JPH10120767A - Cyclic olefin-based copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer composed of each specific recurring units in specified proportions, excellent in transparency, optical isotropy, hydrophilicity and heat resistance, and useful for optical materials, etc. SOLUTION: This copolymer is composed of (A) 2-80mol% of recurring unit of formula I ((p) and (q) are each 0 or 1; R<1> to R<10> are each H or methyl; R<11> and R<12> are each a 1-10C alkyl or 5-10C cycloalkyl) and (B) 98-20mol% of recurring unit of formula II [(r) is 0 or 1; R<a> to R<h> are each H or methyl; R<i> to R<l> are each H, a 6-10C aromatic hydrocarbon or 1-10C (un)saturated hydrocarbon]. This copolymer is obtained by ring opening copolymerization between a polar cyclic olefin of formula III and a nonpolar cyclic olefin of formula IV preferably followed by hydrogenation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic olefin useful for optical materials such as optical discs, substrate materials for liquid crystal displays and optical lenses, medical fields such as disposable syringes and pharmaceutical containers, organic glasses and lenses for glasses. The present invention relates to a system copolymer and a method for producing the same.

[0002]

2. Description of the Related Art Cyclic olefin polymers are excellent in optical properties such as transparency and low birefringence, thermal stability, surface hardness, etc., and are used in optical materials, medical materials, organic glasses, lenses for glasses, etc. A wide range of applications is expected.

[0003] In recent years, in the field of optical recording, the wavelength of lasers has been shortened with the increase in density. However, polycarbonate, which is mainly used for the current optical disc substrate, has excellent heat resistance and high light transmittance, but has a large birefringence of light and absorbs light in the blue region. Is not considered appropriate.
Further, polycarbonate has high heat resistance, but has a problem that warpage due to moisture absorption occurs because the water absorption is too high. Therefore, a new material having excellent dimensional stability, small birefringence, and small light absorption even in the blue region is desired.

As such a material, a cyclic olefin polymer has been proposed. This polymer is an excellent material that has excellent heat resistance and does not contain an aromatic group, has low absorption in the blue region, and has a small birefringence. These are obtained by ring-opening polymerization of a cyclic olefin (US Pat. No. 2,932,630, Japanese Patent Publication No. 41-20111, etc.). Further, the unsaturated bonds remaining in the ring-opened polymer are further hydrogenated (JP-A-51-80400, JP-A-60-80400).
-26024) to improve light resistance and weather resistance.

[0005] Cyclic olefin polymers which do not contain a polar group (JP-A-60-26024, JP-A-6-26024)
No. 0-168708 and JP-A-63-218726) and those containing polar groups such as esters and nitriles (JP-A-48-100500, JP-A-49-77).
999, JP-A-1-132625, JP-A-1-132626, etc.) are known.

[0006] A cyclic olefin polymer containing no polar group has a low water absorption, and is therefore excellent in fields requiring dimensional stability such as optical lenses. However, surface processing of optical discs and substrates for liquid crystal displays (for example,
In fields requiring lamination of a metal thin film, hard coating for increasing surface hardness, lamination with other materials, etc., it is known that adhesion and adhesion are poor.

On the other hand, a ring-opened polymer of a cyclic olefin containing a polar group or a hydrogenated polymer thereof has good adhesiveness and adhesion, but has a water absorption as high as polycarbonate and poor dimensional stability after molding. As such a polymer, for example, a ring-opening polymer comprising a cycloaddition product of a cyclopentadiene and a methacrylate ester or a maleate ester (Diels-Alder adduct) has been proposed (JP-A-1-
No. 132625).

[0008] It is also a very important technical problem to balance the adhesion between a metal thin film and a hard coat agent, heat resistance, and dimensional stability in organic glasses and eyeglass lenses. Unresolved. At the same time, organic glass and eyeglass lenses are often used after dyeing, and high dyeing properties are required. For such a purpose, a cyclic olefin-based polymer containing no polar group is not preferred, and a cyclic olefin-based copolymer containing an appropriately polar group is preferred.

However, in the ring-opening copolymerization of a cyclic olefin containing no polar group such as cyclopentadiene and a cyclic olefin containing a polar group, a catalyst (Ziegler-type catalyst) used for ring-opening polymerization of a nonpolar cyclic olefin is used. Catalyst) has a problem of low activity. Conversely, the catalyst used for ring-opening polymerization of polar cyclic olefins has a problem that if the proportion of the polar cyclic olefin is small, gelation occurs, and it is difficult to obtain a copolymer stably over a wide composition range. .

As described above, without impairing the heat resistance and dimensional stability which are the original characteristics of the cyclic olefin polymer,
In spite of the demand for a material having adhesiveness, adhesion, and dyeing properties, the reality is that there are few excellent materials that satisfy both in a well-balanced manner.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a cyclic olefin polymer, particularly a ring-opening polymer or a ring-opening / hydrogenated polymer, which does not impair heat resistance, optical properties, and dimensional stability. An object of the present invention is to provide a novel cyclic olefin-based ring-opening polymer and a ring-opening / hydrogenated copolymer having adhesiveness, adhesion, and dyeability according to use and purpose.

[0012]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have obtained a cycloadduct (Diels) of an itaconate ester containing two polar ester groups on the same carbon as cyclopentadiene. -Alder adduct) was found to copolymerize with cyclic olefins containing no polar group in a wide copolymerization composition range with high activity without causing undesirable gelling. In addition, they have found that a copolymer having a good balance between the glass transition point and the hydrophilicity can be easily obtained, and have reached the present invention.

That is, the present invention relates to a compound represented by the following general formula (1):

[0014]

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Wherein p and q are each independently 0 or 1, R ^{1 to} R ¹⁰ are the same or different and are a hydrogen atom or a methyl group, R ¹¹ and R ¹² are the same or different and are alkyl having 1 to 10 carbon atoms. Or a cycloalkyl group having 5 to 10 carbon atoms. And a repeating unit represented by the following general formula (2):

[0016]

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Wherein r is 0 or 1, and R ^{a to} R
^h are the same or different hydrogen atom or a methyl group, R ⁱ ~
R ¹ is the same or different and is a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. Where R ⁱ and R ^j , R ^k and R ^l
May form an unsaturated bond in cooperation with each other;
ⁱ or R ^j and R ^k or R ¹ may form a ring. ] The unsaturated cyclic olefin-based copolymer (I) comprising a repeating unit represented by the formula (I):

The present invention also relates to a compound represented by the following general formula (3):

[0019]

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Wherein p and q are 0 or 1, and R ^1-
R ¹⁰ is the same or different and is a hydrogen atom or a methyl group,
R ¹¹ and R ¹² are the same or different and are an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. And a repeating unit represented by the following general formula (4):

[0021]

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[Wherein r is 0 or 1, and R ^{a to} R
^h are the same or different hydrogen atom or a methyl group, R ^w ~
R ^z is the same or different and is a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a saturated hydrocarbon group having 1 to 10 carbon atoms. Here, R ^w or R ^x and R ^y or R ^z may form a ring. And a saturated cyclic olefin-based copolymer (II) comprising a repeating unit represented by the formula: In addition, the present invention provides the following general formula (5)

[0023]

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Wherein p and q are 0 or 1, and R ¹
To R ¹⁰ are the same or different and are each a hydrogen atom or a methyl group;
¹¹ and R ¹² are the same or different and are an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. ]
And the following general formula (6)

[0025]

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[Wherein r is 0 or 1, and R ^{a to} R
^h are the same or different hydrogen atom or a methyl group, R ⁱ ~
R ¹ is the same or different and is a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. Where R ⁱ and R ^j , R ^k and R ^l
May form an unsaturated bond in cooperation with each other;
and ⁱ or R ^j, and R ^k or R ^l may form a ring. And a method for producing an unsaturated cyclic olefin-based copolymer, which is obtained by ring-opening copolymerization with the non-polar cyclic olefin represented by the formula

The present invention also includes a method for producing the above-mentioned saturated cyclic olefin copolymer (II) by hydrogenating the above-mentioned unsaturated cyclic olefin copolymer (I).

Further, the present invention provides an optical material mainly comprising an unsaturated cyclic olefin copolymer (I) and an optical material mainly comprising a saturated cyclic olefin copolymer (II).

Hereinafter, the present invention will be described in detail.

(Unsaturated cyclic olefin-based copolymer (I)) The unsaturated cyclic olefin-based copolymer (I) of the present invention comprises 2 to 80 mol% of the repeating unit represented by the above general formula (1) ( Hereinafter, it may be referred to as a polar unit) and 98 to 20 mol% of the repeating unit represented by the general formula (2) (hereinafter, may be referred to as a nonpolar unit).

The substituent R in the polar unit represented by the formula (1)
^{1 to} R ¹⁰ are the same or different and are a hydrogen atom or a methyl group. Of these, from the availability of polymerization raw materials,
Particularly, a hydrogen atom is preferable.

R ¹¹ and R ¹² are the same or different and are an alkyl group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, preferably 5 to 8 carbon atoms. The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group and a 2-ethylhexyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. These may be appropriately selected in consideration of desired physical properties such as heat resistance and hydrophilicity. In general, a bulky alkyl or cycloalkyl group has a small effect of increasing hydrophilicity and a large decrease in heat resistance. From this perspective,
A methyl group, an ethyl group, an isopropyl group and the like are particularly preferably used.

Q is 0 or 1. A recurring unit of 1 is generally preferable to a recurring unit of q having a higher heat resistance than a recurring unit of q = 0. However, the former is more advantageous in terms of the price of the raw material monomer.

P is 0 or 1. The repeating unit in which p is 0 is derived from a cycloadduct monomer of cyclopentadiene and methylidene malonate. On the other hand, the repeating unit in which p is 1 is derived from a cycloadduct monomer of cyclopentadiene and itaconic acid ester. These may also be selected in consideration of the physical properties of the obtained copolymer, but the latter is more preferable in terms of availability of monomers and economy.

These polar units are derived from the polar cyclic olefin represented by the above formula (5). Illustrating a suitable combination of these in the form of a polar cyclic olefin,

[0036]

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5-methoxycarbonyl-5-methoxycarbonylmethyl-bicyclo [2,2,1] heptene-
2,

[0038]

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5-ethoxycarbonyl-5-ethoxycarbonylmethyl-bicyclo [2,2,1] heptene-
2,

[0040]

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5-Isopropoxycarbonyl-5-isopropoxycarbonylmethyl-bicyclo [2,2,1]
Hepten-2,

[0042]

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[0043] 7-methoxycarbonyl-7-methoxycarbonylmethyl - tetracyclo [6,2,1,1 ^{6, 9,}
0 ^{5, 10} ] dodecene-2,

[0044]

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[0045] 7-ethoxycarbonyl-7-ethoxycarbonylmethyl - tetracyclo [6,2,1,1 ^{6, 9,}
0 ^{5, 10} ] dodecene-2,

[0046]

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7-isopropoxycarbonyl-7-isopropoxycarbonylmethyl-tetracyclo [6,2
1,1 ^{6, 9,} 0 ^{5, 10]} such as dodecene-2 and the like.

[0048] R ^a ~ in apolar unit represented by formula (2)
R ^h are the same or different and are each a hydrogen atom or a methyl group;
ⁱ to R ^l are the same or different hydrogen atom, a carbon number 6 to 10
Or a saturated or unsaturated hydrocarbon having 1 to 10 carbon atoms. Examples of the aromatic group having 6 to 10 carbon atoms include aryl groups such as a phenyl group and a naphthyl group, and these may be substituted with an alkyl group having 1 to 3 carbon atoms. Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 3 carbon atoms such as a methyl group and an ethyl group, and 5 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
And 10 to 10 cycloalkyl groups. 1 to 1 carbon atoms
Examples of the 0 unsaturated hydrocarbon group include an alkenyl group such as a vinyl group and a propenyl group.

[0049] wherein R ⁱ and R ^j, R ^k and R ^l may form an unsaturated bond with each cooperate, R ⁱ or R
^j and R ^k or R ¹ may form a ring.

The fact that R ⁱ and R ^j (R ^k and R ^l ) together form an unsaturated bond is as follows.

[0051]

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(However, R ^m and R ⁿ represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 9 carbon atoms.)
Refers to those that form bonds. For example, R ⁱ and R
^j (R ^k and R ^l) cooperate to ethylidene, refers to a case such as to form a propylidene group.

The fact that R ⁱ or R ^j and R ^k or R ^l form a ring means that R ⁱ and R ^k , R ⁱ and R ^l , R ^j and R ^k , and R ^j and R ^l A bond in which at least one pair forms a ring. For example, it refers to a case in which R ⁱ and R ^l combine to form an alkyl group having 5 to 10 carbon atoms such as a pentylene group and a hexylene group, and form a ring as a whole.

R is 0 or 1. The heat resistance of a repeating unit with r of 1 is higher than that of a repeating unit with r of 0. However, these may be selected in consideration of desired physical properties, moldability, availability of raw materials, and the like.

The nonpolar unit represented by the formula (2) is derived from the nonpolar cyclic olefin represented by the formula (6). Preferred compounds in the form of this nonpolar cyclic olefin include:

[0056]

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Bicyclo [2,2,1] heptene-2 (norbornene),

[0058]

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5-ethylidenebicyclo [2,2,1] heptene-2,

[0060]

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Dicyclopentadiene

[0062]

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Tricyclopentadiene

[0064]

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[0065] tetracyclo [6,2,1,1 ^{6, 9,} 0 ^5,
10 ] Dodecene-2,

[0066]

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7-ethylidenetetracyclo [6,2,
1,1 ^{6, 9,} 0 ^{5, 10]} dodecene -2,

[0068]

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5-phenylbicyclo [2,2,1] heptene-2,

[0070]

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7-phenyltetracyclo [6,2,1,
1 ^{6, 9,} 0 ^{5, 10]} dodecene -2, and the like.

Among them, tetracyclo [6,2,1,16 ^,
9, 0 ^{5, 10]} dodecene-2,7-ethylidene tetracyclo [6,2,1,1 ^{6, 9,} 0 ^{5, 10]} dodecene -2 tetracyclododecene derivatives and polar norbornene-based compounds such as Can obtain a copolymer having high heat resistance and is particularly preferably used for applications such as optical disk substrates. From tetracyclododecene compounds, bicyclo [2,2,1] heptene-2 and 5-ethylidenetetracyclo [2,2,
1] A polymer having much higher thermal stability than a corresponding norbornene-based compound such as heptene-2 can be obtained.

The unsaturated cyclic olefin-based copolymer (I) of the present invention comprises 2 to 80 mol%, preferably 5 to 50 mol% of the repeating unit represented by the above formula (1);
20 mol%, preferably 95 to 50 mol% of the formula (2)
And a repeating unit represented by

(Saturated cyclic olefin copolymer (II))
The saturated cyclic olefin copolymer (II) of the present invention has 2 to 2 parts.
80 mol%, preferably 5 to 50 mol% of the repeating unit represented by the above formula (3), 98 to 20 mol%, preferably 95 to 50 mol% of the repeating unit represented by the above formula (4) Consists of

R ^{1 to} R ¹² , p and q in the formula (3) are the same as those in the formula (1). R ^{a to} R ^h and r in the formula (4) are the same as in the formula (2), and R ^{w to} R ^z also have the formula (2) except that they do not contain an unsaturated hydrocarbon group having 1 to 10 carbon atoms. Is the same as).

The molecular weights of the unsaturated cyclic olefin copolymer (I) and the saturated cyclic olefin copolymer (II) in the present invention are both 0.5 g / dl using toluene as a solvent.
The reduced viscosity at 30 ° C. of a solution having a concentration of ηsp / c =
A range of 0.2 to 5 dl / g, preferably 0.3 to 3 dl / g is used. If it is less than this, the mechanical properties of the molded product become insufficient, and if it exceeds this, the melt viscosity becomes too high and molding becomes difficult.

(Unsaturated cyclic olefin copolymer (I)
In the present invention, the unsaturated cyclic olefin-based copolymer (I) is obtained by ring-opening polymerization of a polar cyclic olefin represented by the above formula (5) and a nonpolar cyclic olefin represented by the above formula (6). Is obtained. The ring-opening polymerization is preferably performed in the presence of a metathesis polymerization catalyst system. Further, it is preferable to carry out the reaction in an inert solvent. The details will be described below.

In the polar cyclic olefin represented by the above formula (5), p, q, R ^{1 to} R ¹² represent p, q, R
Is the same as ^{1 ~R 12.} Such a cyclic olefin can be produced by a cycloaddition reaction (Diels-Alder reaction) in which the corresponding cyclopentadiene or a derivative thereof is used as a diene component and the corresponding methylenemalonic acid ester or itaconic acid ester is used as a parent diene component.

Further, r and R ^{a to} R ^l in the nonpolar cyclic olefin represented by the above formula (6) are the same as those of the above formula (2).
is the same as ^{a ~R l.} Such a cyclic olefin can be produced by a cycloaddition reaction between cyclopentadiene or a derivative thereof and a corresponding diene parent compound.

In the present invention, the charged composition of the polar cyclic olefin represented by the above formula (5) and the nonpolar cyclic olefin represented by the above formula (6) depends on the types of both, the conversion,
The ratio should be appropriately selected according to the type of the catalyst, and the ratio between the polar unit and the nonpolar unit in the produced polymer does not always match. When the conversion is 100%, the charged composition matches the polymer composition. However, when the conversion is controlled to be low, the highly reactive component is polymerized preferentially. Get higher. In the present invention, the charged molar ratio of the polar cyclic olefin (5) to the nonpolar cyclic olefin (6) is in the range of 1:99 to 80:20, preferably 5:95 to 60:40. More preferably, a range of 10:90 to 50:50 is used.

The metathesis polymerization catalyst system is composed of the following two components (A) and (B).

The component (A) generally has a metathesis
Halides such as W, Mo, Re, etc.
Coxy compounds, halogenated alkoxy compounds, oxylated
Compounds, halogenated oxy compounds, carboxylate, acetyl
Luacetonate complex, carbonyl complex, acetonitrile
Complexes, phosphine complexes, pyridine complexes, or these
At least one compound selected from complex complexes, etc.
Specifically, WCl ₆, WCl_Five, WBr₆, W
I₆, MoCl₆, MoCl_Five, MoCl_Four, ReCl
_Three, MOCl_Four, ReOCl_Three, ReOBr_Three, W (O
C₆H_Five)_FourCl_Two, Mo (OC₆H_Five)_FourCl_Two, W
(OC_TwoH_Five)_Four, WO_Two(Acac)_Two, WO (C
O)₆, Mo (CO)₆, WCl₆(PPh_Three)_Two, W
Cl₆(C_FiveH_FiveN)_Two, W (CO)_Three(CH_TwoN)_Two
And preferably WCl.₆, MoCl_FiveUse
Can be. (However, PPh_ThreeIs triphenylphosphine,
acac represents acetylacetonate. ) As the component (B), groups (I) to (III) of the long period rate table
At least one of the elements alkyl, hydride, halogen
At least one compound selected from
To Li (CH_Three), Li (n-C_FourH₉), Al (CH
_Three)_Three, Al (C_TwoH_Five)_Three, Al (i-C
_FourH₉)_Three, AlCl_{1. Five}(C_TwoH_Five)_{1. Five}, AlCl
_Two(C_TwoH_Five)_Three, AlH (C_TwoH_Five)_TwoEtc.
And preferably Al (C_TwoH_Five)_Three, Al (i-C_Four
H₉)_ThreeIs used.

The component (A) and the component (B) are used in an element ratio of 1: 1 to 1:20, preferably 1: 2 to 1:10. If the proportion of the component (B) is less than this, a sufficient polymerization activity cannot be obtained, and if it exceeds this, the active species are excessively reduced and inactivated, which is not preferable.

In general, a metathesis catalyst containing a transition metal complex of an earlier period such as Ti as one component is also used for ring-opening polymerization of a nonpolar olefin. However, such a catalyst is not covered by a polar group in a polar monomer. Poisoning has low polymerization activity.

If necessary, in addition to the above components, the following component (C) may be added as an additive to enhance the activity,
Unwanted gelation can be suppressed. As such additives, trace amounts of water, alcohols, esters, carboxylic acids or anhydrides thereof, ethers, peroxides, aldehydes, ketones, amines, amides, nitrone compounds, azo compounds And heteroorganic compounds such as Among them, tetrahydrofuran,
Cyclic ethers such as dioxane, trioxane, 1,3-dioxolan, and paraaldehyde, ethers such as diethyl ether, and esters such as benzoate and phthalate are used. The use amount of these additives is not particularly limited, and may be selected in consideration of the activating effect and the gelation suppressing effect. Generally, the molar ratio of the additives to the active species is in the range of 2 to 500. Can be If it is less than this, the effect of addition is not recognized, and if it exceeds this, not only the effect of adding is not observed, but also purification becomes difficult, which is not preferable.

In general, when a nonpolar cyclic olefin (6) is subjected to ring-opening polymerization using a metathesis polymerization catalyst system, a gel often occurs. However, in the present invention, even when the polar cyclic olefin (5) and the nonpolar cyclic olefin (6) are copolymerized, a copolymer can be obtained without gelation. This is presumably because the monomer (5) containing a specific polar group acts on the catalytically active site to suppress gelation. Furthermore, in the present invention, gelation does not occur even when the ratio of the polar cyclic olefin (5) to the nonpolar cyclic olefin (6) is small. This is because the polar cyclic olefin (5) used in the present invention has two carbon atoms on the same carbon.
It is considered that the gelation is suppressed by efficiently coordinating to the active site of the catalyst because of containing the ester groups.

In the present invention, the molecular weight of the resulting copolymer can be controlled by adding an appropriate amount of a compound having at least one carbon-carbon unsaturated bond in the molecule in addition to α-olefin. Such compounds include 1-hexene, 1-octene and the like.

In the present invention, the ring-opening polymerization is preferably carried out in an inert solvent. The solvent is used for the purpose of adjusting the viscosity of the polymerization system, absorbing the heat of polymerization, and allowing the reaction to proceed smoothly. The inert solvent is a solvent that not only dissolves the used monomer and catalyst but also does not deactivate the polymerization catalyst. As such a solvent, generally, a paraffinic nonpolar solvent such as hexane and heptane, and an aromatic hydrocarbon solvent such as toluene and xylene are preferably used. The amount of the solvent may be selected in consideration of the effect of suppressing thickening due to polymerization and the effect of removing heat of polymerization, and is generally 0.5 to 100 times, preferably 1 to 100 times the weight of the monomer used.
A range of 0 times is used. If the amount is less than this, the effect of the solvent is not recognized. If the amount exceeds the amount, not only the effect of increasing the amount is not recognized, but also water or oxygen contained in the solvent is not preferable because it deactivates the catalyst. In addition, the step of isolating and purifying the obtained polymer is not preferable because it is complicated. However, a small amount of water in the solvent has an effect of improving the catalytic activity.

In the present invention, the reaction is carried out at 0 to 120 ° C.
It is preferably carried out in the range of 20 to 80 ° C. If it is less than the above range, the reaction rate will be low. If it exceeds the range, it is not preferable because side reactions occur and the catalyst is deactivated.

The unsaturated cyclic olefin copolymer (I) thus obtained is isolated and purified by a method known per se after deactivating the catalyst. The deactivation of the catalyst generally occurs with hydrochloric acid,
Inorganic acids such as sulfuric acid and acetic acid and organic acids are used. For isolation and purification, a so-called reprecipitation method in which a polymerization solution is mixed with a non-solvent for a polymer is generally employed. The non-solvent is not particularly limited, but generally, methanol, ethanol, isopropanol and the like are used. However, in the present invention, when the unsaturated cyclic olefin-based copolymer (I) is further hydrogenated into the saturated cyclic olefin-based copolymer (II), the unsaturated cyclic olefin-based copolymer (II) may be used. Polymer (I) without isolation and purification
Subsequently, a hydrogenation reaction can be performed.

(Production of saturated cyclic olefin copolymer (II)) The saturated cyclic olefin copolymer (II) of the present invention
Can be produced by a hydrogenation reaction of the unsaturated cyclic olefin copolymer (I).

The hydrogenation reaction is preferably carried out by dissolving the unsaturated cyclic olefin copolymer (I) obtained above in an inert solvent and under normal pressure or pressure in the presence of a hydrogenation catalyst.

As the hydrogenation catalyst, Ti, Ni, Ru, R
Examples include a soluble catalyst using a metal element such as h, Pd, and Pt or a compound thereof, or a heterogeneous catalyst in which the metal element is supported on an inorganic compound such as silica or alumina. Preferably, RhCl (PPh ₃ ) ₃ , RuClH (CO) (P
A platinum group complex such as Ph ₃ ) ₃ is used. The amount of catalyst is
Although it depends on its activity and reaction conditions, it is usually 5 to 500 ppm, preferably 10 to 300 pp, based on the polymer.
m is used. If it is less than this, hydrogenation does not proceed sufficiently, and if it exceeds this, it is difficult to remove the catalyst, which is not preferable.

The inert solvent is a solvent that does not substantially deactivate the hydrogenation catalyst, and specific examples thereof include solvents used for ring-opening polymerization. The amount of the solvent used is not particularly limited, but is selected in consideration of the solution viscosity, isolation and purification. Usually, the range of 1 to 50 times, preferably 2 to 20 times the amount of the unsaturated cyclic olefin copolymer (I) is used. If it is less than this, the viscosity of the system becomes too high, and if it exceeds this, it takes a burden on isolation and purification, which is not preferable.

The reaction may be carried out at normal pressure or under pressure in a closed system. However, since the method of blowing hydrogen at normal pressure is not industrially efficient, it is preferably performed under pressure. In this case, the pressure is 5-100 kg / c
m ² , preferably in the range of 10 to 50 kg / cm ² . If it is less than this, the amount of dissolved hydrogen in the reaction system is insufficient, and the reaction does not proceed efficiently, so that the pressurizing effect is small. On the other hand, if it exceeds this, it is not preferable because the load on the high-pressure technology increases.

The reaction is carried out usually at a temperature of 50 to 300 ° C., preferably 100 to 200 ° C. Below that,
It is not preferable because the reaction slows down, and if it exceeds it, it is not preferable because side reactions occur simultaneously.

(Analysis, Molding, etc.) The unsaturated cyclic olefin-based copolymer (I) and the saturated cyclic olefin-based copolymer (II) obtained by the present invention generally have an infrared absorption spectrum and a nuclear magnetic resonance spectrum. The structure can be confirmed by an analysis means such as. As the molecular weight, a value of a reduced solution viscosity [ηsp / c (dl / g)] measured at 30 ° C. using a 0.5 g / dl toluene solution at the present invention is used. ] And gel permeation chromatography.

The unsaturated cyclic olefin copolymer (I) and the saturated cyclic olefin copolymer (II) obtained according to the present invention can be formed into a molded product and a film by a conventional injection molding method or melt extrusion molding method. Each can be formed into a sheet. The temperature of the molten resin at the time of molding is set in consideration of the melt viscosity and the thermal decomposition temperature of the copolymer to be used, but is generally 200 to 350 ° C., preferably 240 to 3 ° C.
A range of 00 ° C is employed. If it is less than this, a uniform molded product cannot be obtained due to low resin fluidity, and if it exceeds that, coloring due to decomposition of the resin occurs, and both are not preferred. Further, a small amount of a deterioration inhibitor such as Irganox 1010 (manufactured by Chiga Geigy) may be added to suppress the thermal decomposition of the resin of the present invention.

[0099]

According to the method disclosed in the present invention, the polar cyclic olefin (5) and the cyclic olefin (6) are efficiently subjected to ring-opening polymerization and hydrogenation reaction, and the polar unit (1) and the non-polar unit ( It is possible to obtain an unsaturated cyclic olefin polymer (I) containing 2) in a wide composition range, and a saturated cyclic olefin polymer (II) containing a polar unit (3) and a nonpolar unit (4) in a wide composition range. I can do it. The resulting polymer has a balance between units containing polar groups and units not containing,
By performing melt molding and dry molding, it is possible to provide a molded article having excellent properties such as heat resistance, optical properties, water absorption, adhesion, and adhesion. As a result, the material can be applied to a wide range of optical materials, medical fields, organic glasses, glasses, and the like.

[0100]

EXAMPLES The present invention will be described below with reference to examples, but it goes without saying that the present invention is not limited to the following examples.

The methods for measuring physical properties used in this example are shown below.

(1) Glass transition temperature (Tg): Measured by differential scanning calorimetry (DSC).

(2) The transmittance and the haze value were measured according to ASTM.
It was measured by the D1003 method.

(3) The water absorption was measured by the ASTM D570 method.

(4) The bending strength was measured according to the ASTM D790 method.

(5) Impact strength was measured by ASTM D256 method.

(6) The cross cut test is performed by peeling 100 squares formed by making 11 cuts at intervals of 1 mm in length and width in an aluminum layer formed by a sputtering method on a smooth resin plate, using tape. went.

(7) The reduced viscosity was measured at 30 ° C. using a solution having a concentration of 0.5 g / dl using toluene as a solvent.

Example 1 5-methoxycarbonyl-5
-Methoxycarbonylmethyl-bicyclo [2,2,1]
Heptene-2, 85 parts by weight (hereinafter referred to as monomer (a)), 7-ethylidenetetracyclo [6,2,1,16 ^,
9, 0 ^{5, 10]} dodecene -2 (hereinafter referred to monomer (b)) 178 parts by weight of toluene 450 parts by weight as a solvent,
As a catalyst component, 1.0 part by weight of WCl _6, 2.0 parts by weight of triisobutylaluminum and 0.5 part of paraaldehyde are used.
Parts by weight and 0.3 parts by weight of 1-hexene as a molecular weight regulator were charged into a reaction vessel and reacted at 25 ° C. for 1 hour. During the reaction, no polymer precipitation due to gelation was observed. After completion of the reaction, the obtained reaction mixture was poured into methanol to precipitate. The precipitated white precipitate was separated by filtration, washed and dried to obtain 140 parts by weight of a copolymer.

The nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of the obtained copolymer showed a peak of hydrogen of ethylidene group at around 5.2 ppm and a peak of vinylene hydrogen formed by ring-opening polymerization at around 5.5 ppm. Indicated. Also,
Since a peak derived from methoxy hydrogen is observed around 3.6 ppm, the unsaturated cyclic olefin-based copolymer composed of a polar unit derived from the monomer (a) and a nonpolar unit derived from the monomer (b) ( I) was confirmed. The molar ratio between the polar unit and the nonpolar unit calculated from the peak area was 13:87. The reduced viscosity (ηsp / c) of this copolymer is 0.70 dl / g.
And showed a high molecular weight.

Comparative Example 1 In the composition prepared in Example 1, monomer (a) was replaced with 5-methyl-5-methoxycarbonyl-
When polymerization was attempted in the same manner as in Example 1 except that bicyclo [2,2,1] heptene-2 was used, the polymerization system solidified in a gel state in several minutes. The resulting material only swelled in toluene and did not dissolve.

[Comparative Example 2] Polymerization was attempted in the same manner as in Example 1 except that no monomer (a) was added.
The polymerization system solidified into a gel in a few minutes. The resulting material only swelled in toluene and did not dissolve.

Example 2 70 parts by weight of the unsaturated cyclic olefin copolymer (I) obtained in Example 1, 0.02 parts by weight of RuClH (CO) (PPh ₃ ) ₃ as a hydrogenation catalyst and a solvent 580 parts by weight of toluene was charged into an autoclave, hydrogen was introduced at a pressure of 30 kg / cm ^{2 in} terms of 25 ° C., and the mixture was reacted at 170 ° C. for 5 hours. The reaction mixture was poured into methanol for reprecipitation, followed by filtration, washing and drying to obtain 66 parts by weight of a saturated cyclic olefin copolymer (II) corresponding to the unsaturated cyclic olefin copolymer (I). I got

The ¹ H-NMR spectrum of the obtained copolymer was 5.2 ppm and 5.5 derived from unsaturated carbon.
The ppm peak disappeared, confirming that the hydrogenation was completed. The reduced viscosity (ηsp / c) obtained from the toluene solution was 0.85 dl / g, and no reduction in molecular weight due to reduction was observed. The glass transition temperature (Tg) of the saturated cyclic olefin copolymer is 13
5 ° C.

To the obtained saturated cyclic olefin copolymer (II), Irganox 1010 was added in an amount of 0.5% by weight, and injection molding was performed at a resin temperature of 280 ° C. to obtain a thickness of 2%.
mm was obtained. This molded plate had a transmittance of 92% and a haze value of 1.0%, and was extremely high in transparency. In addition, the bending strength is 1.0 × 10 ³ kg / c.
m ² , flexural modulus 2.3 × 10 ⁴ kg / cm ² , and Izod impact strength 2.9 kg · cm / cm, which was extremely strong.

The water absorption of the obtained molded plate was 0.1%, and polycarbonate (0.3%), polymethyl methacrylate (0.4%) and 2-methyl-2-methoxycarbonyltetracyclo [6 , 2,1,1 ^{6, 9,} 0 ^5,
10 ] The water absorption of the ring-opening / hydrogenated polymer of dodecene-7 (0.2
%).

Further, an aluminum thin film having a thickness of 110 nm was provided on the obtained molded plate by a sputtering method, and the adhesion of the aluminum thin film was evaluated by a cross cut test. As a result, the aluminum thin film did not come off at all and showed good adhesion. Further, the test piece was kept at 60 ° C / RH95.
%, Accelerated deterioration under severe conditions for 20 days, but no peeling of the thin film was observed by the cross cut test.

[Examples 3 to 5] By changing the ratio of the monomer (a) and the monomer (b) shown in Example 1, the composition ratio of the polar unit and the nonpolar unit was changed according to the method of Example 1. An unsaturated cyclic olefin copolymer (I) was synthesized. Table 1 shows the polymerization conditions and the results. As is clear from the results, a copolymer having a high molecular weight and a wide range was obtained without gelation.

[0119]

[Table 1]

[Example 6] In the charge composition of Example 1, 85 parts by weight of the monomer (a) was added to 65 parts of 5-isopropoxycarbonyl-5-isopropoxycarbonylmethyl-bicyclo [2,2,1] heptene-2. 178 parts by weight of the monomer (b) was changed to 189 parts by weight,
For 1 hour to obtain 70 parts by weight of a white polymer of the unsaturated cyclic olefin copolymer (I).

The molar ratio of polar units to non-polar units in the obtained copolymer was 10:90 from ¹ H-NMR. The reduced viscosity of this copolymer was 0.80 dl / g. Further, its glass transition temperature was 189 ° C., indicating extremely high heat resistance.

By hydrogenating 42 parts by weight of the obtained unsaturated cyclic olefin copolymer (I) in accordance with the method of Example 2, 36 parts by weight of the saturated cyclic olefin copolymer (II) ) Got. In the ¹ H-NMR spectrum,
No peak derived from unsaturated bonds was observed. And
The glass transition temperature was 139 ° C.

[Example 7] In the charge composition of Example 1, 85 parts by weight of the monomer (a) was added to 5-secbutoxycarbonyl-5-secbutoxycarbonylmethyl-bicyclo [2,2,1] heptene-2 32 The polymer was polymerized at 25 ° C. for 1 hour by changing 178 parts by weight of the monomer (b) to 59 parts by weight to obtain 53 parts by weight of an unsaturated cyclic olefin copolymer white polymer. The glass transition temperature of the obtained copolymer was 149 ° C.

Example 8 In the charge composition of Example 1, 85 parts by weight of the monomer (a) was added to 81 parts by weight, and 178 parts by weight of the monomer (b) was added to 5-ethylidenebicyclo [2,
2,1] Heptene-2 at 166 parts by weight and 25 ° C
For 1 hour to obtain 100 parts by weight of an unsaturated cyclic olefin copolymer white polymer. The glass transition temperature of the obtained copolymer was 105 ° C.

Example 9 In the charge composition of Example 1, 85 parts by weight of the monomer (a) was added with 187 of 5-cyclohexyloxycarbonyl-5-cyclohexyloxycarbonylmethyl-bicyclo [2,2,1] heptene-2. By changing 178 parts by weight of the monomer (b) to 106 parts by weight and polymerizing at 25 ° C. for 1 hour, a white polymer of an unsaturated cyclic olefin-based copolymer was obtained. The glass transition temperature of the obtained copolymer was 140 ° C.

Claims (6)

[Claims] 1 to 80 mol% of the following general formula (1): Wherein p and q are each independently 0 or 1, and R ^{1 to} R
¹⁰ are the same or different and are a hydrogen atom or a methyl group, R ¹¹ ,
R ¹² is the same or different and is an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. And 98 to 20 mol% of the following general formula (2): [In the formula, r is 0 or 1, R ^{a to} R ^h are the same or different, a hydrogen atom or a methyl group, R ^{i to} R ^l are the same or different, a hydrogen atom, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. Or a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. Here, R ⁱ and R ^j , R ^k and R ^l may form an unsaturated bond in cooperation with each other, and R ⁱ or R ^j
And R ^k or R ¹ may form a ring. ] The unsaturated cyclic olefin copolymer which consists of a repeating unit shown by these. 2. 2-80 mol% of the following general formula (3): [Wherein p and q are 0 or 1, R ^{1 to} R ¹⁰ are the same or different and are a hydrogen atom or a methyl group, R ¹¹ and R ¹² are the same or different and are an alkyl group having 1 to 10 carbon atoms or 5 to 5 carbon atoms. 10 cycloalkyl groups. And 98 to 20 mol% of the following general formula (4): Wherein r is 0 or 1, R ^{a to} R ^h are the same or different, and are a hydrogen atom or a methyl group; R ^{w to} R ^z are the same or different, a hydrogen atom; and an aromatic hydrocarbon group having 6 to 10 carbon atoms. Alternatively, it is a saturated hydrocarbon group having 1 to 10 carbon atoms. Here, R ^w or R ^x and R ^y or R ^z may form a ring. A saturated cyclic olefin-based copolymer comprising a repeating unit represented by the formula: 3. The following general formula (5): [Wherein p and q are 0 or 1, R ^{1 to} R ¹⁰ are the same or different and are a hydrogen atom or a methyl group, R ¹¹ and R ¹² are the same or different and are an alkyl group having 1 to 10 carbon atoms or 5 to 5 carbon atoms. 10 cycloalkyl groups. And a cyclic cyclic olefin represented by the following general formula (6): [In the formula, r is 0 or 1, R ^{a to} R ^h are the same or different, and are a hydrogen atom or a methyl group, R ^{i to} R ^l are the same or different, a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or It is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. Here, R ⁱ and R ^j , R ^k and R ^l may form an unsaturated bond together, and R ⁱ or R ^j
And R ^k or R ¹ may form a ring. ] A method for producing an unsaturated cyclic olefin-based copolymer, which is subjected to ring-opening copolymerization with the non-polar cyclic olefin represented by the formula: 4. The method for producing a saturated cyclic olefin copolymer according to claim 2, wherein the unsaturated cyclic olefin copolymer according to claim 1 is hydrogenated. 5. An optical material mainly comprising the unsaturated cyclic olefin-based copolymer according to claim 1. 6. An optical material mainly comprising the saturated cyclic olefin-based copolymer according to claim 2.