JPH06228380A - Cycloolefin polymer composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. having improved impact strength, transparency, and heat resistance by compounding two specific cycloolefin random copolymers. CONSTITUTION:The compsn. is prepd. by compounding 8-40wt.% cycloolefin polymer which is a random copolymer obtd. by copolymerizing a 2C or higher alpha-olefin, a cycloolefin of formula I or II, and a diene compd. if necessary or is a ring-opening polymer of the cycloolefin or a hydrogenation product thereof and has an intrinsic viscosity (eta, 135 deg.C, in decalin) of 0.5-5.0dl/g, a glass transition point (Tg, DSC) lower than 150 deg.C, a content of cycloolefin units of 3mol% or higher, and a refractive index (D, 25 deg.C) of 1.500-1.650 with 92-60wt.% cycloolefin polymer which is the cycloolefin random copolymer, the ring-opening polymer, or the hydrogenation product and has an eta of 0.1-5.0dl/g, a Tg of 70 deg.C or higher, and an etaD of 1.500-1.650. The two kinds of cycloolefin polymer are selected so that the difference (DELTAetaD) in refractive index (etaD) between them is 0.015 or lower.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cyclic olefin polymer composition, and more particularly to a cyclic olefin polymer composition which is excellent in impact resistance, transparency and heat resistance, and has a good balance thereof. .

[0002]

TECHNICAL BACKGROUND OF THE INVENTION The present applicant has previously found that a cyclic olefin random copolymer obtained by copolymerizing ethylene and a cyclic olefin such as tetracyclododecene is excellent in transparency and heat resistance. Resistance, heat aging resistance, chemical resistance,
It has been found that it is a synthetic resin having well-balanced solvent resistance, dielectric properties, and rigidity, and exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers, and has already been disclosed in JP-A-60-168708. JP, JP-A-61-98780, JP-A-61-11591
No. 2, JP 61-115916, and JP 6
It is proposed in JP-A No. 1-120816 and JP-A No. 62-252407. The cyclic olefin random copolymers described in these publications are also known to exhibit excellent performance in the field of structural materials.

However, although these cyclic olefin-based copolymers have excellent heat resistance and rigidity, there is room for improvement in impact resistance, and the transparency possessed by these cyclic olefin-based copolymers is maintained. At the same time, further improvement in impact resistance is required.

Further, the applicant of the present invention has found that a specific softening temperature (TM
A composition comprising a cyclic olefin-based random copolymer having A) and a specific α-olefin-based elastic copolymer,
It has been found that a resin having improved impact resistance can be obtained without impairing excellent properties such as heat resistance, heat aging resistance, and chemical resistance, and it has already been proposed in JP-A-1-163241.

Further, the present applicant has proposed, as a cycloolefin polymer composition having improved impact resistance, a specific cyclic olefin random copolymer and a specific soft copolymer as an organic peroxide. A cyclic olefin-based copolymer composition comprising a product obtained by the reaction in the presence of the above has been already proposed in JP-A-2-167318.

However, the cycloolefin polymer compositions proposed in JP-A-1-163241 and JP-A-2-167318 have improved impact resistance, but are not sufficiently transparent. No, there was room for improvement.

Therefore, the inventors of the present invention have a specific glass transition temperature and a specific refractive index and a specific refractive index difference.
A cyclic olefin polymer composition composed of various types of cyclic olefin polymers, and further, this composition is reacted with a radical by using an organic peroxide and optionally adding a radically polymerizable polyfunctional monomer. The inventors have found that the cyclic olefin polymer composition thus obtained has an excellent balance of impact resistance, transparency and heat resistance, and have completed the present invention.

[0008]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a cyclic olefin polymer composition which is excellent in impact resistance, transparency and heat resistance, and is also excellent in the balance thereof.

[0009]

SUMMARY OF THE INVENTION Cyclic olefin polymer assembly according to the present invention
The product is [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
A cyclic olefin random copolymer obtained by [A-2] represented by the following formula [I] or [II],
Both are ring-opening polymers of one kind of cyclic olefin [A-3] represented by the following formula [I] or [II],
Both consist of hydrogenated products of ring-opening polymers of one type of cyclic olefin.
A cyclic olefin polymer selected from the group
Intrinsic viscosity [η] in decalin at 35 ° C is 0.5 to 5.0
dl / g, glass transition temperature measured by DSC
(Tg) is less than 15 ° C and derived from cyclic olefin
The content of constituent units is 3 mol% or more, and at 25 ℃
Measured refractive index n _D(A) is 1.500 to 1.650
A cyclic olefin polymer [A], [B-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
A cyclic olefin random copolymer obtained by [B-2] represented by the following formula [I] or [II],
Both are ring-opening polymers of one kind of cyclic olefin [B-3] represented by the following formula [I] or [II]
Is it a hydrogenated product of a ring-opening polymer of at least one cyclic olefin?
It is a cyclic olefin polymer selected from the group consisting of
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.1
~ 5.0 dl / g, glass transition measured by DSC
Transfer temperature (Tg) was 70 ° C or higher, measured at 25 ° C
Refractive index n_D(B) is a ring with 1.500 to 1.650
Cyclic olefin-based polymer composed of reffin-based polymer [B]
Refractive index n of polymer [A]_D(A) and cyclic olefin type
Refractive index n of polymer [B]_DDifference from (B) Δn_D= | N
_D(A) -n_D(B) | is 0.015 or less, and [A]
/ [B] (weight ratio) is 8/92 to 40/60
Is characterized by.

[0010]

[Chemical 13]

(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer, q is 0 or 1, and R
^{1 to} R ¹⁸ and R ^a and R ^b are each independently
A hydrogen atom, a halogen atom or a hydrocarbon group, R ¹⁵
To R ¹⁸ may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R ¹⁵ and R ¹⁶ are each represented by Or R ¹⁷ and R ¹⁸ may form an alkylidene group),

[0012]

[Chemical 14]

(In the formula [II], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2,
R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
An aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, wherein the carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or R ¹¹ The carbon atom to which R is bonded may be bonded directly or through an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R
¹⁹ and may be bonded to each other to form a monocyclic or polycyclic aromatic ring).

Such a cyclic olefin polymer composition, and further, the cyclic olefin polymer composition is radically reacted in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. The cyclic olefin polymer composition obtained by the reaction has excellent impact resistance, transparency and heat resistance.

In the present invention, the cyclic olefin polymer composition is a cyclic olefin polymer [A] and a cyclic olefin polymer [B] is [A-1] (i) α having a carbon number of 2 or more. A cyclic olefin-based random copolymer obtained by copolymerizing an olefin, (ii) at least one cyclic olefin represented by the above formula [I] or [II], and optionally (iii) a diene It is preferably a polymer.

Further, the cyclic olefin polymer [A] is
A random copolymer of an α-olefin having 2 or more carbon atoms and a cyclic olefin represented by the above formula [II] is particularly preferable. The cyclic olefin polymer [B] is an α-olefin having 2 or more carbon atoms. -A random copolymer of an olefin and a cyclic olefin represented by the above formula [I] is particularly preferable.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The cycloolefin polymer composition according to the present invention will be described below. In the present invention, the term "polymer" may be used to mean not only a homopolymer but also a copolymer, and "polymerization"
The term may be used to mean not only homopolymerization but also copolymerization.

The cyclic olefin polymer composition according to the present invention comprises a cyclic olefin polymer [A] selected from the group consisting of the following [A-1], [A-2] and [A-3]: [A-1] (i) an α-olefin having 2 or more carbon atoms, (ii) at least one cyclic olefin represented by the following formula [I] or [II], and optionally (iii) Cycloolefin random copolymer obtained by copolymerizing with diene [A-2] Ring-opening polymer of at least one cyclic olefin represented by the following formula [I] or [II] [A-3 ] A hydrogenated product of a ring-opening polymer of at least one cyclic olefin represented by the following formula [I] or [II]: [B-1], [B-2] and [B-3] And a cyclic olefin polymer [B] selected from the group. [B-1] (i) an α-olefin having 2 or more carbon atoms, (ii) at least one cyclic olefin represented by the following formula [I] or [II], and optionally (iii) Cycloolefin-based random copolymer obtained by copolymerizing with diene [B-2] Ring-opening polymer of at least one cyclic olefin represented by the following formula [I] or [II] [B-3 ] Hydrogenated product of a ring-opening polymer of at least one cyclic olefin represented by the following formula [I] or [II] The cyclic olefin random copolymer [A-1] and the cyclic olefin used in the present invention -Based random copolymer [B-
1] are both (i) an α-olefin having 2 or more carbon atoms, (ii) at least one cyclic olefin represented by the following formula [I] or [II], and (ii)
i) A cyclic olefin-based random copolymer obtained by copolymerizing with a diene.

Cyclic olefin random copolymer [A-
1] and the α-olefin having 2 or more carbon atoms (i) used in copolymerizing the random olefin-based random copolymer [B-1], specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Examples of the α-olefin having 2 to 20 carbon atoms include pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Of these, ethylene is particularly preferably used.

Cycloolefin random copolymer [A-
The cyclic olefin (ii) used when copolymerizing 1] and the cyclic olefin random copolymer [B-1] is a cyclic olefin represented by the following formula [I] or [II].

The cyclic olefin represented by the following formula [I] or [II] will be specifically described below.

[0022]

[Chemical 15]

In the formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, the ring represented by q is a member ring, and when q is 0, this ring is a 5-membered ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group is usually an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms or an aromatic hydrocarbon group. Is mentioned. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

The cycloalkyl group includes a cyclohexyl group, and the aromatic hydrocarbon group includes a phenyl group and a naphthyl group. Furthermore, the above formula [I]
, R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ , R ¹⁵ and R
¹⁷ and R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R
¹⁶ and R ¹⁷ may be bonded to each other (cooperate with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group thus formed forms a double bond. You may have. Specific examples of the monocycle or polycycle formed here include the following.

[0027]

[Chemical 16]

In the above exemplification, the carbon atoms numbered 1 or 2 are each R in the formula [I].
^It represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0029]

[Chemical 17]

In the formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. Also,
R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the above formula [I]. Further, as the hydrocarbon group,
Usually, an alkyl group having 1 to 20 carbon atoms, 3 carbon atoms
-15 cycloalkyl groups or aromatic hydrocarbon groups. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group, examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group, and specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, Examples thereof include a phenylethyl group.

Examples of the alkoxy group include methoxy group and eth
Examples thereof include xy group and propoxy group. Where R⁹
And R^TenThe carbon atom to which R is attached, and R¹³Combined with
Carbon atom or R¹¹The carbon atom to which is bound is
Directly or through an alkylene group having 1 to 3 carbon atoms
May be combined. That is, the above two carbon atoms are
When linked via an alkylene group, R⁹And R
¹³Or or R^TenAnd R ¹¹Together with each other,
Ren group (-CH₂-), Ethylene group (-CH₂CH₂-) Or propylene
Group (-CH₂CH₂CH₂-) Form any alkylene group
Is made.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, n = m = 0
In this case, the following aromatic ring formed by R ¹⁵ and R ¹² can be mentioned.

[0035]

[Chemical 18]

Here, q is the same as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] include bicyclo-2-heptene derivative (bicyclohept-2-ene derivative), tricyclo-3-decene derivative, tricyclo- 3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-
Pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative,
Heptacyclo-5-eicosene derivative, heptacyclo-4-
Eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docosene derivative, nonacyclo-5
-Pentacocene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,
4-methano-1,4,4a, 9a-tetrahydrofluorene derivative,
1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative and the like can be mentioned.

In the following, the above formula [I] or [I
Specific examples of the cyclic olefin represented by [I] are shown below.

[0038]

[Chemical 19]

[0039]

[Chemical 20]

[0040]

[Chemical 21]

[0041]

[Chemical formula 22]

[0042]

[Chemical formula 23]

[0043]

[Chemical formula 24]

[0044]

[Chemical 25]

[0045]

[Chemical formula 26]

[0046]

[Chemical 27]

[0047]

[Chemical 28]

[0048]

[Chemical 29]

[0049]

[Chemical 30]

[0050]

[Chemical 31]

[0051]

[Chemical 32]

[0052]

[Chemical 33]

[0053]

[Chemical 34]

[0054]

[Chemical 35]

[0055]

[Chemical 36]

[0056]

[Chemical 37]

[0057]

[Chemical 38]

[0058]

[Chemical Formula 39]

The cyclic olefin represented by the above general formula [I] or [II] is produced by subjecting cyclopentadiene and olefins having a structure corresponding to cyclopentadiene to Diels-Alder reaction. be able to.

The structural unit derived from the cyclic olefin represented by the above formula [I] or [II] is the following formula [I '] or [I] in the cyclic olefin random copolymer.
It is considered that the repeating unit having the structure represented by I '] is formed.

[0061]

[Chemical 40]

(In the formula [I '], m, n, q and R ¹ to
R ¹⁸ and R ^a and R ^b are the same as defined in the above formula [I]. )

[0063]

[Chemical 41]

(In the formula [II '], n, m, p, q and R ¹
R ¹⁹ are the same as defined in the above formula [II]. ) These cyclic olefins can be used alone or in combination of two or more kinds.

Cyclic Olefin Random Copolymer [A-
1] and the cyclic olefin-based random copolymer [B-1] are optionally used as the (iii) diene, as represented by the following formulas [III] to [VI]: Non-conjugated dienes having a number of 5 to 20 can be exemplified.

[0066]

[Chemical 42]

As the non-conjugated diene represented by the above formula [III], 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1, 9-
Dekaji et emissions, 1,11 dodecadiene, and the like can be exemplified 1,19 Eikojien.

As the diene represented by the above formula [IV],

[0069]

[Chemical 43]

Examples thereof include the following. As the non-conjugated diene represented by the above formula [V],

[0071]

[Chemical 44]

Examples thereof include: The above formula [V
As the non-conjugated diene represented by [I],

[0073]

[Chemical formula 45]

Examples thereof include: In the above-mentioned diene, a hydrogen atom bonded to carbon other than carbon forming a carbon-carbon double bond may be substituted with a hydrocarbon group.

Among the dienes represented by the above formulas [III] to [VI], 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 5-vinyl-bicyclo [2.2.1] hept-2-ene, 8-vinyl - tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10] -3-dodecene, bicyclo [2.2.1] hept-2,5-diene, tetracyclo [4.4.0.1 ^{2, 5} .1 ^{7,10]-3,8-dodecadiene} is preferably used.

Furthermore, in the present invention, as (iii) diene,
In addition to the dienes represented by the above general formulas [III], [IV], [V] and [VI], the following diene compounds can be used.

Cyclic dienes such as 5-ethylidene-2-norbornene, 5-methylene-2-norbornene and 5-isopropylidene-2-norbornene. The cyclic olefin random copolymer [A-1] used in the present invention comprises (i) an α-olefin having 2 or more carbon atoms and (i)
i) At least one cyclic olefin represented by the above formula [I] or [II], and optionally (iii) a diene, as described below, a soluble vanadium compound and an organoaluminum compound (A). A metallocene compound of a transition metal selected from Group IVB of the periodic table or a lanthanide and an organoaluminumoxy compound, and optionally an organoaluminum compound (B). It can be produced by copolymerizing in the presence of a catalyst (b).

The soluble vanadium compound forming such catalyst (a) is specifically represented by the following general formula. VO (OR) _a X _b or V (OR) _c X _d where R is a hydrocarbon group and a, b, c, d are 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦, respectively. a + b ≦ 3,0
≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied. More specifically, VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ ,
VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ )
Cl ₂ , VO (O-n-C ₄ H ₉ ) Cl ₂ , VO (OC _{2
H 5) 3, VOBr 2,} VCl 4, VOCl 2 VO (O-n-C 4 H 9) 3, VOCl 3 · 2OC 8 H 17
A vanadium compound such as 7OH is used.

These compounds can be used alone or in combination of two or more kinds. The soluble vanadium compound can also be used as an electron donor adduct obtained by contacting an electron donor as shown below.

Examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acid or inorganic acid esters, ethers, diethers and acid amides. , Acid anhydrides, oxygen-containing electron donors such as alkoxysilane, and nitrogen-containing electron donors such as ammonia, amines, nitriles, pyridines, and isocyanates.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, and halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; phenol, cresol, xylenol, ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone , Acetaldehyde, propionaldehyde, octyl aldehyde,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
2 to 2 carbon atoms such as ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate
18 organic acid esters; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride; methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride; ethyl silicate, diphenyldimethoxysilane Acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, etc. Amines; nitriles such as acetonitrile, benzonitrile, trinitrile;
Pyridines such as pyridine, methylpyridine, ethylpyridine and dimethylpyridine can be exemplified.

When preparing an electron donor adduct of a soluble vanadium compound, these electron donors can be used alone or in combination of two or more kinds. The organoaluminum compound (A) that forms the catalyst (a) with the above-mentioned soluble vanadium compound has at least one Al-C bond in the molecule, and for example, the following (a) and (b) It is represented by a formula.

(A) General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² usually have 1 to 15 carbon atoms,
It is preferably 1 to 4 hydrocarbon groups, which may be the same or different. X is a halogen atom, m is 0 ≦ m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <
3 and q are numbers 0 ≦ q <3, and m + n + p +
q = 3) (b) Complex of a Group 1 metal represented by the general formula M ¹ AlR ¹ (wherein M ¹ is Li, Na and K, and R ¹ is the same as above) with aluminum. Alkylated compound As the organoaluminum compound represented by the above (a), the following compounds can be specifically exemplified.

(1) General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above, and m is preferably a number of 1.5 ≦ m <3. (2) General formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above, X is halogen, and m is preferably a number of 0 <m <3) (3) General Formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above, and m is preferably 2 ≦
m <3 is a number) (4) General formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as defined above, X is a halogen, and 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3,
m + n + q = 3) More specifically, the organoaluminum compound (A) represented by (a) can be exemplified by the following compounds.

Examples of the organoaluminum compound represented by (1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisopropenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide. Ethyl aluminum sesquiethoxide, butyl aluminum sesquibutoxide, and R ¹ _2.5 Al (O
Partially alkoxylated alkylaluminum having an average composition represented by R ² ) _{0.5 and the} like can be mentioned.

Examples of the organoaluminum compound represented by (2) include dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide and the like. Alkyl aluminum sesquihalides; partially halogenated alkyl aluminum such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide and the like can be mentioned.

Examples of the organoaluminum compound represented by (3) include dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride and propyl aluminum dihydride. Can be mentioned.

Examples of the organoaluminum compound represented by (4) include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide.

Further, it may be a compound similar to the compound represented by the above general formula (a), for example, an organoaluminum compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (C ₄ H
₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C _{6
H 5) Al (C 2 H} 5) 2, and the like can be exemplified.

Further, as the compound belonging to the above (b),
_{LiAl (C 2 H 5) 4} , LiAl (C 7 H 15) 4 and the like can be exemplified. Of these, alkylaluminum halides, alkylaluminum dihalides, and mixtures thereof are particularly preferable.

Next, a catalyst (b) formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table or a lanthanide and an organoaluminum oxy compound, and optionally an organoaluminum compound (B) will be described. To do.

As the transition metal compound of Group IVB or lanthanide of the periodic table containing such a ligand having a cyclopentadienyl skeleton, compounds represented by the following general formula [VII] are exemplified. it can.

ML _X ... [VII] In the above general formula [VII], M is a transition metal selected from Group IVB of the periodic table and lanthanides, and specifically, zirconium, titanium, hafnium, neodymium, samarium. Or yttrium, L is a ligand that coordinates to a transition metal, and at least one L is
L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group. Group, SO ₃ R
(However, R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen.) Or a hydrogen atom, and x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Of these ligands which coordinate to the transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula [VII] contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene, It may be bonded via a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and neophyll group It is illustrated.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. A phenoxy group etc. are illustrated as an aryloxy group.

As halogen, fluorine, chlorine, bromine,
Examples thereof include iodine. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

Examples of the compound represented by the above general formula [IV] include
For example, when the valence of the transition metal is 4, more specifically,
It is represented by the following general formula [VII ']. R¹ _aR² _bR³ _cR^Four _dM ... [VII '] (In the formula [VII'], M is zirconium, titanium, or hafnium.
Mu, Neodymium, Samarium or Ytterbium
R¹Is a group having a cyclopentadienyl skeleton
R², R³And R^FourIs the cyclopentadienyl skeleton
Group having, alkyl group, cycloalkyl group, aryl
Group, aralkyl group, alkoxy group, aryloxy group, ha
Rogen atom, trialkylsilyl group, SO₃R or water
Elementary atom, a is an integer of 1 or more, and a + b + c +
d = 4. ) In the present invention, the odor of the above general formula [VII ′]
R², R³And R^FourOne of them is cyclopentadiene
A transition metal compound having a nyl skeleton, for example, R¹
And R ²Is a group having a cyclopentadienyl skeleton
Transition metal compounds are preferably used. These shiku
The groups having a lopentadienyl skeleton are ethylene and propylene.
Alkylene groups such as benzene, and alkyl groups such as isopropylidene
Substituted alkylene such as lidene group and diphenylmethylene
Group, silylene group or dimethylsilylene, diphenyl
Substituted silylenes such as rylene and methylphenylsilylene groups
It may be bound via a group or the like. Also, R³And
And R^FourIs a group having a cyclopentadienyl skeleton,
Group, cycloalkyl group, aryl group, aralkyl group,
Alkoxy group, aryloxy group, halogen atom, thoria
Rukyril silyl group, SO₃R or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis (Indenyl) zirconium bis (p-toluenesulfonato), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonato), ethylenebis (4,5, 6,7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) ) Dimethyl zirconium, dimethyl silylene bis (cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (methyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (dimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadiene) (Enyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (Indenyl) zirconium bis (trifluoromethanesulfonato), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) Zirconium dichloride, methylphenylsilylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclo Pentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium,
Bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluene) Sulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) Zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (dimethylcyclopentadienyl) dimethyl zirconium, bis (eth Rucyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene (Enyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl)
Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples of transition metal compounds, the disubstituted cyclopentadienyl ring is 1,2- and 1,2-
3-substitutes are included, and tri-substitutes include 1,2,3- and 1,2,4-substitutes. In addition, alkyl groups such as propyl and butyl are
It includes isomers such as n-, i-, sec-, and tert-.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal, hafnium metal, neodymium metal, samarium metal or ytribium metal in the above zirconium compound can be used.

The organoaluminum oxy compound which forms the catalyst (b) together with the transition metal compound of Group IVB of the periodic table or the lanthanide containing the ligand having the cyclopentadienyl skeleton as described above is a conventionally known aluminum compound. It may be nooxane or a benzene-insoluble organoaluminum oxy compound.

Such a conventionally known aluminoxane is specifically represented by the following general formula.

[0105]

[Chemical formula 46]

(In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group and a butyl group, preferably a methyl group and an ethyl group, particularly preferably a methyl group, and m
Is an integer of 2 or more, preferably 5 to 40. ) Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OA1 (R ¹ )) and a formula (OA1).
Alkyloxyaluminum unit represented by (R ² )) [wherein, R ¹ and R ² can exemplify the same hydrocarbon group as R, and R ¹ and R ² represent different groups] May be formed from mixed alkyloxyaluminum units.

The conventionally known aluminoxane is prepared, for example, by the following method and is usually recovered as a solution of an aromatic hydrocarbon solvent. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to an aromatic hydrocarbon solvent in which is suspended and reacted to recover a solution of the aromatic hydrocarbon solvent.

(2) Water (water, ice or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a solution of an aromatic hydrocarbon solvent. how to.

(3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

Of these methods, the method (1) is preferably adopted. As the organoaluminum compound used in preparing the solution of aluminoxane, specifically, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum, tri
Trialkyl aluminum such as tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, and tridecyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diethyl Aluminum bromide,
Dialkyl aluminum halides such as diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Dialkyl aluminum aryloxides such as diethyl aluminum phenoxide be able to.

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula can also be used.

[0112] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) The organic aluminum such as The compounds may be used alone or in combination.

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or an organoaluminum compound and water as described above. It can be obtained by a method of contacting.

[0114] In benzene-insoluble organoaluminum oxy-compound used in the present invention, the compound was analyzed by infrared spectroscopy (IR), the absorbance at around 1220 cm ^-1 and (D _1220), the absorbance at around 1260 cm ^-1 (D ₁₂₆₀₎ and the ratio of (D _{12 60} / D ₁₂₂₀₎ is 0.09
Or less, preferably 0.08 or less, particularly preferably 0.4 to
It is desirable that the range is 0.07.

The above benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxy aluminum unit represented by the following formula.

[0116]

[Chemical 47]

In the formula, R ³ is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group.
Examples thereof include a butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound may contain an oxyaluminum unit represented by the following formula in addition to the alkyloxyaluminum unit represented by the above formula.

[0119]

[Chemical 48]

In the formula, R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a halogen or a hydrogen atom. Further, R ⁴ and R ³ in the above formula represent different groups from each other.

When the benzene-insoluble organoaluminum oxy compound contains an oxyaluminum unit,
An organoaluminumoxy compound having an alkyloxyaluminum unit containing an alkyloxyaluminum unit in a proportion of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is desirable.

Such a benzene-insoluble organoaluminum oxy compound is an Al that dissolves in benzene at 60 ° C.
The component is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble or hardly soluble in benzene.

The organoaluminum oxy compound used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum. Organoaluminum compound (B) optionally used in the catalyst (B)
For example, an organoaluminum compound represented by the following general formula [VIII] can be exemplified.

R ⁵ _n AlX _3-n ... [VIII] (In the formula [VIII], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1
~ 3. ) In the above general formula [VIII], R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group. , Isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

As such an organoaluminum compound, the following compounds are specifically used. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminium chloride, diisopropylaluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; methyl Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (B), a compound represented by the following general formula [IX] can also be used. During ^{_{R 5 n AlY 3-n ...}} [IX] ( wherein [IX], R ⁵ are as defined above, Y is -OR ⁶
Group, -OSiR ⁷ ₃ group, -OAlR ⁸ ₂ group, -NR ⁹ ₂ group, -
SiR ¹⁰ ₃ group or —N (R ¹¹ ) AlR ¹² ₂ group, and n is 1
To R 2, R ⁶ , R ⁷ , R ⁸ and R ¹² are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ⁹ is a hydrogen atom, a methyl group, an ethyl group, It is an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁰ and R ¹¹ are a methyl group, an ethyl group or the like. ) As such an organoaluminum compound, the following compounds are specifically used. (I) a compound represented by R ⁵ _n Al (OR ⁶ ) _3-n , such as dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (ii) R ⁵ _n Al (OSiR ⁷ ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OS
iMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (iii) A compound represented by R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n ,
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOA
(iv) a compound represented by R ⁵ _n Al (NR ⁹ ₂ ) _3-n , such as l (iso-Bu) ₂ ; for example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNH
EtEt ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiM
e ₃ ) _{2 and the} like, (v) compounds represented by R ⁵ _n Al (SiR ¹⁰ ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ , and (vi) R ⁵ _n Al (N (R ¹¹ ) AlR ¹² ₂ ) _3-n represented by compounds such as Et ₂ AlN (Me) AlEt ₂ , (iso
Etc. _{-Bu) 2 AlN (Et) Al} (iso-Bu) 2.

Among the organoaluminum compounds represented by the above general formulas [VIII] and [IX], the general formula R ⁵ ₃ Al,
The organoaluminum compounds represented by R ⁵ _n Al (OR ⁶ ) _3-n and R ⁵ _n Al (OAlR ⁸ ₂ ) _3-n can be given as preferred examples, wherein R ⁵ is an isoalkyl group and n = 2 is particularly preferable. These organoaluminum compounds are
It is also possible to use a mixture of two or more kinds.

The ring-opening polymer of cyclic olefin [A-2] and the ring-opening polymer of cyclic olefin used in the present invention [B-
2] is a ring-opening polymer of at least one cyclic olefin represented by the above formula [I] or [II].

The ring-opening polymer of such a cyclic olefin can be prepared by ring-opening polymerization of the cyclic olefin represented by the above formula [I] or [II] alone or in combination. That is, a ring-opening polymer is prepared by subjecting at least one cyclic olefin represented by the above formula [I] or [II] to ring-opening polymerization in the presence of a ring-opening polymerization catalyst.

As the ring-opening polymerization catalyst used here,
For example, a catalyst comprising a metal halide such as ruthenium, rhodium, osmium, indium, platinum, molybdenum and tungsten, a nitrate of these metals and an acetylacetone compound of these metals, and a reducing agent such as an alcohol or a tin compound, In addition, a halogen compound of a metal such as titanium, vanadium, zirconium, tungsten and morbutene, a catalyst composed of an acetylacetone compound of these metals and a metal aluminum compound can be mentioned.

When preparing the above ring-opening polymer, at least 1 of the above formula [I] or [II] is used.
Other cyclic olefins other than certain cyclic olefins may be used, and examples of such other cyclic olefins include cyclobutene, cyclopentene, cyclooctene, cyclononene, methylcyclopentene, methylcycloheptene, methylcyclooctene, and methylcyclooctene. Carbon such as nonene, methylcyclodecene, ethylcyclopentene, ethylcycloheptene, ethylcyclooctene, ethylcyclononene, dimethylcycloheptene, dimethylcyclooctene, dimethylcyclononene, dimethylcyclodecene, cyclooctadiene, cyclodecadiene Number 4
The above monocyclic olefins and 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene and the like. To be

As the molecular weight regulator, propylene,
Alkenes such as 1-butene, 1-pentene, 1-hexene can be used as a copolymerization component. In such a ring-opening polymer, at least part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [Ia], and the above formula [II] ] It is considered that at least a part of the cyclic olefin represented by the formula has a structure represented by the following formula [II-a].

[0133]

[Chemical 49]

(In the formula [Ia], n, m, q, R ^{1 to} R ¹⁸
And R ^a and R ^b have the same meaning as in formula [I].

[0135]

[Chemical 50]

(In the formula [II-a], n, m, p, q, R ¹ to
(R ¹⁹ has the same meaning as in formula [II]) The hydrogenated product [A-3] of the ring-opened polymer of the cyclic olefin and the hydrogenated product [B-3 of the ring-opened polymer of the cyclic olefin used in the present invention. ] Is a hydrogenated product of a ring-opening polymer of at least one cyclic olefin represented by the above formula [I] or [II].

The hydrogenated product of the ring-opening polymer of cyclic olefin can be obtained by hydrogenating the ring-opening polymer of cyclic olefin prepared as described above. For hydrogenation of the ring-opening polymer, a usual hydrogenation method performed in the presence of a hydrogenation catalyst can be adopted.

As the hydrogenation catalyst used here,
A hydrogenation catalyst such as a heterogeneous catalyst or a homogeneous catalyst generally used for hydrogenating an olefin compound can be used. Specific examples of heterogeneous catalysts include metals such as nickel, palladium and platinum,
And a solid catalyst in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina and titanium oxide (eg nickel / silica, nickel /
Diatomaceous earth, palladium / carbon, palladium / silica,
Palladium / diatomaceous earth, palladium / alumina, etc.). Further, examples of the homogeneous catalyst are catalysts based on a metal of Group VIII of the periodic table, and examples of such catalysts include cobalt naphthenate, triethylaluminum, cobalt octenoate / n-butyllithium, An organometallic compound formed from a nickel compound such as nickel acetylacetonate / triethylaluminum or a cobalt compound and a metal of Group I to III of the periodic table can be mentioned, and an Rh compound can also be used.

The hydrogenation reaction using the hydrogenation catalyst as described above can be carried out in either a heterogeneous system or a homogeneous system, depending on the type of the catalyst. The reaction conditions in such a system are usually 0 to 180 ° C., preferably 20 to 100 ° C. under a hydrogen atmosphere of 1 to 150 atm.
Is set to the temperature of. The hydrogenation rate under such conditions can be adjusted by appropriately setting conditions such as hydrogen pressure, reaction temperature, reaction time, and catalyst concentration, but the double bond present in the main chain of the polymer Of these,
50% or more, preferably 80% or more, more preferably 90% or more is hydrogenated.

In such a hydrogenated cyclic polymer,
At least a part of the cyclic olefin represented by the above formula [I] is considered to have a structure represented by the following formula [Ib], and at least one of the cyclic olefins represented by the above formula [II]. The part is considered to have a structure represented by the following formula [II-b].

[0141]

[Chemical 51]

(In the formula [Ib], n, m, q, R ^{1 to} R ¹⁸
And R ^a and R ^b have the same meaning as in formula [I].

[0143]

[Chemical 52]

(In the formula [II-b], n, m, p, q, R ¹ to
R ¹⁹ has the same meaning as in formula [II].] Next, the cycloolefin-based polymer [A] and the cycloolefin-based polymer [B] that form the cycloolefin-based polymer composition of the present invention are more specifically described. Explained.

The cyclic olefin-based polymer [A] which forms the cyclic olefin-based polymer composition of the present invention is the above-mentioned [A-1] cyclic olefin-based random copolymer [A-].
2] A cyclic olefin polymer selected from the group consisting of a ring-opening polymer of a cyclic olefin and a hydrogenated product of [A-3] a ring-opening polymer of a cyclic olefin, and the cyclic olefin polymer [B] is And a hydrogenated product of the above-mentioned [B-1] cyclic olefin-based random copolymer, [B-2] cyclic olefin ring-opening polymer, and [B-3] cyclic olefin ring-opening polymer. It is a cyclic olefin polymer selected from the group.

In the cyclic olefin random copolymer [A-1], the repeating unit derived from the α-olefin component is
It is usually desirable to be present in an amount in the range of 60 to 97 mol%, preferably 70 to 95 mol%, and the above formula [I]
Or, the repeating unit derived from the cyclic olefin represented by [II] is usually 3 to 40 mol%, preferably 5 to 30.
It is desirable to be present in an amount in the range of mol%. The diene compound is preferably present in an amount of 10 mol% or less.

The intrinsic viscosity [η] in decalin at 135 ° C. is 0.5 to 5.0 dl / g, preferably 0.15 to 4.5 dl.
It is preferably in the range of / g. The glass transition temperature (Tg) measured by DSC is desirably lower than 15 ° C, preferably in the range of -30 ° C to 15 ° C.

The refractive index n _D (A) measured at 25 ° C. is usually 1.500 to 1.650, preferably 1.510.
The range of 1.600 is desirable. In the present invention, the refractive index means the Abbe refractometer (D line, 589).
nm) at 25 ° C.

The iodine value is preferably 30 or less. The intrinsic viscosity [η] of the hydrogenated product of the ring-opening polymer of [A-2] cyclic olefin and the ring-opening polymer of [A-3] cyclic olefin in decalin at 135 ° C. is 0.5 to 5. It is desirable that the range is 0 dl / g, preferably 0.15 to 4.5 dl / g.

Glass transition temperature (T
g) is less than 15 ° C, preferably -30 ° C to 15 ° C.
It is preferably in the range of ° C. The refractive index n _D (A) measured at 25 ° C. is usually 1.50 to 1.650, preferably 1.510 to 1.600.

The iodine value is preferably 30 or less. The repeating unit derived from the α-olefin component of the [B-1] cyclic olefin random copolymer is usually 40 to 85.
The amount of the repeating unit derived from the cyclic olefin represented by the above formula [I] or [II] is usually 15 to 60 mol%. Desirably, it is present in an amount ranging from 20 to 58 mol%. The diene compound is preferably present in an amount of 10 mol% or less.

Intrinsic viscosity [η] in decalin at 135 ° C.
Is 0.1-5.0 dl / g, preferably 0.15-4.
A range of 5 dl / g is desirable. The glass transition temperature (Tg) measured by DSC is 70 ° C. or higher, preferably 90 to 200 ° C.

The refractive index n _D (B) measured at 25 ° C. is usually 1.500 to 1.650, preferably 1.510.
The range of 1.600 is desirable. Further, the iodine value is preferably 30 or less.

[B-2] Ring-opening polymer of cyclic olefin and hydrogenated product of ring-opening polymer of [B-3] cyclic olefin 1
The intrinsic viscosity [η] in decalin at 35 ° C. is 0.1 to 5.
It is desirable that the range is 0 dl / g, preferably 0.15 to 4.5 dl / g.

Glass transition temperature (T
It is desirable that g) is 70 ° C. or higher, preferably 90 to 200 ° C. Refractive index n measured at 25 ° C
It is desirable that _D (B) is usually 1.500 to 1.650, preferably 1.510 to 1.600.

The iodine value is preferably 30 or less. The cycloolefin polymer composition according to the present invention comprises the cycloolefin polymer [A] and the cycloolefin polymer [B], and has a refractive index n _{D of the} cycloolefin polymer [A]. Difference between (A) and refractive index n _{D of} cyclic olefin polymer [B] (B) Δn _D = | n
_{D (A) -n D (B} ) | is 0.015 or less, preferably 0.
It is 012 or less, more preferably 0.010 or less.

Difference in refractive index between cyclic olefin polymer [A] and cyclic olefin polymer [B] Δn _D = | n
_{D (A) -n D (B} ) | When exceeding 0.015, the transparency of the resulting composition may be impaired.

In the cyclic olefin polymer composition according to the present invention, the ratio of the cyclic olefin polymer [A] to the cyclic olefin polymer [B] ([A] / [B],
It is desirable that the weight ratio) is 8/92 to 40/60 (total of [A] and [B] is 100), preferably 10/90 to 40/60.

Such a cyclic olefin polymer composition can be prepared, for example, by the following method. (1) A method of mechanically blending the separately prepared cyclic olefin polymer [A] and cyclic olefin polymer [B] using an extruder, a kneader, or the like.

(2) The cyclic olefin polymer [A] and the cyclic olefin polymer [B] are combined with an appropriate solvent (for example, saturated hydrocarbon such as heptane, hexane, decane and cyclohexane; toluene, benzene and xylene). Aromatic hydrocarbon such as) and a method of blending by dissolving (solution blending method).

(3) A method in which the cyclic olefin polymer [A] and the cyclic olefin polymer [B] are synthesized in different polymerization vessels, and the resulting copolymer is blended in another container.

The cyclic olefin polymer composition thus obtained has a small difference in refractive index between the cyclic olefin polymer [A] and the cyclic olefin polymer [B]. It is excellent and has a good balance of transparency, heat resistance and impact strength.

The cyclic olefin polymer composition of the present invention comprises the above cyclic olefin polymer [A] and the cyclic olefin polymer [B], an organic peroxide and, if necessary, It may be a composition obtained by a radical reaction in the presence of a radically polymerizable polyfunctional monomer.

The radical reaction is carried out by reacting the cyclic olefin polymer [A] and the cyclic olefin polymer [B] in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. It is carried out by radical reaction.

As the organic peroxide used here, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert -Butylperoxy) octane and other peroxyketals; tert-butylhydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroxyperoxide, 1,1,3,3-tetramethyl Hydroperoxides such as butyl hydroperoxide; di-ter
t-Butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-diethyl-2,5-di (ter
t-Butylperoxy) hexyne-3 and other dialkyl peroxides, lauroyl peroxide, benzoyl peroxide and other diacyl peroxides; tert-butylperoxyacetate, tert-butylperoxybenzoate, 2,5-dimethyl- Examples include peroxyesters such as 2,5-di (benzoylperoxy) hexane.

As the radical-polymerizable polyfunctional monomer used as necessary, for example, divinylbenzene, vinyl acrylate, vinyl methacrylate, triaryl isocyanurate, diaryl phthalate, ethylene dimethacrylate trimethylolpropane trimethacrylate, etc. Can be mentioned.

In the present invention, the cyclic olefin polymer [A] and the cyclic olefin polymer [B] are added in the presence of an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer. When the composition is prepared by radical reaction,
The composition may be prepared by using one reactor, or a plurality of reactors may be used, and the cyclic olefin polymer [A] and the cyclic olefin polymer [B] may be used in one reactor. The reaction may be carried out, the cyclic olefin polymer [A] and the cyclic olefin polymer [B] may be reacted in the other reactor, and then both of them may be blended to obtain a final composition.

In such a radical reaction, the organic peroxide is added to 100 parts by weight of the total amount of the cyclic olefin polymer [A] and the cyclic olefin polymer [B].
The radically polymerizable polyfunctional monomer, which is usually used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and used as necessary, is a cyclic olefin polymer [A]. , A total of 10 with the cyclic olefin polymer [B]
It is usually used in an amount of 0.01 to 15 parts by weight, preferably 0.1 to 10 parts by weight, based on 0 parts by weight.

In the radical reaction of the cyclic olefin polymer [A] and the cyclic olefin polymer [B], it is desirable that the reaction be carried out at a temperature at which the organic peroxide decomposes. In the reaction, the respective raw materials can be mixed and reacted at the same time, but the cyclic olefin polymer [A]
And a cyclic olefin polymer [B] are mixed, and then an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer are mixed and reacted. The organic peroxide is desirably added in a state where the cyclic olefin polymer [A] and the cyclic olefin polymer [B] are sufficiently mixed.

To mix the cyclic olefin polymer [A] and the cyclic olefin polymer [B], the separately prepared cyclic olefin polymer [A] and the cyclic olefin polymer [B] are mixed. A method of mechanically blending with an extruder or the like, or a cyclic olefin polymer [A] and a cyclic olefin polymer [B] in a suitable solvent (eg, saturated hydrocarbon such as heptane, hexane, decane, and cyclohexane; A method of sufficiently dissolving it in an aromatic hydrocarbon such as toluene, benzene, xylene, etc. and blending (solution blending method), and further separating the cyclic olefin polymer [A] and the cyclic olefin polymer [B] The method of synthesizing in the other polymerization vessel and blending the obtained copolymer in another container can be adopted.

To the mixture of the cyclic olefin polymer [A] thus obtained and the cyclic olefin polymer [B], an organic peroxide and, if necessary, a radically polymerizable polyfunctional monomer are added. And blend and react at a temperature at which the organic peroxide decomposes.

Such a radical reaction can be carried out in a state in which the mixture of raw materials is melted, or in a solution in which the mixture of raw materials is dissolved in a solvent. When the radical reaction is carried out in a molten state, a kneading device such as a mixing roll, a Banbury mixer, an extruder, a kneader or a continuous mixer is used to melt and mix the mixture of raw materials to react. The radical reaction is at a temperature equal to or higher than the one-minute half-life of the organic peroxide, usually 150 to 300 ° C., preferably 170.
It is desirable to carry out at a temperature of ˜270 ° C. for usually 10 seconds to 30 minutes, preferably 3 to 10 minutes.

As the solvent used when carrying out the radical reaction in a solution state, the same solvent as that used in the solution blending method can be used. The radical reaction is carried out at a temperature not lower than the 10-minute half-life of the organic peroxide, usually 50 to 300.
It is desirable to carry out the treatment at a temperature of ° C for 10 seconds to 2 hours.

From the reaction product obtained as described above, a composition is obtained by removing the solvent by a method such as distillation. When the cyclic olefin polymer [A] and the cyclic olefin polymer [B] are radically reacted in this manner, the organic peroxide is decomposed to cause a radical reaction, and the cyclic olefin polymer [A] and It is presumed that a reaction product excellent in transparency and impact resistance can be obtained because the interpolymer bond reaction partially occurs with the cyclic olefin polymer [B].

When a double bond is present in the cyclic olefin polymer [A] and the cyclic olefin polymer [B], or when a structural unit derived from a radical-polymerizable polyfunctional monomer is present, Further, the binding reaction is likely to occur, and a reaction product having excellent transparency and impact resistance can be obtained.

This composition can be used alone or as a blend with another transparent resin. The cyclic olefin polymer composition provided by the present invention is molded by a well-known method. For example,
Single screw extruder, vent type extruder, twin screw extruder,
Extrusion molding, injection molding, blow molding, rotation by conical twin screw extruder, co-kneader, practicator, mixer extruder, twin-screw conical screw extruder, planetary screw extruder, gear type extruder, screwless extruder, etc. Molded.

In the cyclic olefin polymer composition of the present invention, a rubber component is blended in order to further improve the impact strength of the composition, and a heat stabilizer, A weather resistance stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax and the like can be appropriately added.

For example, a stabilizer to be added as an optional component is specifically tetrakis [methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamide bis [ethyl-3 (3,5- Phenolic antioxidants such as di-t-butyl-4-hydroxyphenyl)] propionate; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate, glycerin monolaurate, glycerin Examples thereof include fatty acid esters of polyhydric alcohols such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate.

These may be blended alone or in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and stearin. Examples thereof include a combination with zinc acid and glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination, and the fatty acid ester of the polyhydric alcohol is one of the alcoholic hydroxyl groups of the trihydric or higher polyhydric alcohol. The part is preferably a polyhydric alcohol fatty acid ester esterified. As such fatty acid ester of polyhydric alcohol, specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, glycerin fatty acid ester such as glycerin dilaurate, Pentaerythritol monostearate, pentaerythritol monolaurate,
Fatty acid esters of pentaerythritol such as pentaerythritol dilaurate, pentaerythritol distearate and pentaerythritol tristearate are used. Such a phenolic antioxidant is 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and more preferably 0 to 2 parts by weight with respect to 100 parts by weight of the cyclic olefin resin.
The fatty acid ester of polyhydric alcohol is used in an amount of 0.
It is used in an amount of -10 parts by weight, preferably 0-5 parts by weight.

In the present invention, the cyclic olefin-based random copolymer composition may contain silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, water insofar as the object of the present invention is not impaired. Aluminum oxide, magnesium hydroxide, basic magnesium carbonate,
Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber Fillers such as silicon carbide fibers, α-olefin fibers having 2 or more polycarbons, polypropylene fibers, polyester fibers, and polyamide fibers may be blended.

[0182]

The cyclic olefin polymer composition according to the present invention is excellent in impact resistance, transparency and heat resistance, and is also excellent in its balance.

[0183]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

In the present invention, various physical property values were measured and evaluated as follows. (1) Intrinsic viscosity ([η]) It was measured at 135 ° C. in a decalin solution using an Ubbelohde viscometer. (2) Glass transition point (Tg) Using a DSC-220C manufactured by Seiko Instruments Inc., the temperature was measured at a temperature rising rate of 10 ° C./min in an N ₂ atmosphere. (3) Refractive index Using an Abbe refractometer (D line, 589 nm), 25 ° C
It was measured at. (4) Monomer composition ratio in polymer Measured by ¹³ C-NMR. (5) Iodine value Measured by the iodine monochloride method according to JIS K3331. (6) Preparation of test piece Using an injection molding machine IS50EPN manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold, molding was performed under the following molding conditions.

The test pieces were subjected to measurement after molding at room temperature for 48 hours. Molding conditions: Cylinder temperature: 260 ° C., mold temperature: 60 ° C., injection pressure primary / secondary = 1000/800 kg / cm ² (7) Light transmittance Using Shimadzu spectrophotometer MPS-2000, thickness The light transmittance was defined as the transmittance at a wavelength of 780 nm in the visible spectrum measured using a 2 mm press sheet as a sample. (8) Izod impact strength It was measured according to ASTM D256.

Test piece shape: 5/2 × 1/8 × 1/2 ^t inch (with notch) Test temperature: 23 ° C. (9) Heat distortion temperature (HDT) It was measured according to ASTM D648.

Test piece shape: 5 × 1/4 × 1/2 ^t inch Load: 264 psi

[0188]

[Production example]

Using vanadium catalyst [Synthesis of Copolymer a], ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene (hereinafter sometimes abbreviated as "TCD") and The copolymerization was continuously carried out by the following method.

1 liter glass polymerization equipped with stirrer
Cyclohexane solution of TCD from the top of the reactor into the polymerization reactor
So that the supply concentration of TCD is 60 g / liter
Was continuously supplied. Also, from the top of the polymerization reactor
VO (O.ethyl) Cl₂Cyclohexane solution
At a vanadium concentration of 0.5 mmol / liter in the polymerization vessel.
Ethyl Aluminum Sesquichlore
De (Al (C₂H_Five)_1.5Cl _1.5) Cyclohexane solution
The aluminum concentration in the polymerization vessel was 4.0 mmol / liter.
It is continuously fed into the polymerization vessel so that
It was In addition, ethylene was added to the polymerization system by using a bubbling tube.
6.0 liters / hour, nitrogen 35.0 liters / hour
During the period, hydrogen was supplied in an amount of 1.0 liter / hour.

Copolymerization reaction was carried out while the polymerization system was kept at 10 ° C. by circulating a heating medium in a jacket attached to the outside of the polymerization vessel. The polymerization solution of the copolymer produced by the above-mentioned copolymerization reaction is continuously conducted from the upper part of the polymerization vessel so that the polymerization solution in the polymerization vessel is always 1 liter (that is, the average residence time is 0.5 hours). I pulled it out. A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to terminate the polymerization reaction. Then, the aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the polymerization solution were brought into contact with each other under strong stirring with a homomixer at a ratio of 1: 1 to transfer the catalyst residue to the aqueous phase.
After leaving this contact mixture still, after separating and removing the aqueous phase,
Further, it was washed twice with distilled water to purify and separate the polymerization liquid phase.

Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer,
The solid portion was collected by filtration and thoroughly washed with acetone. Furthermore, in order to extract the unreacted TCD existing in the copolymer, this solid part was put into acetone so that the concentration became 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part was collected by filtration and dried at 130 ° C. and 350 mmHg for 12 hours under a nitrogen flow.

Ethylene.T obtained as described above
The CD copolymer has an intrinsic viscosity [η]; 0.53 dl / g, T
g; 140 ° C., TCD content was 36.5 mol%, iodine value was 0.1 g iodine / 100 g.
The results are shown in Table 1.

[Synthesis of Copolymer b] Toluene 239 ml
To a 1 liter-stainless steel autoclave charged with, was added norbornene (hereinafter sometimes abbreviated as "NB") (134 g) at room temperature under a nitrogen stream, and the mixture was stirred for 5 minutes. Subsequently, ethylene was circulated at normal pressure while stirring to create an ethylene atmosphere in the system. Keep the internal temperature of the autoclave at 70 ° C, and use ethylene to increase the internal pressure to 4 kg / cm ^2.
It was pressurized so that. After stirring for 10 minutes, 5.2 from the previously prepared toluene solution containing ethylenebis (indenyl) zirconium dichloride and methylalumoxane.
The copolymerization reaction of ethylene and NB was started by adding ml to the system. At this time, the catalyst concentration was 0.10 mmol / liter of ethylenebis (indenyl) zirconium dichloride and 20 mmol / liter of methylalumoxane with respect to the whole system.

During the polymerization, ethylene is continuously fed into the system.
The internal pressure is 4 kg / cm ²Held in. 20
After a minute, the polymerization reaction can be performed by adding isopropyl alcohol.
And stopped by. After depressurizing, take out the polymer solution,
An aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water
Using a homomixer at a ratio of 1: 1, contact with vigorous stirring.
The catalyst residue was transferred to the aqueous phase. Allow this contact mixture to
After placing, the aqueous phase is separated and removed, and then rinsed with distilled water.
The polymerization liquid phase was purified and separated twice.

Next, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and washed sufficiently with acetone. did. Further, in order to extract unreacted NB existing in the polymer, this solid part was put into acetone at 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid part is collected by filtration, and under nitrogen flow, 130 ° C., 350 mmHg
And dried for 12 hours.

The ethylene / norbornene copolymer obtained as described above has an intrinsic viscosity [η]; 0.60 dl /
g, Tg; 151 ° C., NB content is 47.0 mol%.
Met. Furthermore, the iodine value of the obtained copolymer is 0.
It was 2. The results are shown in Table 1.

[Synthesis of Copolymer c] In the synthesis of the copolymer a, ethylidene norbornene (hereinafter sometimes abbreviated as “ENB”) as a diene is adjusted to 0.9 g / liter, and ethylene is added. 36.0 liters / hour, nitrogen 35.0 liters / hour, hydrogen 1.0
Polymerization was performed in the same manner as in the case of the copolymer a except that the amount was supplied in the amount of 1 / hour. The results are shown in Table 1.

[Synthesis of Copolymers d to g] In the synthesis of the copolymer a, 5-phenyl-bicyclo [2,2,1] hept-ene (hereinafter referred to as "PhB
Abbreviated as “H”), and nitrogen and hydrogen were supplied in the amounts shown in Table 1.
Synthesis was carried out in the same manner as the copolymer a. The results are shown in Table 1.

[Synthesis of Copolymer h] In the synthesis of copolymer a, NB was used instead of TCD as the cyclic olefin, and NB was supplied so as to have the supply concentration shown in Table 1, and nitrogen and hydrogen were supplied. The synthesis was carried out in the same manner as the copolymer a, except that the amount of 1 was supplied. The results are shown in Table 1.

[Synthesis of Copolymer i] In the synthesis of copolymer d, except that PhBH and ENB were supplied at the supply concentrations shown in Table 1 and nitrogen and hydrogen were supplied in the amounts shown in Table 1, The synthesis was performed in the same manner as in the combination a. The results are shown in Table 1.

[0201]

Example 1 4 pellets of copolymer e (component [A]) were used.
00.0 g, 1 pellet of copolymer a (component [B])
600.0 g was weighed and mixed well in a plastic bag under a nitrogen atmosphere, and nitrogen substitution was carried out for 2 hours. The mixture was melt-blended by a twin-screw extruder (BT-30 manufactured by Plastic Engineering Laboratory Co., Ltd.) at a cylinder maximum temperature of 260 ° C. and a residence time of 1 minute, and pelletized by a pelletizer.

The pellets thus obtained were molded and evaluated. The light transmittance of the 2 mm thick sheet is 75%, the Izod impact strength is 7.1 kg · cm / cm, and it is 264 psi.
The lower heat distortion temperature was 122 ° C. The results are shown in Table 2.

[0203]

Example 2 Example 2 was repeated except that 600.0 g of pellets of the copolymer e (component [A]) and 1400.0 g of pellets of the copolymer a (component [B]) were used. Blending was carried out as in 1. The results are shown in Table 2.

[0204]

Example 3 The procedure of Example 1 was repeated except that the copolymer d ([A] component) and the copolymer b ([B] component) were used.
Blending was performed in the same manner as in Example 1. The results are shown in Table 2.

[0205]

Example 4 Blending was performed in the same manner as in Example 1 except that the copolymer b was used as the component [B]. The results are shown in Table 2.

[0206]

Example 5 Example 5 was repeated except that 500.0 g of pellets of copolymer f (component [A]) and 1500.0 g of pellets of copolymer a (component [B]) were used. Blending was carried out as in 1. The results are shown in Table 2.

[0207]

Comparative Example 1 Example 1 was repeated except that 400.0 g of pellets of copolymer g (component [A]) and 1600.0 g of pellets of copolymer a (component [B]) were used. Blending was carried out as in 1. The results are shown in Table 2.

When the Tg of the component (A) was out of the claimed range, it was shown that the composition had a low impact strength.

[0209]

Comparative Example 2 Example 2 was repeated except that 600.0 g of pellets of copolymer g (component [A]) and 1400.0 g of pellets of copolymer a (component [B]) were used in Example 1. Blending was carried out as in 1. The results are shown in Table 2.

When the Tg of the component [A] was out of the claimed range, it was shown that the impact strength of the composition was low even if the amount of the component [A] was increased.

[0211]

[Comparative Example 3] Example 3 except that 400.0 g of pellets of copolymer h (component [A]) and 1600.0 g of pellets of copolymer a (component [B]) were used in Example 1. Blending was carried out as in 1. The results are shown in Table 2.

It was shown that when the difference in refractive index between the component [A] and the component [B] was large, the transparency was poor.

[0213]

Comparative Example 4 Example 4 was repeated except that 400.0 g of pellets of the copolymer h (component [A]) and 1600.0 g of pellets of the copolymer b (component [B]) were used. Blending was carried out as in 1. The results are shown in Table 2.

It was shown that when the difference in refractive index between the component [A] and the component [B] was large, the transparency was poor.

[0215]

Example 6 In a dry nitrogen atmosphere, in a 1-liter glass flask, 3.0 g of copolymer i (component [A]),
12.0 g of copolymer c (component [B]) was charged, 470 ml of orthodichlorobenzene was added, and the mixture was heated to 160 ° C. to completely dissolve it and obtain a polymer solution.

Perfmill D (dicumyl peroxide, hereinafter sometimes abbreviated as "DCP") manufactured by NOF CORPORATION 0.1
5 g was dissolved in 30 ml orthodichlorobenzene.

While stirring at 160 ° C., the DCP solution was added dropwise to the polymer solution over 30 minutes to initiate a radical reaction. After that, the reaction is continued at 160 ° C. and 2 after the dropping is completed.
After a while, the heating was stopped and the mixture was allowed to cool to room temperature.

Then, the polymer solution was brought into contact with a large amount of acetone under vigorous stirring to precipitate a reaction product. Only white solids are separated by filtration and washed with a large amount of acetone to remove residual unreacted DCP.
Was removed. The solid part was collected by filtration, and under nitrogen flow,
It was dried at 130 ° C. and 350 mmHg for 12 hours.

The cyclic olefin polymer composition thus obtained had a light transmittance of 87%, an Izod impact strength of 5.1 kg.cm/cm, and a heat distortion temperature of 120.degree.
Met. The results are shown in Table 3.

[0220]

Example 7 A composition was prepared in the same manner as in Example 6 except that DCP was not supplied.
The results are shown in Table 3.

[0221]

Example 8 In a dry nitrogen atmosphere, in a 1-liter glass flask, 3.0 g of copolymer d (component [A]),
12.0 g of copolymer b (component [B]) was charged, 440 ml of orthodichlorobenzene was added, and the mixture was heated to 160 ° C. to completely dissolve it to obtain a polymer solution.

0.15 g of DCP was dissolved in 30 ml of orthodichlorobenzene. Separately, 0.30 g of divinylbenzene (sometimes abbreviated as “DVB” hereinafter) manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in 30 ml of ortho-dichlorobenzene.

With stirring at 160 ° C., the DCP solution and the DVB solution were added dropwise to the above polymer solution over 30 minutes to initiate a radical reaction. After that, the reaction was continued at 160 ° C., heating was stopped 2 hours after the completion of dropping, and the mixture was allowed to cool to room temperature.

Subsequently, the polymer solution was brought into contact with a large amount of acetone under vigorous stirring to precipitate a reaction product. Only white solids are separated by filtration and washed with a large amount of acetone to remove residual unreacted DC.
P and DVB were removed. The solid part was collected by filtration and dried under a nitrogen stream at 130 ° C. and 350 mmHg for 12 hours.

The evaluation results are shown in Table 3.

[0226]

Example 9 4 pellets of copolymer e (component [A]) were added.
00.0 g, copolymer a (component [B]) 1600.0
g, Perhexin 25B (trademark) manufactured by NOF CORPORATION (hereinafter “PH
25B "may be abbreviated) 4 g and DVB 8 g, and well mixed in a plastic bag under a nitrogen atmosphere,
The atmosphere was replaced with nitrogen for 2 hours. The mixture was melt-reacted by a twin-screw extruder (BT-30 manufactured by Plastic Engineering Laboratory Co., Ltd.) at a cylinder maximum temperature of 260 ° C. and a residence time of 1 minute, and pelletized by a pelletizer. The obtained pellets were molded and evaluated.

The results are shown in Table 3.

[0228]

[Table 1]

[0229]

[Table 2]

[0230]

[Table 3]

Claims (6)

[Claims] 1. [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
A cyclic olefin random copolymer obtained by [A-2] represented by the following formula [I] or [II],
Both are ring-opening polymers of one kind of cyclic olefin [A-3] represented by the following formula [I] or [II],
Both consist of hydrogenated products of ring-opening polymers of one type of cyclic olefin.
A cyclic olefin polymer selected from the group
Intrinsic viscosity [η] in decalin at 35 ° C is 0.5 to 5.0
dl / g, glass transition temperature measured by DSC
(Tg) is less than 15 ° C and derived from cyclic olefin
The content of constituent units is 3 mol% or more, and at 25 ℃
Measured refractive index n _D(A) is 1.500 to 1.650
A cyclic olefin polymer [A], [B-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
A cyclic olefin random copolymer obtained by [B-2] represented by the following formula [I] or [II],
Both are ring-opening polymers of one kind of cyclic olefin [B-3] represented by the following formula [I] or [II], at least
Both consist of hydrogenated products of ring-opening polymers of one type of cyclic olefin.
A cyclic olefin polymer selected from the group
Intrinsic viscosity [η] in decalin at 35 ° C is 0.1 to 5.0
dl / g, glass transition temperature measured by DSC
Refractive index (Tg) of 70 ° C. or higher, measured at 25 ° C.
n_D(B) 1.500 to 1.650 cyclic olefins
And the refractive index n of the cyclic olefin polymer [A]._D(A),
Refractive index n of cyclic olefin polymer [B]_DWith (B)
Difference Δn_D= | N_D(A) -n_D(B) | is less than 0.015
Yes, [A] / [B] (weight ratio) is 8/92 to 40/60
A cyclic olefin-based polymer composition characterized by:(In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹~ R¹⁸Nara
Bini R^aAnd R^bAre each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
A group may be formed), and(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹Or R^TenCarbon to which is bound
Child and R¹³The carbon atom to which is bound or R¹¹Combined
The carbon atoms that are present are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group, and n = m
When = 0, R¹⁵And R¹²Or R¹⁵And R¹⁹Is tied to each other
May combine to form a monocyclic or polycyclic aromatic ring
I). 2. [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the above formula
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
A cyclic olefin random copolymer obtained by [A-2] represented by the following formula [I] or [II],
Both are ring-opening polymers of one kind of cyclic olefin [A-3] represented by the following formula [I] or [II],
Both consist of hydrogenated products of ring-opening polymers of one type of cyclic olefin.
A cyclic olefin polymer selected from the group
Intrinsic viscosity [η] in decalin at 35 ° C is 0.5 to 5.0
dl / g, glass transition temperature measured by DSC
(Tg) is less than 15 ° C and derived from cyclic olefin
The content of constituent units is 3 mol% or more, and at 25 ℃
Measured refractive index n _D(A) is 1.500 to 1.650
A cyclic olefin polymer [A], [B-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
A cyclic olefin random copolymer obtained by [B-2] represented by the following formula [I] or [II],
Both are ring-opening polymers of one kind of cyclic olefin [B-3] represented by the following formula [I] or [II], at least
Both consist of hydrogenated products of ring-opening polymers of one type of cyclic olefin.
A cyclic olefin polymer selected from the group
Intrinsic viscosity [η] in decalin at 35 ° C is 0.1 to 5.0
dl / g, glass transition temperature measured by DSC
Refractive index (Tg) of 70 ° C. or higher, measured at 25 ° C.
n_D(B) 1.500 to 1.650 cyclic olefins
And the refractive index n of the cyclic olefin polymer [A]._D(A),
Refractive index n of cyclic olefin polymer [B]_DWith (B)
Difference Δn_D= | N_D(A) -n_D(B) | is less than 0.015
Yes, [A] / [B] (weight ratio) is 8/92 to 40/60
A cyclic olefin polymer composition containing an organic peroxide and, if necessary, a radically polymerizable polyfunctional compound.
Cyclic olefins formed by radical reaction in the presence of monomers
Polymer composition:(In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹~ R¹⁸Nara
Bini R^aAnd R^bAre each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
A group may be formed),(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹Or R^TenCarbon to which is bound
Child and R¹³The carbon atom to which is bound or R¹¹Combined
The carbon atoms that are present are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group, and n = m
When = 0, R¹⁵And R¹²Or R¹⁵And R¹⁹Is tied to each other
May combine to form a monocyclic or polycyclic aromatic ring
I). 3. [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
Is a cyclic olefin-based random copolymer obtained by
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.5
~ 5.0 dl / g, glass transition measured by DSC
Transfer temperature (Tg) is less than 15 ° C
The content of the constituent units derived from 3 mol% or more, 2
Refractive index n measured at 5 ° C _D(A) is 1.500 to 1.65
A cyclic olefin polymer [A] which is 0, [B-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
Is a cyclic olefin-based random copolymer obtained by
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.1
~ 5.0 dl / g, glass transition measured by DSC
Transfer temperature (Tg) was 70 ° C or higher, measured at 25 ° C
Refractive index n_D(B) is a ring with 1.500 to 1.650
A refining polymer [B], and a refractive index n of the cyclic olefin polymer [A]_D(A),
Refractive index n of cyclic olefin polymer [B]_DWith (B)
Difference Δn_D= | N_D(A) -n_D(B) | is 0.015 or less
And [A] / [B] (weight ratio) is 8/92 to 40/60.
A cyclic olefin-based polymer composition characterized by:(In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹~ R¹⁸Nara
Bini R^aAnd R^bAre each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
A group may be formed),(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹Or R^TenCarbon to which is bound
Child and R¹³The carbon atom to which is bound or R¹¹Combined
The carbon atoms that are present are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group, and n = m
When = 0, R¹⁵And R¹²Or R¹⁵And R¹⁹Is tied to each other
May combine to form a monocyclic or polycyclic aromatic ring
I). 4. [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
Is a cyclic olefin-based random copolymer obtained by
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.5
~ 5.0 dl / g, glass transition measured by DSC
Transfer temperature (Tg) is less than 15 ° C
The content of the constituent units derived from 3 mol% or more, 2
Refractive index n measured at 5 ° C _D(A) is 1.500 to 1.65
A cyclic olefin polymer [A] which is 0, [B-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one ring represented by [I] or [II]
Copolymerization of olefin and (iii) diene as required
Is a cyclic olefin-based random copolymer obtained by
And the intrinsic viscosity [η] in decalin at 135 ° C is 0.1
~ 5.0 dl / g, glass transition measured by DSC
Transfer temperature (Tg) was 70 ° C or higher, measured at 25 ° C
Refractive index n_D(B) is a ring with 1.500 to 1.650
A refining polymer [B], and a refractive index n of the cyclic olefin polymer [A]_D(A),
Refractive index n of cyclic olefin polymer [B]_DWith (B)
Difference Δn_D= | N_D(A) -n_D(B) | is less than 0.015
Yes, [A] / [B] (weight ratio) is 8/92 to 40/60
A cyclic olefin polymer composition containing an organic peroxide and, if necessary, a radically polymerizable polyfunctional compound.
Cyclic olefins formed by radical reaction in the presence of monomers
Polymer composition:(In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹~ R¹⁸Nara
Bini R^aAnd R^bAre each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
A group may be formed), and(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹Or R^TenCarbon to which is bound
Child and R¹³The carbon atom to which is bound or R¹¹Combined
The carbon atoms that are present are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group, and n = m
When = 0, R¹⁵And R¹²Or R¹⁵And R¹⁹Is tied to each other
May combine to form a monocyclic or polycyclic aromatic ring
I). 5. [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula [I:
I] represented by at least one cyclic olefin,
A ring obtained by copolymerizing (iii) a diene, if necessary.
Olefin-based random copolymer having a temperature of 135 ° C
Intrinsic viscosity [η] in decalin is 0.5-5.0 dl / g
Yes, the glass transition temperature (Tg) measured by DSC
Compositions below 15 ° C and derived from cyclic olefins
The content of the unit is 3 mol% or more, and the measured value at 25 ° C
Folding rate n _DCyclic ole in which (A) is 1.500 to 1.650
Fin-based polymer [A], [B-1] (i) α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one cyclic olefin represented by [I]
And (iii) diene, if necessary,
A cyclic olefin-based random copolymer having
Intrinsic viscosity [η] in decalin at ℃ is 0.1-5.0dl /
g, and the glass transition temperature (T
g) is 70 ° C. or higher, and the refractive index n measured at 25 ° C._D
Cyclic olefins in which (B) is 1.500 to 1.650
The polymer [B] and the refractive index n of the cyclic olefin polymer [A]_D(A),
Refractive index n of cyclic olefin polymer [B]_DWith (B)
Difference Δn_D= | N_D(A) -n_D(B) | is 0.015 or less
And [A] / [B] (weight ratio) is 8/92 to 40/60.
A cyclic olefin polymer composition comprising: [Chemical 9](In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹~ R¹⁸Nara
Bini R^aAnd R^bAre each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
A group may be formed),(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹Or R^TenCarbon to which is bound
Child and R¹³The carbon atom to which is bound or R¹¹Combined
The carbon atoms that are present are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group, and n = m
When = 0, R¹⁵And R¹²Or R¹⁵And R¹⁹Is tied to each other
May combine to form a monocyclic or polycyclic aromatic ring
I). 6. [A-1] (i) an α-olefin having 2 or more carbon atoms, and (ii) the following formula [I:
I] represented by at least one cyclic olefin,
A ring obtained by copolymerizing (iii) a diene, if necessary.
Olefin-based random copolymer having a temperature of 135 ° C
Intrinsic viscosity [η] in decalin is 0.5-5.0 dl / g
Yes, the glass transition temperature (Tg) measured by DSC
Compositions below 15 ° C and derived from cyclic olefins
The content of the unit is 3 mol% or more, and the measured value at 25 ° C
Folding rate n _DCyclic ole in which (A) is 1.500 to 1.650
Fin-based polymer [A], [B-1] (i) α-olefin having 2 or more carbon atoms, and (ii) the following formula:
At least one cyclic olefin represented by [I]
And (iii) diene, if necessary,
A cyclic olefin-based random copolymer having
Intrinsic viscosity [η] in decalin at ℃ is 0.1-5.0dl /
g, and the glass transition temperature (T
g) is 70 ° C. or higher, and the refractive index n measured at 25 ° C._D
Cyclic olefins in which (B) is 1.500 to 1.650
The polymer [B] and the refractive index n of the cyclic olefin polymer [A]_D(A),
Refractive index n of cyclic olefin polymer [B]_DWith (B)
Difference Δn_D= | N_D(A) -n_D(B) | is less than 0.015
Yes, [A] / [B] (weight ratio) is 8/92 to 40/60
A cyclic olefin polymer composition containing an organic peroxide and, if necessary, a radically polymerizable polyfunctional compound.
Cyclic olefins formed by radical reaction in the presence of monomers
Polymer composition:(In the formula [I], n is 0 or 1, and m is 0 or positive.
Is an integer, q is 0 or 1, and R¹~ R¹⁸Nara
Bini R^aAnd R^bAre each independently a hydrogen atom,
Rogen atom or hydrocarbon group, R¹⁵~ R¹⁸Are mutual
May be bonded to each other to form a monocycle or polycycle, or
The monocycle or polycycle may have a double bond,
R¹⁵And R¹⁶Or with or R¹⁷And R¹⁸And Alkylidene
A group may be formed),(In the formula [II], p and q are 0 or an integer of 1 or more.
, M and n are 0, 1 or 2, and R¹~ R¹⁹Is
Independently hydrogen atom, halogen atom, aliphatic hydrocarbon
Elementary groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups or
R is a Coxy group⁹Or R^TenCarbon to which is bound
Child and R¹³The carbon atom to which is bound or R¹¹Combined
The carbon atoms that are present are either directly or having 1 to 3 carbon atoms.
May be bonded via an alkylene group, and n = m
When = 0, R¹⁵And R¹²Or R¹⁵And R¹⁹Is tied to each other
May combine to form a monocyclic or polycyclic aromatic ring
I).