymer of dicyclopentadiene. It is preferable that the number of carbon atoms in each accessory ring is also in the above range. Further, the ring may contain a substituent. The structural unit of the hydrocarbon ring is represented by the following formula [4].

[0016]

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(A represents a hydrocarbon ring, preferably 4 to
It is an 8-membered ring, more preferably a 5- to 6-membered ring, and may be a polycyclic ring having one or two to five additional rings. ) As the hydrocarbon ring, there are cycloalkane, cycloalkene and aromatic ring, and in the present invention, cycloalkane is particularly preferred.

The cyclic olefin ring-opening polymer of the present invention comprises:
Another component is a straight chain that directly connects a hydrocarbon ring to another hydrocarbon ring. A straight chain has a minimum carbon number of 2
Individual. The straight chain having 3 or more carbon atoms is present in an amount of 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight based on the entire straight chain. The carbon-carbon bond in the straight chain may have a double bond. The ratio of the number of double bonds to the total number of carbon-carbon bonds in the straight chain of the cyclic olefin ring-opened polymer of the present invention is 50% or less, preferably 40% or less.
%, More preferably 20% or less. If the proportion of double bonds is too large, the heat resistance of the molded article may be reduced. Also, the ratio of the number of double bonds in the hydrocarbon ring to the total number of carbon-carbon bonds is preferably 50% or less, more preferably 40% or less, and particularly preferably 20% or less. The straight-chain constituent units include the formulas [2] and [3].

[0019]

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(The bond composed of a solid line and a broken line between carbon and carbon represents a single bond or a double bond. Each R is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Or a substituent containing any one of a halogen atom, a silicon atom, an oxygen atom, and a nitrogen atom.
It is a symbol meaning two when it is a single bond and one when it is a double bond. )

[0021]

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(The meaning of each symbol is the same as in formula [2].) If the proportion of the straight chain having 3 or more carbon atoms is too small, that is, if the straight chain having 2 carbon atoms is too large, the molded article May have too high rigidity and the modulus of elasticity may be too high.
If the proportion of linear chains of two or more is too large, that is, if the linear chain having two carbon atoms is too small, elastic recovery may not be exhibited.

The cyclic olefin ring-opening polymer of the present invention comprises
M in polystyrene by GPC using THF as a solvent
w is 1,000 to 1,000,000, preferably 5,000 to 800,000, and more preferably 7000
0 to 500,000, particularly preferably 10,000 to 2
00,000. If Mw is too small, mechanical properties may be inferior. Conversely, if Mw is too large, meltability during molding may be poor. Further, the cyclic olefin ring-opening polymer of the present invention hardly contains a crosslinked polymer. Therefore, 1 part of the cyclic olefin ring-opened polymer is dissolved in 9 parts of chloroform, and the insoluble content recovered by filtration through a 10-micron Teflon filter is 0.1% by weight or less, preferably 0.05% by weight. %, More preferably 0.01% by weight or less. If the chloroform-insoluble content is too large, the hydrogenation reaction does not proceed sufficiently, a defect due to an unmelted product occurs when formed into a film or the like, the mechanical strength decreases, and the transparency decreases.

Although the method for producing the above polymer of the present invention is not particularly limited, a preferred production method is a method in which a specific cyclic olefin-based monomer is subjected to ring-opening polymerization and hydrogenated.
Thus, the method for producing the cyclic olefin-based ring-opened polymer of the present invention comprises: a cyclic olefin-based monomer A which forms a straight chain having 2 carbon atoms by a ring-opening reaction; Is subjected to ring-opening copolymerization with the cyclic olefin monomer B which forms a straight chain, and then the double bond is hydrogenated. The number of carbon atoms forming a linear chain by a ring-opening reaction of a cyclic olefin-based monomer is determined by forming only the ring that opens in the carbon atoms constituting the ring that opens during ring-opening polymerization. Is determined by the number of carbon atoms N ₀ . N ₀ is 2
, The straight-chain carbon number is two, and if N ₀ is three or more, the straight-chain carbon number is three or more.

Examples of the cyclic olefin monomer A include a norbornene monomer represented by the following formula [1] and a 3,4-disubstituted cyclobutene represented by the following formula [5].

[0026]

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Wherein R ¹ , R ² , R ³ and R
⁴ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
Or represents a substituent containing a halogen atom, a silicon atom, one atom of oxygen atom and nitrogen atom, R ¹ and R
³ or R ² and R ⁴ may combine with each other to form another ring. n is 0, 1 or 2. )

[0028]

Embedded image (In the formula, Ra and Rb are bonded to each other to form another ring outside the cyclic olefin.) The carbon atoms at the 3- and 4-positions of the 3,4-disubstituted cyclobutene are different rings. And the number of carbon atoms in the straight chain formed by the ring-opening reaction is 2 of the carbon atoms at the 1- and 2-positions.
Individual.

Examples of the cyclic olefin-based monomer B include a monomer represented by the following formula [6].

[0030]

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(Wherein R ⁵ , R ⁶ , R ⁷¹ ,
^{R 72, R 73, R 81} , R 82 and ^{R 8 3} each independently represent a hydrogen atom, a carbon number 1 to 20 hydrocarbon group,
Or a substituent containing any of a halogen atom, a silicon atom, an oxygen atom and a nitrogen atom. m ₁ is 0
10 integer, _{m 2} is an integer of 0 to _{5, (m} 1 + 2m
₂ ) is 0 to 10. Part of (m ₁ + 2m ₂ -1) carbon-carbon bonds also includes those having a double bond.
R ⁷² and R ⁷³ or R ⁸² and R ⁸³ may combine to form a ring, in which case a monocyclic or polycyclic ring is formed. )

The cyclic olefin-based monomer B represented by the formula [6] is ring-opening copolymerized with the norbornene-based monomer of the cyclic olefin-based monomer A to form a carbon as shown in the following formula [7]. A straight chain having a number of 3 or more, preferably 3 to 10 is formed.

[0033]

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Examples of norbornene monomers which are specific examples of the cyclic olefin monomer A include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5
Norbornenes having an unsubstituted or alkyl group such as -cyclopentylnorbornene; norbornenes having an alkenyl group such as 5-ethylidene norbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene and 5-cyclopentenylnorbornene; Norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene,
5-methyl-5-methoxycarbonylnorbornene, 5
-Methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctaneate, norbornene-5,6-
Dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene,
Norbornenes having a polar group containing an oxygen atom, such as 5,5-di (hydroxymethyl) norbornene, 5-hydroxyisopropylnorbornene, 5,6-dicarboxynorbornene, and 5-methoxycarbonyl-6-carboxynorbornene;

5-cyano norbornene, norbornene
Norbornenes having a polar group containing a nitrogen atom such as 5,6-dicarboxylic imide; dicyclopentadiene, tricyclo [4.3.1 ^2,5 . 0] dec-3-ene,
Tricyclo ^{[4.4.1 2,} 5. 0] under-3-ene and the like. In addition, tetracyclo ^{[6.5.1 2,5.} 0 ^1,6 . 0 ^8,13] trideca -3,8,10,12- tetraene (1,4-methano -1,4,4a, also referred 9a- tetrahydrofluorene), tetracyclo ^{[6.6.1 2,5.} 0
^1,6 . 0 ^8,13] tetradeca -3,8,10,1
2-tetraene (1,4-methano-1,4,4a, 5
Norbornenes having an aromatic ring, such as 10,10a-hexahydroanthracene);

Tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8
Unsubstituted or alkyl-containing tetracyclododecenes such as cyclohexyltetracyclododecene and 8-cyclopentyltetracyclododecene; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetra Tetracyclododecenes having an exocyclic double bond, such as cyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, and 8-cyclopentenyltetracyclododecene; 8-phenyltetracyclo Tetracyclododecenes having an aromatic ring such as dodecene;

8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9 Tetracyclododecenes having a substituent containing an oxygen atom, such as dicarboxylic acid and tetracyclododecene-8,9-dicarboxylic anhydride; 8-cyanotetracyclododecene, tetracyclododecene-8,9
Tetracyclododecenes having a substituent containing a nitrogen atom such as dicarboxylic imide; tetracyclododecenes having a substituent containing a halogen atom such as 8-chlorotetracyclododecene; 8-trimethoxysilyltetracyclo Tetracyclododecenes having a substituent containing a silicon atom such as dodecene;

Hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, etc. Heptadecenes; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenyl Hexacycloheptadecenes having an exocyclic double bond such as hexacycloheptadecene; hexacycloheptadecenes having an aromatic ring such as 12-phenylhexacycloheptadecene

12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene-12,1
3-dicarboxylic acid, hexacycloheptadecene-12,
Hexacycloheptadecenes having a substituent containing an oxygen atom such as 13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene-
Hexacycloheptadecenes having a substituent containing a nitrogen atom such as 12,13-dicarboxylic imide; hexacycloheptadecenes having a substituent containing a halogen atom such as 12-chlorohexacycloheptadecene; 12-
Hexacycloheptadecenes having a substituent containing a silicon atom such as trimethoxysilylhexacycloheptadecene.

A straight chain having 3 or more carbon atoms by a ring opening reaction
Specific examples of the cyclic olefin monomer B which forms
Is cyclopropene, cyclobutene, cyclopentene,
Methylcyclopentene, cyclohexene, methylcyclo
Cyclic such as hexene, cycloheptene and cyclooctene
Monoolefin; cyclohexadiene, methylcyclohexene
Xadiene, cyclooctadiene, methylcycloocta
Cyclic diols such as diene and phenylcyclooctadiene
Fin; bicyclo [3.3.0] octene (formula
[8]), tricyclo [5.2.1.0 ^2,6] Big
-3-ene (Formula [9]), bicyclo [4.3.0] nona
And 3,7-diene (formula [10]).
Wear.

[0041]

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[0042]

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[0043]

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According to the production method of the present invention, the cyclic olefin
-Opening Copolymerization of Cyclic A and Cyclic Olefin B
Between the hydrocarbon ring
A straight chain of carbon number is formed. Formed between two rings
The length of the straight chain (the number of carbon atoms) depends on the cyclic olefin monomer A
Length of straight chain and straight chain derived from cyclic olefin monomer B
Determined by the length of Two cyclic olefin monomers
When A undergoes ring-opening polymerization, the number of carbon atoms in the straight chain between the rings is two.
is there. The cyclic olefin monomer B is represented by the above formula [6]
R⁷², R ⁷³Between or R⁸², R⁸³Hydrocarbons between
When not forming an elementary ring, two cyclic olefin-based monomers
Cyclic olefinic monomer between rings of monomer unit derived from isomer A
In the sequence sandwiching r B-derived monomer units, two cyclic
The direction of the monomer unit derived from the olefin monomer A is head
 depending on whether to tail or head to head
The straight-chain carbon number is [2 + r × (3 + m₁+2
m₂)] Or r × (3 + m₁ + 2m₂)
Is [4 + r × (3 + m₁+ 2m₂)] Pieces. Ma
In addition, the cyclic olefin-based monomer B is⁷², R
⁷³Between or R⁸², R⁸³Form a hydrocarbon ring between
The two cyclic olefin monomers B-derived monomers
The number of linear carbon atoms between the unit rings is two cyclic olefins
(3 + m
₁) Pieces or 2 × (3 + m)₁) Pcs
Rings and cyclic olefins of monomer units derived from quinone monomer A
The number of straight-chain carbon atoms between the rings of the monomer unit derived from monomer B is
(3 + m₁) Or two, or
(5 + m₁) Pieces. Where m₁Is 0-10
Integer, m₂Is an integer from 0 to 5, (m₁+ 2m₂) Is 0
And r is an integer of 1 to several hundreds.

The charge ratio of the cyclic olefin monomer A and the cyclic olefin monomer B at the time of conducting the polymerization reaction is determined by the ratio of the straight chain having 3 or more carbon atoms to the total straight chain of the ring-opened polymer to be produced. The proportion must be determined so as to be 5 to 95% by weight, preferably 10 to 90% by weight, more preferably 20 to 80% by weight. The relationship between the charging ratio of both monomers and the ratio of the straight chain having 3 or more carbon atoms in the straight chain can be understood by conducting preliminary experiments. Percentage number of two linear carbon, ^{1 H-NMR} of a simple case obtained polymer
By determining the ratio of both monomer units by analysis or the like, the range of existence can be determined. Also, ¹³ C-NM
By R analysis, the ratio of each of the carbon directly bonded to the ring (both straight chains having two carbon atoms correspond to two) and the carbon not directly bonded to the ring was determined. Can be calculated. The ratio of the straight chain having 3 or more carbon atoms is determined as the remainder of the ratio of the straight chain having 2 carbon atoms.

The metathesis polymerization catalyst for the ring-opening copolymerization of the cyclic olefin monomer A and the cyclic olefin monomer B is a carbene compound containing a transition metal belonging to Groups 4 to 9 of the periodic table. When a carbene compound containing a transition metal belonging to Groups 4 to 9 of the periodic table is used, it is possible to obtain a cyclic olefin-based ring-opened polymer having a very small amount of a crosslinked polymer and, therefore, containing 0.1% by weight or less of a chloroform-insoluble component. It is. The carbene compounds containing a transition metal belonging to Groups 4 to 9 of the periodic table include:
It can be shown by equation [11].

[0047]

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(Wherein M represents a transition metal belonging to Groups 4 to 9 of the periodic table, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, X represents a substituent containing any of a silicon atom, an oxygen atom, a sulfur atom and a nitrogen atom, and X is an arbitrary ligand.
p is 0, 1 or 2. ) As transition metals of Groups 4 to 9 of the periodic table, Ti, Nb, T
a, Mo, W, Re, Ru, Os, Rh, and Ir are preferred, and Mo, W, and Ru are particularly preferred. Preferred examples of the Mo-containing carbene compound or the W-containing carbene compound include at least one imide group that binds to Mo or W, and further include an alkoxy group, an aryloxy group, an alkylamide group, and an arylamide group. Compounds having at least one selected substituent can be mentioned. Specific examples include a compound represented by the following formula [12].

[0049]

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(Wherein, R ¹¹ represents an alkyl group or an aryl group, and X ¹ and X ² independently represent an alkoxy group, an aryloxy group, an alkylamide group, or an arylamide group. X ¹ and X ² good .R ¹² and R ¹³ may be bonded to each other, independently of one another are hydrogen, is 1-20 hydrocarbon group having carbon atoms, or a halogen atom, a silicon atom, an oxygen atom, a sulfur atom and A substituent containing any atom of a nitrogen atom, L is an electron-donating neutral ligand, q is 0, 1, or 2. N is a nitrogen atom, M is Mo or W When R ¹¹ in the formula is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. , For example, methyl group, ethyl group, propyl , Isopropyl group, butyl group, tert- butyl group, or a cyclohexyl group. When R ¹¹ is an aryl group, it preferably has 6 to 20 carbon atoms, for example, a phenyl group or 1 to 3 having a substituent at any of 2, 3, 4, 5, and 6 positions. It is a 5-substituted phenyl group.

X ¹ and X ² are an alkoxy group,
It is an aryloxy group, an alkylamide group or an arylamide group, and X ¹ and X ² may be bonded to each other. The alkoxy group preferably has 1 to 20 carbon atoms and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-
Butoxy group or cyclohexyl group.
The aryloxy group is preferably, for example, a phenoxy group or a 1 to 5 substituted phenoxy group having a substituent at any of the 2, 3, 4, 5, and 6 positions. Examples of the substituents of the substituted phenyl group and the substituted phenoxy group include an alkyl group or a cycloalkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group and a cyclohexyl group; a phenyl group and a naphthyl An aryl group such as a group; an alkyl group or an alkylaryl group such as a trimethylsilyl group and a dimethylphenylsilyl group; a halogen such as fluorine, chlorine, bromine or iodine;
Alkoxy groups such as methoxy, ethoxy and propoxy groups; cyano groups; naphthyl groups and 1-7-substituted naphthyl groups having the same substituent at any of the 2- to 8-positions.

Further, as the alkylamide group or the arylamide group, the alkyl group preferably has 1 to 2 carbon atoms.
0 alkylamide groups or aryl groups have 6 to 6 carbon atoms.
20 arylamide groups, for example, N, N-dimethylamide group, N-methyl (N-tert-butyl)
An amide group, an N-methyl (N-trimethylsilyl) amide group, an N-phenyl-N-methylamide group, an N-phenyl (N-trimethylsilyl) amide group, an N- (2,6-dimethylphenyl) -N-methylamide group, N- (2,6
-Diisopropylphenyl) -N-methylamide group, N
-(2,6-dimethylphenyl) -N- (trimethylsilyl) amide group, N- (2,6-diisopropylphenyl) -N- (trimethylsilyl) amide group and the like.

Further, R ¹² and R ^{13 in the} above formula [12]
Specific examples of hydrogen, alkenyl, alkynyl, alkyl, aryl, carboxyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkoxycarbonyl, alkylthio, alkenylthio, arylthio Group, alkylsulfonyl group, alkylsulfinyl group and the like. Among them, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group is preferable because of high polymerization activity. Further, L is an electron donating neutral ligand. The electron-donating neutral ligand may be any ligand as long as it has a neutral charge when separated from the central metal, and is generally an electron-donating compound having a hetero atom. Specific examples include phosphines, ethers, and amines.
Examples of the phosphines include those having 6 to 20 carbon atoms, such as trimethylphosphine, triisopropylphosphine, tricyclohexylphosphine, and triphenylphosphine.
Trialkylphosphine having 1 to 20 carbon atoms or a triarylphosphine having 6 to 20 carbon atoms in the alkyl group which may contain 2 or more aryl groups. Ethers include diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and the like, and amines include trialkylamines such as trimethylamine and triethylamine, pyridine, lutidine and the like.

Preferred examples of the Ru-containing carbene compound include a neutral ligand having a strong electron donating property, and a carbene compound selected from the group consisting of a halogen atom, an alkoxy group, an aryloxy group, an alkylamide group and an arylamide group. Compounds having two selected substituents can be mentioned. Specifically, the following formula [13]

[0055]

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(Wherein R¹⁴And R^FifteenAre independent of each other
And a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or
Represents a halogen atom, silicon atom, oxygen atom, sulfur atom,
And a substituent containing any one of a nitrogen atom and a nitrogen atom. X³And
And X⁴Is independent of any anionic ligands
Show. L¹And L²Are independent of each other
Shows a donating neutral ligand. R¹⁴, R^Fifteen, X³,
X⁴, L¹And L² Multiple permutations selected from
Groups combine with each other to form a multidentate chelating ligand
Is also good. Here, the anionic ligand is separated from the central metal
Sometimes any ligand with a negative charge
Good. X³, X⁴Are specific examples of F, Br, C
a halogen atom such as l or I; hydrogen, acetylacetate
, Diketonate group, cyclopentadienyl group, allyl
Group, alkenyl group, alkyl group, aryl group, alkoxy
Group, aryloxy group, alkoxycarbonyl group,
Reel carboxyl group, carboxyl group, alkyl or
Arylsulfonate group, alkylthio group, alkenyl
Luthio, arylthio, alkylsulfonyl or
An alkylsulfinyl group can be mentioned. in
Also halogen atom, cyclopentadienyl group, allyl
Group, alkyl group or aryl group is excellent in polymerization activity
I have.

Specific examples of L ¹ and L ² in the above formula [13] include oxygen, water, carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, and phosphinite. , Phosphites, stibines, sulfoxides, thioethers, amides, aromatics, cyclic diolefins, olefins, isocyanides, thiocyanates, heterocyclic carbene compounds and the like. Among them, pyridines,
Phosphines, aromatics, cyclic diolefins, and heterocyclic carbene compounds are preferred because of their high polymerization activity. Further, specific examples of R ¹⁴ and R ¹⁵ in the above formula [13] include hydrogen, alkenyl group, alkynyl group, alkyl group, aryl group, carboxyl group, alkoxy group,
Examples include an alkenyloxy group, an alkynyloxy group, an aryloxy group, an alkoxycarbonyl group, an alkylthio group, an alkenylthio group, an arylthio group, an alkylsulfonyl group, and an alkylsulfinyl group. Among them, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group is preferable because of high polymerization activity.

In the present invention, the polymerization reaction may be carried out in a solvent or without a solvent, but it is preferable to carry out the polymerization in a solvent because the hydrogenation reaction can be easily carried out after the polymerization reaction.
The polymerization solvent is not particularly limited as long as it dissolves the polymer and does not inhibit the polymerization reaction. Examples of solvents that can be used for the polymerization include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, and tricyclohexane. Alicyclic hydrocarbons such as cyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; diethyl ether and tetrahydrofuran Ethers; examples thereof include halogen-containing hydrocarbons such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene. Among them, industrially used aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons or ethers are preferable, which are inert to polymerization or hydrogenation reaction, and have excellent polymer solubility. From the viewpoint of the above, an alicyclic hydrocarbon is most preferable.

When the polymerization is carried out in a solvent, the concentration of the monomers (cyclic olefin monomer A and cyclic olefin monomer B) is preferably 1 to 60% by weight, and more preferably 2 to 55% by weight. Is more preferable, and 5 to 50% by weight is particularly preferable.
If the concentration of the monomer is too low, the productivity becomes worse, and conversely,
If the concentration is excessively high, the viscosity of the reaction solution after the polymerization is too high, so that the subsequent hydrogenation reaction may be difficult. The molar ratio of the polymerization catalyst used to the cyclic olefin monomer is preferably from 1: 100 to 1: 2,000,000, more preferably from 1: 500 to 1: 1,000,000. And particularly preferably 1: 1,000 to 1: 500,00.
0. If the amount of the catalyst is too large, it is difficult to remove the catalyst after the polymerization reaction, and if the amount is too small, sufficient polymerization activity cannot be obtained. The polymerization reaction is started by mixing the above monomer and a polymerization catalyst. The polymerization temperature is not particularly limited, but is usually -30C to 200C, preferably 0C to 180C. The polymerization time is usually from 1 minute to 100 hours.

In the present invention, in order to adjust the molecular weight of the cyclic olefin ring-opening polymer, a molecular weight modifier can be added during the polymerization reaction. Specific examples of the molecular weight modifier include α-olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether and the like. Ethers; halogen-containing vinyl compounds such as allyl chloride; allyl acetate, allyl alcohol,
Oxygen-containing vinyl compounds such as glycidyl methacrylate and methyl acrylate; and nitrogen-containing vinyl compounds such as acrylamide. The amount of the molecular weight modifier used is 0.1 to 1 with respect to the cyclic olefin monomer.
It can be arbitrarily selected between 0 mol%. further,
At the end of the polymerization, the above-mentioned vinyl compound may be added to release the catalyst from the polymer molecular chain terminals. In the present invention, by performing ring-opening copolymerization of the cyclic olefin-based monomer A and the cyclic olefin-based monomer B using the above-described catalyst, a linear polymer formation reaction is exclusively performed by metathesis ring-opening polymerization. Therefore, a three-dimensional crosslinked polymer is hardly formed. Therefore, the polymer has substantially no gel component insoluble in the good solvent. Considering the subsequent hydrogenation reaction, the molecular weight of the obtained polymer is Mw of 1,0 in terms of polystyrene by GPC using THF as an eluent.
00 to 1,000,000, preferably 5,000 to 8
00,000, more preferably 7,000 to 50.
It is 0000. In the present invention, when a ruthenium-containing carbene compound is used as a polymerization catalyst, the remaining ruthenium-containing carbene compound can be used as a hydrogenation catalyst, and there is no need to newly add a hydrogenation catalyst. Further, the polymerization reaction solvent can be used as it is as the hydrogenation reaction solvent.

The cyclic olefin ring-opening polymer of the present invention comprises
By hydrogenation after the polymerization reaction, the ratio of double bonds in the straight chain can be reduced to 50% or less, preferably 40%, more preferably 20%. The hydrogenation catalyst used for hydrogenation is not particularly limited as long as it is generally used for the hydrogenation reaction of olefins and aromatic compounds. Specific examples thereof include (1) palladium, platinum, nickel, and rhodium. Or a supported metal catalyst in which a transition metal such as ruthenium is supported on a carrier such as carbon, alumina, silica or diatomaceous earth; (2) an organic transition metal compound such as titanium, cobalt or nickel, and lithium, magnesium or aluminum Or a homogeneous catalyst comprising an organometallic compound such as tin; and (3) a metal complex catalyst such as rhodium and ruthenium.

As specific examples of the supported metal catalyst (1), in the form of “transition metal / support”, nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, Palladium / diatomaceous earth, palladium / alumina, platinum / silica, platinum / alumina, rhodium / silica, rhodium /
Catalysts such as alumina, ruthenium / silica, ruthenium / alumina and the like can be mentioned. As the homogeneous catalyst (2), “organic transition metal compound /
In the form of "organic metal compound", cobalt acetate /
Triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / s
ec-butyllithium, a combination of tetrabutoxytitanate / dimethylmagnesium and the like. Examples of the metal complex catalyst (3) include dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium, dihydridotetra (triphenylphosphine) ruthenium,
Dihydrido (acetonitrile) tris (triphenylphosphine) ruthenium; dihydrido (tetrahydrofuran) tris (triphenylphosphine) ruthenium;

The hydrogenation reaction is usually carried out in an inert organic solvent. The inert organic solvent may be any as long as it is excellent in the solubility of the produced hydrogenated cyclic olefin ring-opening polymer. Examples of such an organic solvent include: aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and n-hexane; alicyclic hydrocarbons such as cyclohexane and decalin; tetrahydrofuran and ethylene glycol dimethyl ether. Ethers and the like. When the solvent used for the hydrogenation reaction is the same as the solvent used for the polymerization reaction, the hydrogenation reaction can be advantageously performed by directly adding a hydrogenation catalyst to the polymer solution after the polymerization reaction.

The optimum conditions for the hydrogenation reaction vary depending on the type of hydrogenation catalyst used, but the hydrogenation temperature is usually -2.
0 ° C to 250 ° C, preferably -10 to 220 ° C, more preferably 0 to 200 ° C, and the hydrogen pressure is usually 0.0
1 to 10 MPa, preferably 0.05 to 7.5 MPa,
More preferably, it is 0.10 to 5 MPa. If the temperature of the hydrogenation reaction is too low, the reaction rate may be reduced,
Conversely, if the temperature is too high, side reactions may occur.
On the other hand, if the hydrogen pressure is too low, the hydrogenation rate may be reduced. Conversely, if the hydrogen pressure is too high, side reactions may easily occur. 0.1-
After 10 hours, the proportion of carbon-carbon double bonds in the linear chain of the cyclic olefin ring-opened polymer can be reduced to 50% or less, preferably 40% or less, and more preferably 20% or less. When the hydrocarbon ring of the polymer has a carbon-carbon double bond, the ratio of the double bond under the above hydrogenation reaction conditions is 50% or less, preferably 60% or less, more preferably 50% or less. And particularly preferably 30% or less.

When the supported metal catalyst of the above (1) is used, the hydrogenation catalyst after the completion of the hydrogenation reaction can be removed by filtering the reaction solution after the hydrogenation reaction with a filter. As a method for removing the catalyst after the reaction using the homogeneous catalyst (2) or the metal complex catalyst such as rhodium or ruthenium (3), an adsorbent is added to the reaction solution to be adsorbed and separated. A method or a method in which an organic acid and / or an inorganic acid and water or a lower alcohol are added to the reaction solution, followed by washing and removal can be employed.

The ring-opening olefin polymer of the present invention is
Antioxidants, ultraviolet absorbers, weather stabilizers, anti-opacity agents,
It is subjected to molding as a resin composition prepared by appropriately blending various blending agents such as an antistatic agent and an organic or inorganic filler.

Examples of the antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like. Among them, a phenol-based antioxidant, particularly an alkyl-substituted phenol-based antioxidant is preferable. . The addition of these antioxidants is particularly important as a compounding agent because it can prevent coloring and strength reduction of a molded product due to oxidative deterioration during molding without reducing transparency and low water absorption. Examples of the phenolic antioxidant include octadecyl-3- (3,5-di-t-butyl-4).
-Hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakismethylene-3- (3 ′, 5′-di-t-) Butyl-4′-hydroxyphenylpropionate) methane [ie,
Pentaerythrimethyl-tetrakis 3- (3,5-di-
t-butyl-4-hydroxyphenylpropionate)], triethylene glycol bis {3- (3-t-
Alkyl-substituted phenolic compounds such as butyl-4-hydroxy-5-methylphenyl) propionate};
-Tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-tert-amyl-6- {1- (3,5-
Acrylate compounds such as di-t-amyl-2-hydroxyphenyl) ethyl} phenyl acrylate described in JP-A-63-179953 and JP-A-1-168463; 6- (4-hydroxy-3, 5-di-t-butylanilino) -2,4-bisoctylthio-
1,3,5-triazine, 4-bisoctylthio-1,
3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino)-
Examples thereof include triazine group-containing phenol compounds such as 1,3,5-triazine.

As the phosphorus-based antioxidant, a general resin
There is no special limitation as long as it is commonly used in the industry,
For example, triphenyl phosphite, diphenyl isodecyl
Phosphite, phenyldiisodecyl phosphite,
Lis (nonylphenyl) phosphite, tris (dinoni
Ruphenyl) phosphite, tris (2,4-di-t-
Butylphenyl) phosphite, 10- (3,5-di-
t-butyl-4-hydroxybenzyl) -9,10-di
Hydro-9-oxa-10-phosphaphenanthrene-
Monophosphite compounds such as 10-oxide;
4,4'-butylidene-bis (3-methyl-6-t-butyl
Tylphenyl-di-tridecyl phosphite), 4,
4 'isopropylidene-bis [phenyl-di-alkyl
(C₁₂~ C _Fifteen) Phosphite]
G-based compounds. As a sulfur-based antioxidant
For example, dilauryl-3,3-thiodipropione
, Dimyristyl 3,3'-thiodipropionone
G, distearyl-3,3-thiodipropionate, la
Urylstearyl-3,3-thiodipropionate,
Antaerythritol-tetrakis-β-lauryl-thio
-Propionate, 3,9-bis (2-dodecylthioe
Tyl) -2,4,8,10-tetraoxaspiro [5
5] undecane and the like. These antioxidants
Can be used alone or in combination of two or more
Can be used, and the amount thereof is appropriately selected.
To 100 parts by weight of olefin ring-opened polymer
0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight
It is.

Examples of the ultraviolet absorber and weather stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate and bis (2,2,6,6-tetramethyl-
4-piperidyl) sebacate, bis (1,2,2,6)
6-pentamethyl-4-piperidyl) -2- (3,5-
Di-tert-butyl-4-hydroxybenzyl) -2-n-
Butyl malonate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy]-
1- {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} -2,
Hindered amine compounds such as 2,6,6-tetramethylpiperidine; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-t-butyl-
2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2)
Benzotriazole compounds such as -hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2,4-di-t-butylphenyl-3 , 5-
Bezoate compounds such as di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate are exemplified.
These UV absorbers and weather stabilizers can be used alone or in combination of two or more. The amount of the ultraviolet absorber and the weather stabilizer is usually 0.001 to 100 parts by weight of the cyclic olefin ring-opening polymer.
To 5 parts by weight, preferably 0.01 to 2 parts by weight.

Further, by blending a soft polymer or an alcoholic compound with the ring-opening olefin ring-opening polymer of the present invention, various properties such as transparency, low water absorption and mechanical strength are not reduced. In addition, it is possible to obtain a molded article that is hardly clouded even when used in a high-temperature, high-humidity environment for a long time. Also, if these are blended in a large amount, the impact resistance can be improved. The soft polymer is a polymer having a Tg of usually 30 ° C. or lower, and when a plurality of Tg exist, at least the lowest Tg may be 30 ° C. or lower. Specific examples of these soft polymers include, for example, liquid polyethylene, polypropylene, poly-1-butene, ethylene.
α-olefin copolymer, propylene / α-olefin copolymer, ethylene / propylene / diene copolymer (E
PDM), olefin-based soft polymers such as ethylene-propylene-styrene copolymer; isobutylene-based soft polymers such as polyisobutylene, isobutylene / isoprene rubber, isobutylene / styrene copolymer; polybutadiene, polyisoprene, butadiene / styrene random Copolymer, isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, butadiene / styrene / block copolymer, styrene / butadiene / styrene / block copolymer, isoprene / Diene-based soft polymers such as styrene / block copolymers and styrene / isoprene / styrene / block copolymers;

Silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane and dihydroxypolysiloxane; polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate / styrene copolymer, etc. Soft polymers consisting of α, β-unsaturated acids: polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl acetate.
Soft polymers composed of unsaturated alcohols such as styrene copolymers and amines or their acyl derivatives or acetal; Epoxy soft polymers such as polyethylene oxide, polypropylene oxide, epichlorohydrin rubber; vinylidene fluoride rubber, tetrafluoride Fluorine-based soft polymers such as ethylene-propylene rubber; and other soft polymers such as natural rubber, polypeptide, protein, polyester-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer. These soft polymers may have a crosslinked structure, or may have a functional group introduced by a modification reaction. Among the above soft polymers, diene-based soft polymers are preferred, and hydrides obtained by hydrogenating carbon-carbon unsaturated bonds of the soft polymer are particularly excellent in rubber elasticity, mechanical strength, flexibility and dispersibility.

The alcoholic compound is a compound having at least one non-phenolic hydroxyl group in the molecule, and preferably has at least one hydroxyl group and at least one ether bond or ester bond. Specific examples of such compounds include, for example, dihydric or higher polyhydric alcohols, more preferably trihydric or higher polyhydric alcohols,
More preferably, an alcoholic ether compound or an alcoholic ester compound in which one of the hydroxyl groups of a polyhydric alcohol having 3 to 8 hydroxyl groups is etherified or esterified is used. Examples of the dihydric or higher polyhydric alcohol include polyethylene glycol, glycerol,
Trimethylolpropane, pentaerythritol, diglycerol, triglycerol, dipentaerythritol, 1,6,7-trihydroxy-2,2-di (hydroxymethyl) -4-oxoheptane, sorbitol,
-Methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxoheptane, 1,5,6-trihydroxy-3-oxohexanepentaerythritol, tris (2-hydroxyethyl) isocyanurate and the like. However, a polyhydric alcohol having 3 or more valences, and more preferably a polyhydric alcohol having 3 to 8 hydroxyl groups is preferred. When obtaining an alcoholic ester compound,
Glycerol, diglycerol, triglycerol and the like, from which alcoholic ester compounds containing α, β-diol can be synthesized, are preferred.

Examples of such alcoholic compounds include glycerin monostearate, glycerin monolaurate, glycerin monobehenate, diglycerin monostearate, glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, and pentaerythritol Polyhydric alcoholic esters such as monolaurate, pentaerythritol monobeherate, pentaerythritol distearate, pentaerythritol dilaurate, pentaerythritol tristearate, dipentaerythritol distearate; 3- (octyloxy) -1, 2-propanediol, 3- (decyloxy) -1,2-propanediol, 3- (lauryloxy) -1,2-propanediol, 3- (4-no L-phenyloxy) -1,2-propanediol, 1,6-dihydroxy-2,2-di (hydroxymethyl) -7- (4-nonylphenyloxy) -4-oxoheptane, p-nonylphenyl ether and Alcoholic ether compound obtained by reaction of formaldehyde condensate with glycidol, alcoholic ether compound obtained by reaction of p-octylphenyl ether and formaldehyde with glycidol, condensate of p-octylphenyl ether and dicyclopentadiene And glycidol with alcoholic ether compounds. These polyhydric alcoholic compounds are used alone or in combination of two or more. Although the molecular weight of these polyhydric alcoholic compounds is not particularly limited, it is usually 500 to 200.
Those having 0, preferably 800 to 1500 have little decrease in transparency. The amount of the soft polymer or alcoholic compound to be added is usually 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, particularly preferably 100 parts by weight of the cyclic olefin-based ring-opening polymer. It is 0.05 to 2 parts by weight.

Examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol; sodium alkyl sulfonate and phosphonium alkyl sulfonate; fatty acid esters such as glyceryl stearate; hydroxyamine compounds; alkyl phosphate amines; Polyoxyethylene alkylamine; alkyldiethanolamide; polyoxyethylene-polyoxypropylene block copolymer; organoboron-based surfactant; cationic surfactant; amorphous carbon, tin oxide powder, antimony-containing tin oxide powder, and the like. can do. The amount of the antistatic agent is usually in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the cyclic olefin-based ring-opening polymer.

As the organic filler, ordinary organic polymer particles or crosslinked organic polymer particles can be used, for example, polyolefins such as polyethylene and polypropylene; halogen-containing vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; Polymers derived from α, β-unsaturated acids such as polyarylate and polymethacrylate; polymers derived from unsaturated alcohols such as polyvinyl alcohol and polyvinyl acetate; derived from polyethylene oxide or bisglycidyl ether Polymers; aromatic condensation polymers such as polyphenylene oxide, polycarbonate, and polysulfone; polyurethanes; polyamides; polyesters; aldehyde / phenolic resins; . As the inorganic filler, for example, lithium fluoride, borax (sodium borate hydrate)
Group 2 element compounds such as magnesium carbonate, magnesium phosphate, calcium carbonate, strontium titanate, barium carbonate; Group 4 element compounds such as titanium dioxide (titania) and titanium monoxide; molybdenum dioxide, trioxide Group 6 element compounds of molybdenum; Group 7 element compounds such as manganese chloride and manganese acetate; Group 8 to 10 element compounds such as cobalt chloride and cobalt acetate; Group 11 element compounds such as cuprous iodide; zinc oxide and zinc acetate Group 13 element compounds such as aluminum oxide (alumina), aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite); silicon oxide (silica, silica gel), graphite, carbon, graphite, glass Group 14 element compounds such as;
Examples include particles of natural minerals such as kernalite, kainite, mica (mica, kinmo), and virose ore.

The resin composition of the present invention may optionally contain
As other compounding agents, light stabilizers, near-infrared absorbing agents, coloring agents such as dyes and pigments, lubricants, plasticizers, antiblocking agents, fluorescent brighteners, deodorants, etc. can be compounded, and these can be used alone. , Or a mixture of two or more kinds, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.

The molded article of the cyclic olefin ring-opened polymer of the present invention has not only excellent transparency and heat resistance but also an appropriate elastic modulus and a high elastic recovery rate. Tensile modulus is usually 10 kgf / cm ^{2 to} 2,000 k
gf / cm ² , preferably 50 kgf / cm ² to 1,
500 kgf / cm ² , and the elastic recovery rate is usually
60% or more, preferably 70% or more, more preferably 8% or more
It is as high as 0% or more. By having these properties, the cyclic olefin-based ring-opened polymer of the present invention can be produced by various molding methods such as extrusion molding, inflation molding, vacuum molding, cast molding, injection molding, and press molding. Is molded. The cyclic olefin-based ring-opening polymer of the present invention includes packaging materials such as tapes and buffer sheets; consumer materials such as trays, cups, stationery, rearranging boxes, closet storage boxes; transparent cases for storing goods; food wrap films, shrink films. , Sealant film, pallet stretch film, agricultural film, and other films; vibration damping materials; pipes, tubes, foam tubes;
It can be used for automobile parts such as side moldings, mudguards, bumpers, etc .; lighting parts, home electric parts parts; toys; civil engineering materials such as water-blocking sheets and drain materials; building materials; furniture materials; Among these uses, it is particularly suitable for tapes, sheets, films, tubes, etc., and is a flexible and tough olefin which could not be realized with conventional olefin polymers, α-olefin / cycloolefin addition copolymers, etc. A resin-based molded article can be provided.

[0078]

The present invention will be described more specifically below with reference to examples and comparative examples. Parts and% are based on weight unless otherwise specified. The measuring method was as follows. (1) Cyclic olefin ring-opening polymer (including hydride)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of were measured in terms of polystyrene by GPC using THF as an eluent. (2) The hydrogenation rate was measured by a ¹ H-NMR spectrum. (3) The glass transition temperature (Tg) and the melting point (Tm) were measured by a differential scanning calorimeter (DSC). (4) The tensile modulus can be measured by JIS K using an autograph.
Measured according to 7113. (5) The elastic recovery rate was determined by preparing a sample having a thickness of 0.5 mm formed by a casting method and formed into a strip having a width of 6 mm and a length of 60 mm, and using an autograph, a sample of 50 mm (L0) between clamps. 150 per minute
% And held for 5 minutes, returned to the original 50 mm, and measured the sample length (L1) between the clamps after one minute,
It was determined by the following equation. Elastic recovery rate = [1-{(L1-L0) / L0}] × 10
0

Example 1 In a glass reactor equipped with a stirrer,
110 parts of cyclohexane, dicyclopentadiene (DC
PD), 12 parts of cyclopentene (CPE), and 0.3 part of 1-hexene as a molecular weight modifier were charged. Next, bis (tricyclohexylphosphine) benzylidine ruthenium dichloride dissolved in 10 parts of cyclohexane was added.
After adding 029 parts and polymerizing at 60 ° C. for 3 hours, the polymerization reaction solution was poured into a large amount of isopropanol to completely precipitate the polymer, and the polymer was separated by filtration, washed, and dried under reduced pressure at room temperature for 40 hours. The yield of the obtained cyclic olefin ring-opened polymer is 1
5.5 parts, Mn is 16,900, Mw is 30,900
The DCPD / CPE constituent monomer ratio in the copolymer measured by ¹ H-NMR spectrum was 56/44.
(Mol / mol). When 1 part of the obtained ring-opened copolymer was dissolved in 9 parts of chloroform, the polymer was completely dissolved. The insoluble content recovered by filtration through a 10 micron Teflon filter was 0.01% or less.

Subsequently, 10 parts of the above ring-opening copolymer and 90 parts of cyclohexane were charged into an autoclave equipped with a stirrer, and 1.0 part of a nickel / alumina-supported hydrogenation catalyst was added. The hydrogen pressure was 4.0 MPa, and the temperature was 160 ° C. For 5 hours. After completion of the reaction, the reaction solution was cooled, the reaction solution was filtered with a filter, and the hydrogenation catalyst was removed to obtain a colorless and transparent filtrate. The filtrate was poured into a large amount of isopropanol to completely precipitate the polymer. The polymer was separated by filtration, washed, and dried under reduced pressure at room temperature for 40 hours. The yield of the obtained hydrogenated cyclic olefin-based ring-opening polymer was 9.8 parts, and Mn was 17,8.
00, Mw 31,100, hydrogenation rate is 99.4%,
The ratio of the number of double bonds in the straight chain was 0.1%.
As a result of DSC measurement, Tg was 5.5 ° C. and Tm was not observed. When 1 part of the hydride of the ring-opening copolymer was dissolved in 9 parts of chloroform, the polymer was completely dissolved, and the insoluble content recovered by filtration through a 10 μm Teflon filter was 0.01% or less. there were. After dissolving 10 parts of the obtained hydride of ring-opening polymer in 15 parts of carbon tetrachloride, it was opened on a glass plate to prepare a cast film having a thickness of 0.5 mm. The obtained film was colorless and transparent.
The tensile modulus of this film is 320 kgf / cm ² ,
The elastic recovery was 93%, and it was elastomeric. When the obtained hydrogenated cyclic olefin-based ring-opened polymer is described collectively for each constituent monomer unit, almost all of the double bonds can be regarded as hydrogenated, and thus the following formula [14] is obtained. .

[0081]

Embedded image

In the formula [14], the main chain of the polymer comprises a hydrocarbon ring having 5 carbon atoms (provided that a 5-membered ring is attached to the outside of the ring) and a straight chain having 2 or more carbon atoms. . When a large number of CPEs are bonded in blocks, the number of carbon atoms in the straight chain increases to several tens or several hundreds. The total number of straight-chain carbon atoms per mole of the polymer structural unit is 3.32 from the calculation of the following formula. 2 × 0.56 + 5 × 0.44 = 3.32 In addition, looking at the weight ratio of the straight chain having two carbon atoms in the straight chain, the maximum is the case where all DCPDs are connected by blocks. Is 33.7% by weight from the calculation of the following equation. (2 × 0.56) /3.32=0.337 When the ratio of the straight chain having two carbon atoms is the minimum, CP
Residual D when E is alternately copolymerized with equimolar DCPD
Since it is the ratio of the straight chain in the CPD block, 12 mol% of the difference between 56 mol% and 44 mol% has two carbon atoms, and the weight ratio is 7.2 wt% from the calculation of the following formula. (2 × 0.12) /3.32=0.072 The actual weight ratio of the straight chain having two carbon atoms is 7.2 to 33.
The proportion of linear chains having 3 or more carbon atoms is between 66.3 and 92.8% by weight.

[Comparative Example 1] The procedure of Example 1 was repeated, except that 30 parts of DCPD was added and ring-opening polymerization was carried out without adding CPE. The yield of the obtained cyclic olefin ring-opened polymer was 29 parts, Mn was 12,400, and M
w was 28,200. The chloroform-insoluble content was 0.01% or less. Further, the yield of the hydrogenated cyclic olefin ring-opened polymer was 28 parts, and Mn was 1 part.
8,100, Mw was 42,700, and the ratio of double bonds in the linear portion was 0.1%. Tg was 92 ° C. and Tm was not observed. Chloroform insoluble content is 0.01%
It was below. The cast film having a thickness of 0.5 mm is colorless and transparent, and has a tensile modulus of 2100 kgf / cm ² .
Since the sample was cut during stretching, the elastic recovery could not be measured. The main chain of the polymer has a five-membered ring and two carbon atoms.
It has a structure in which two straight chains are alternately arranged. Therefore, all of the straight chains had 2 carbon atoms, and the molded article had an excessively large elastic modulus and a small elastic recovery.

[Second Embodiment] In the first embodiment, the DCPD
Example 1 was repeated except that 12 parts of 8-ethyltetracyclododecene (hereinafter referred to as ETCD) was used instead of 12 parts. The yield of the obtained cyclic olefin ring-opened polymer was 18 parts, Mn was 14,100, and Mw was 30,4.
00. Constituent monomer ratio in the copolymer ETCD /
The CPE was 45/55 (mol / mol). Also,
The chloroform-insoluble content was 0.01% or less. The yield of the hydrogenated cyclic olefin ring-opened polymer was 18 parts, Mn was 16,600, and Mw was 33,200.
The ratio of linear double bonds was 0.05%. T
g was 24.5 ° C., and no Tm was observed. The chloroform-insoluble content was 0.01% or less. 0.5m thick
m cast film is colorless and transparent and has a tensile modulus of 41.
It was 0 kgf / cm ² and the elastic recovery rate was 85%. The actual weight ratio of the straight chain having 3 or more carbon atoms is determined in the same manner as in Example 1 and is between 25 and 87% by weight.

Comparative Example 2 Polymerization was conducted in the same manner as in Example 1 except that CPE was not added and 30 parts of ETCD was used instead of DCPD. The yield of the obtained cyclic olefin-based ring-opened polymer was 28.5 parts, Mn was 32,200, and Mw was 68,100. When 1 part of the obtained cyclic olefin-based ring-opening polymer was dissolved in 9 parts of chloroform, the polymer was completely dissolved. The insoluble content recovered by filtration through a 10 micron Teflon filter was 0.0%.
It was less than 1%. Subsequently, a hydrogenated cyclic olefin-based ring-opened polymer was obtained in the same manner as in Example 1. The yield is 9.8 parts, Mn is 33,200, Mw is 68,800.
And the hydrogenation rate was 99.2%. Tg is 14
At 5.5 ° C., no Tm was observed. After dissolving 10 parts of the obtained hydrogenated ring-opening polymer in 15 parts of carbon tetrachloride, it was opened on a glass plate to prepare a cast film having a thickness of 0.5 mm. The obtained film was colorless and transparent.
Further, since all the straight chains in the main chain of the polymer had 2 carbon atoms, the tensile modulus was 21,000 kgf / cm ² and the rigidity was extremely large, and the elastic recovery could not be measured.

[0086]

Industrial Applicability According to the present invention, there is provided a cyclic olefin-based ring-opened polymer having a large elastic recovery property, an appropriate elastic modulus, and excellent transparency and heat resistance, and a method for producing the same.

Claims (3)

[Claims] 1. A polymer in which a straight chain having 2 or more carbon atoms and a hydrocarbon ring are alternately arranged, wherein the ratio of a straight chain having 3 or more carbon atoms to the total straight chain is 5 to 95.
The ratio of the number of double bonds to the total number of carbon-carbon bonds in the linear chain is 50% or less, and the weight average molecular weight in terms of polystyrene by gel permeation chromatography is 1,000 to 1,000.
A cyclic olefin-based ring-opened polymer having a content of chloroform of 0.1% by weight or less. 2. A cyclic olefin monomer forming a straight chain having 2 carbon atoms by a ring opening reaction and a cyclic olefin monomer forming a straight chain having 3 or more carbon atoms by a ring opening reaction. Ring-opening polymerization using a carbene compound containing a transition metal belonging to Groups 4 to 9 of the periodic table to obtain a polymer in which linear chains having 2 or more carbon atoms and hydrocarbon rings are alternately arranged; Of the carbon-carbon double bond in the straight chain to make the ratio of the number of double bonds to the total number of carbon-carbon bonds in the straight chain 50
% Of the ring-opened cyclic olefin polymer. 3. A cyclic olefin-based ring-opening polymer composition comprising the cyclic olefin-based ring-opening polymer according to claim 1 and an antioxidant.