JP2006298957A - Oligosiloxane-modified norbornene resin and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cage-like oligosiloxane-modified norbornene resin having characteristics such as transparency, heat resistance, low hygroscopicity, low water-absorbing properties, chemical resistance, moisture resistance, water resistance, and low birefringence and improved mold-release characteristics and dispersibility, and to provide a method for producing the same. <P>SOLUTION: The norbornene resin is obtained by ring-opening metathesis polymerization of monomers including one or more norbornene monomers and is modified with a linear, branched or monocyclic oligosiloxane group at the polymer terminal. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a norbornene-based resin modified with a novel oligosiloxane group and a method for producing the same. The norbornene resin in which the polymer terminal of the present invention is modified with an oligosiloxane group can be used as a norbornene resin having improved properties such as releasability and dispersibility.

Norbornene-based ring-opening polymers and their hydrogenated products are used as transparent, heat-resistant, low-hygroscopic, low-water-absorbing, chemical-resistant, moisture-resistant, water-resistant, low-birefringent resins, optical materials, automotive parts It is used for electrical insulation materials. In particular, norbornene-based ring-opening polymers and hydrogenated products thereof are excellent in low birefringence as compared with other transparent thermoplastic resins and are important as optical materials.
As described above, although norbornene-based resins are important as optical materials, when precision processing of conventional norbornene-based resins is attempted, mold release and processing accuracy are not sufficient, and productivity and yield are not improved. Therefore, a norbornene-based resin excellent in releasability has been desired.
As a method for improving the releasability of a norbornene resin, there is known a method of adding a compound having a hydroxyacyloxy group having 16 or more carbon atoms and / or a saturated alcohol having 16 or more carbon atoms to the norbornene resin (patent) Document 1: JP-A-9-241484). However, since it is necessary to add a mold release agent later, there exists a fault that a process becomes complicated.
Further, siloxane compounds generally have releasability, and it is known that when added to a resin, the releasability of the resin is improved (Non-patent Document 1: Silicone is expanding its application fields and technological trends Ono. Edited by Yoshiaki, pages 60-64). However, like the above-mentioned patent document 1, since it is necessary to add a mold release agent later, a process becomes complicated.

On the other hand, by using a norbornene derivative having a cage oligosiloxane group as a substituent as a monomer as a norbornene polymer having a siloxy group, a ring-opening metathesis polymerization reaction is performed, so that a norbornene system having a cage oligosiloxane group in the polymer chain Resin is synthesized. However, norbornene derivatives having a cage oligosiloxane group as a substituent are difficult to obtain industrially and have low industrial utility (Non-patent Document 2: Macromolecules 1999, 32, 1194 to 1203).
In addition, as a compound having an unsaturated bond as a chain transfer agent in a ring-opening metathesis polymerization reaction of a norbornene-based monomer, an unsaturated group-containing alkylsilane such as vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, or allyltriisopropylsilane (Refer to Patent Documents 2 to 4: JP-A-11-158256, JP-A-11-193323, and JP-A-11-209460). There is a problem that cannot be expected.

  Based on the above, using a cocoon-like siloxane compound that can be synthesized from industrially readily available raw materials, transparency, heat resistance, low moisture absorption, low water absorption, and chemical resistance, which are the characteristics of norbornene resins Development of norbornene-based resins containing siloxy groups that have characteristics such as good releasability without degrading moisture resistance, water resistance, low birefringence, and without adding a release agent component Was desired.

JP-A-9-241484 JP-A-11-158256 JP-A-11-193323 JP-A-11-209460 Silicone Application Fields and Technical Trends Expanded by Yoshiaki Ono, pages 60-64 Macromolecules 1999, 32, 1194-1203

  The present invention responds to the above-mentioned demands, and has properties such as transparency, heat resistance, low moisture absorption, low water absorption, chemical resistance, moisture resistance, water resistance, low birefringence and the like. An object of the present invention is to provide a cage oligosiloxane-modified norbornene resin having improved properties and dispersibility and a method for producing the same.

  As a result of intensive studies to achieve the above object, the present inventor has converted a norbornene-based monomer into a metathesis catalyst in the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond. The present inventors have found that a norbornene-based resin having an oligosiloxane group at a polymer terminal synthesized by carrying out a ring-opening metathesis polymerization reaction can satisfy the above-mentioned demands, and has led to the present invention.

（式中、Ｒ¹〜Ｒ¹⁶は水素原子、置換又は非置換の炭素数１〜１０の１価炭化水素基、ハロゲン原子、水酸基、カルボキシル基、炭素数１〜１０のアシルオキシ基、炭素数２〜１０のオルガノオキシカルボニル基、炭素数１〜１０のアルコキシル基、シアノ基、アミド基、イミド基、又はＳｉＲ¹⁹ ₃基（Ｒ¹⁹は水素原子、炭素数１〜１０の１価炭化水素基、炭素数１〜１０のオルガノオキシ基、又はＯ（ＳｉＲ²⁰ ₂Ｏ）_pＳｉＲ²⁰ ₃（Ｒ²⁰は置換又は非置換の炭素数１〜１０の１価炭化水素基、ｐは０〜２０の整数である。）で表されるシロキシ基である。）を表し、互いに同一であっても異なっていてもよく、Ｒ¹〜Ｒ¹⁶のうちの２つで酸無水物基を作ってもよい。Ｒ¹⁷は水素原子又は炭素数１〜１０の１価炭化水素基、Ｒ¹⁸は単結合又は２価の有機基であり、Ｘは直鎖状、分岐状又は単環状のオリゴシロキサン基である。ｍは０，１又は２であり、ｎは１０〜１，０００，０００の整数である。）
で表されるポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサン基により変性されたノルボルネン系樹脂。
請求項４：
下記一般式（２）
ＣＨ₂＝ＣＲ¹⁷（Ｒ¹⁸）Ｘ （２）
（式中、Ｒ¹⁷は水素原子又は炭素数１〜１０の１価炭化水素基、Ｒ¹⁸は単結合又は２価の有機基であり、Ｘは直鎖状、分岐状又は単環状のオリゴシロキサン基である。）
で表されるエチレン性不飽和結合を有する直鎖状、分岐状又は単環状のオリゴシロキサン化合物の存在下に、下記一般式（３）

（式中、Ｒ¹〜Ｒ¹⁶は水素原子、置換又は非置換の炭素数１〜１０の１価炭化水素基、ハロゲン原子、水酸基、カルボキシル基、炭素数１〜１０のアシルオキシ基、炭素数２〜１０のオルガノオキシカルボニル基、炭素数１〜１０のアルコキシル基、シアノ基、アミド基、イミド基、又はＳｉＲ¹⁹ ₃基（Ｒ¹⁹は水素原子、炭素数１〜１０の１価炭化水素基、炭素数１〜１０のオルガノオキシ基、又はＯ（ＳｉＲ²⁰ ₂Ｏ）_pＳｉＲ²⁰ ₃（Ｒ²⁰は置換又は非置換の炭素数１〜１０の１価炭化水素基、ｐは０〜２０の整数である。）で表されるシロキシ基である。）を表し、互いに同一であっても異なっていてもよく、Ｒ¹〜Ｒ¹⁶のうちの２つで酸無水物基を作ってもよい。ｍは０，１又は２である。）
で表されるノルボルネン系モノマーを、メタセシス触媒により開環メタセシス重合反応させることを特徴とする、請求項３記載の一般式（１）で表されるポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサン基により変性されたノルボルネン系樹脂の製造方法。
請求項５：
請求項３記載の一般式（１）で表されるポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサンにより変性されたノルボルネン系樹脂を水素添加することにより得られる下記一般式（４）

（式中、Ｒ¹〜Ｒ¹⁶は水素原子、置換又は非置換の炭素数１〜１０の１価炭化水素基、ハロゲン原子、水酸基、カルボキシル基、炭素数１〜１０のアシルオキシ基、炭素数２〜１０のオルガノオキシカルボニル基、炭素数１〜１０のアルコキシル基、シアノ基、アミド基、イミド基、又はＳｉＲ¹⁹ ₃基（Ｒ¹⁹は水素原子、炭素数１〜１０の１価炭化水素基、炭素数１〜１０のオルガノオキシ基、又はＯ（ＳｉＲ²⁰ ₂Ｏ）_pＳｉＲ²⁰ ₃（Ｒ²⁰は置換又は非置換の炭素数１〜１０の１価炭化水素基、ｐは０〜２０の整数である。）で表されるシロキシ基である。）を表し、互いに同一であっても異なっていてもよく、Ｒ¹〜Ｒ¹⁶のうちの２つで酸無水物基を作ってもよい。Ｒ¹⁷は水素原子又は炭素数１〜１０の１価炭化水素基、Ｒ¹⁸は単結合又は２価の有機基であり、Ｘは直鎖状、分岐状又は単環状のオリゴシロキサン基である。ｍは０，１又は２であり、ｎは１０〜１，０００，０００の整数である。また、式中の実線と点線で表される結合は、単結合でも二重結合でもよいが、少なくとも一部は単結合である。）
で表されるポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサンにより変性された水素添加ノルボルネン系樹脂。
請求項６：
請求項４記載の一般式（２）で表されるエチレン性不飽和結合を有する直鎖状、分岐状又は単環状のオリゴシロキサン化合物の存在下に、一般式（３）で表されるノルボルネン系モノマーをメタセシス触媒により開環メタセシス重合反応させた後、触媒の存在下に水素化反応を行うことを特徴とする請求項５記載の一般式（４）で表されるポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサンにより変性された水素添加ノルボルネン系樹脂の製造方法。
請求項７：
直鎖状、分岐状又は単環状のオリゴシロキサン基のケイ素原子数が５以下であることを特徴とする請求項１，３又は５記載のポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサンにより変性されたノルボルネン系樹脂。
請求項８：
直鎖状、分岐状又は単環状のオリゴシロキサン化合物のケイ素原子数が５以下であることを特徴とする請求項２，４又は６記載のポリマー末端が直鎖状、分岐状又は単環状のオリゴシロキサンにより変性されたノルボルネン系樹脂の製造方法。 That is, the present invention provides a norbornene-based resin having a linear, branched or monocyclic oligosiloxane group at the following polymer terminal and a method for producing the same.
Claim 1:
A norbornene obtained by ring-opening metathesis polymerization of a monomer containing a single or two or more types of norbornene-based monomers and having a polymer terminal modified with a linear, branched or monocyclic oligosiloxane group Resin.
Claim 2:
A ring-opening metathesis polymerization reaction of a monomer containing a single or two or more types of norbornene monomers in the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond, using a metathesis catalyst. A method for producing a norbornene-based resin in which a polymer terminal is modified with a linear, branched, or monocyclic oligosiloxane.
Claim 3:
The following general formula (1)

(Wherein R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and 2 carbon atoms. 10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, organo group having 1 to 10 carbon atoms, or _{^{O (SiR 20 2 O) p}} SiR 20 3 (R 20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0-20 integer And may be the same or different from each other, and two of R ^{1 to} R ¹⁶ may form an acid anhydride group. R ¹⁷ is a monovalent hydrocarbon group hydrogen atom or a C1-10, R ¹⁸ represents a single bond or The valence of the organic radical, X is a linear, branched or monocyclic oligosiloxane groups .m is 0, 1 or 2, n is an integer of 10 to 1,000,000.)
The norbornene-type resin by which the polymer terminal represented by this was modified | denatured by the linear, branched or monocyclic oligosiloxane group.
Claim 4:
The following general formula (2)
CH ₂ = CR ¹⁷ (R ¹⁸ ) X (2)
(Wherein R ¹⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁸ is a single bond or a divalent organic group, and X is a linear, branched or monocyclic oligosiloxane. Group.)
In the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond represented by the following general formula (3)

(Wherein R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and 2 carbon atoms. 10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, organo group having 1 to 10 carbon atoms, or _{^{O (SiR 20 2 O) p}} SiR 20 3 (R 20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0-20 integer And may be the same or different from each other, and two of R ^{1 to} R ¹⁶ may form an acid anhydride group. m is 0, 1 or 2.)
The polymer terminal represented by the general formula (1) according to claim 3 is linear, branched, or monocyclic, wherein the norbornene-based monomer represented by the formula is subjected to ring-opening metathesis polymerization reaction using a metathesis catalyst. Of a norbornene-based resin modified with an oligosiloxane group.
Claim 5:
The following general formula (4) obtained by hydrogenating a norbornene-based resin in which the polymer terminal represented by the general formula (1) according to claim 3 is modified with a linear, branched or monocyclic oligosiloxane.

(Wherein R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and 2 carbon atoms. 10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, organo group having 1 to 10 carbon atoms, or _{^{O (SiR 20 2 O) p}} SiR 20 3 (R 20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0-20 integer And may be the same or different from each other, and two of R ^{1 to} R ¹⁶ may form an acid anhydride group. R ¹⁷ is a monovalent hydrocarbon group hydrogen atom or a C1-10, R ¹⁸ represents a single bond or X is a linear, branched or monocyclic oligosiloxane group, m is 0, 1 or 2, and n is an integer of 10 to 1,000,000. The bond represented by the solid line and the dotted line in the formula may be a single bond or a double bond, but at least a part is a single bond.)
A hydrogenated norbornene resin in which a polymer terminal represented by the formula is modified with a linear, branched, or monocyclic oligosiloxane.
Claim 6:
The norbornene system represented by the general formula (3) in the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond represented by the general formula (2) according to claim 4 The polymer terminal represented by the general formula (4) according to claim 5, wherein the monomer is subjected to a ring-opening metathesis polymerization reaction with a metathesis catalyst, and then a hydrogenation reaction is performed in the presence of the catalyst. A method for producing a hydrogenated norbornene resin modified with a branched or monocyclic oligosiloxane.
Claim 7:
The linear, branched or monocyclic oligo of claim 1, 3 or 5, wherein the linear, branched or monocyclic oligosiloxane group has 5 or less silicon atoms. Norbornene resin modified with siloxane.
Claim 8:
The linear, branched or monocyclic oligo of claim 2, 4 or 6, wherein the linear, branched or monocyclic oligosiloxane compound has 5 or less silicon atoms. A method for producing a norbornene resin modified with siloxane.

  The norbornene resin in which the polymer terminal of the present invention is modified with a linear, branched or monocyclic oligosiloxane group and its hydrogenated product are transparent, heat resistant, low hygroscopic, low water absorbing, chemical resistant In addition, the physical properties such as releasability and dispersibility are improved without impairing the properties of norbornene resins such as moisture resistance, water resistance, and low birefringence, and productivity during precision processing can be improved.

  The norbornene resin of the present invention is a norbornene resin in which the polymer terminal is modified with a linear, branched or monocyclic oligosiloxane group. The norbornene resin is a linear resin having an ethylenically unsaturated bond. In the presence of a branched or monocyclic oligosiloxane compound, a monomer containing a single or two or more types of norbornene monomers can be produced by a ring-opening metathesis polymerization reaction using a metathesis catalyst.

  In this case, specific examples of the norbornene resin in which the terminal of the present invention is modified with a linear, branched or monocyclic oligosiloxane include those represented by the following general formula (1). Examples thereof include a hydrogenated norbornene resin represented by the following general formula (4) obtained by hydrogenating the norbornene resin of the formula (1).

（式中、Ｒ¹〜Ｒ¹⁶は、水素原子、置換又は非置換の炭素数１〜１０の１価炭化水素基、ハロゲン原子、水酸基、カルボキシル基、炭素数１〜１０のアシルオキシ基、炭素数２〜１０のオルガノオキシカルボニル基、炭素数１〜１０のアルコキシル基、シアノ基、アミド基、イミド基、又はＳｉＲ¹⁹ ₃基（Ｒ¹⁹は、水素原子、炭素数１〜１０の１価炭化水素基、炭素数１〜１０のオルガノオキシ基、又はＯ（ＳｉＲ²⁰ ₂Ｏ）_pＳｉＲ²⁰ ₃（Ｒ²⁰は置換又は非置換の炭素数１〜１０の１価炭化水素基、ｐは０〜２０の整数である。）で表されるシロキシ基である。）を表し、互いに同一であっても異なっていてもよく、Ｒ¹〜Ｒ¹⁶のうちの２つで酸無水物基を作ってもよい。Ｒ¹⁷は水素原子又は炭素数１〜１０の１価炭化水素基、Ｒ¹⁸は単結合又は２価の有機基であり、Ｘは直鎖状、分岐状又は単環状のオリゴシロキサン基である。ｍは０，１又は２であり、ｎは１０〜１，０００，０００の整数である。また、式中の実線と点線で表される結合は、単結合でも二重結合でもよいが、少なくとも一部は単結合である。）

(In the formula, R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and a carbon number. 2-10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon having 1 to 10 carbon atoms Group, an organooxy group having 1 to 10 carbon atoms, or O (SiR ²⁰ ₂ O) _p SiR ²⁰ ₃ (R ²⁰ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0 to 20 Or a siloxy group represented by the formula ( ¹ ), which may be the same as or different from each other, and may form an acid anhydride group with two of R ^{1 to} R ^16. good .R ¹⁷ is hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁸ is a single bond Is a divalent organic group, X is a linear, branched or monocyclic oligosiloxane group, m is 0, 1 or 2, and n is an integer of 10 to 1,000,000. In addition, the bond represented by the solid line and the dotted line in the formula may be a single bond or a double bond, but at least a part is a single bond.)

Here, R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and a carbon number of 2 to 2. 10 organooxycarbonyl groups, alkoxy groups having 1 to 10 carbon atoms, cyano groups, amide groups, imide groups, or SiR ¹⁹ ₃ groups (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, carbon 1 to 10 organooxy group, or O (SiR ²⁰ ₂ O) _p SiR ²⁰ ₃ (R ²⁰ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is an integer of 0 to 20 And a siloxy group represented by the formula ( ¹ )), which may be the same or different from each other, and may form an acid anhydride group with two of R ^{1 to} R ¹⁶ .

  Specifically, as a monovalent hydrocarbon group, an alkyl group such as a methyl group, an ethyl group, a butyl group, a hexyl group and a decyl group, a cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, and an alkenyl group such as a vinyl group and a propenyl group Cyclic alkenyl groups such as cyclopentenyl group and cyclohexenyl group, aryl groups such as phenyl group and tolyl group, aralkyl groups such as benzyl group, carboxymethyl group, methoxycarbonylmethyl group, trimethylsilylmethyl group, triethylsilylmethyl group, tri Methoxysilylmethyl group, triethoxysilylmethyl group, [methylbis (trimethylsiloxy) methylsilyl] methyl group, [tris (trimethylsiloxy) silyl] methyl group, 2-trimethylsilylethyl group, 2-triethylsilylethyl group, 2-trimethoxy Silylethyl , Substituted alkyl groups such as 2-triethoxysilylethyl group, 2- [methylbis (trimethylsiloxy) methylsilyl] ethyl group, 2- [tris (trimethylsiloxy) silyl] ethyl group, etc., hydrogen atom, fluorine Halogen atoms such as chlorine and bromine, acyloxy groups such as hydroxyl groups, carboxyl groups, acryloxy groups and methacryloxy groups, organooxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, alkoxy groups such as methoxy groups, ethoxy groups and propoxy groups , Cyano group, amide group, imide group, trimethylsilyl group, triethylsilyl group, triisopropyl group, t-butyldimethylsilyl group, triphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, methylbis (trimethylsiloxy) silyl group The Silyl groups such as s (trimethylsiloxy) silyl group, 1,3,3,5,5-pentamethylcyclotrisiloxane group, 1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane group, Examples thereof include a siloxane group.

Examples of the combination of the substituents R ^{1 to} R ¹⁶ forming the acid anhydride group include a combination of R ¹¹ and R ¹² , and R ¹³ and R ¹⁴ .

R ¹⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a hexyl group, and decyl. R ¹⁸ is a single bond or a divalent organic group, specifically, a single bond, an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group or a hexylene group, a phenylene group, a phenylmethylene group, —CO—. _{, -COO -, - COOCH 2 -} , - COO (CH 2) 2 -, - COO (CH 2) 3 -, - Si (CH 3) 2 O -, - (CH 2) Si (CH 3) 2 O _{-, - Si (C 6 H} 5) 2 O -, - (CH 2) Si (C 6 H 5) 2 O- and the like. In this case, as CH ₂ = R ¹⁷ (R ¹⁸ ), specifically, vinyl group, allyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, 7-octenyl group, 9-decenyl group, Linear alkenyl groups such as 10-undecenyl group, 17-octadecenyl group, aromatic ethylenically unsaturated groups such as styryl group and allylphenyl group, (methacryloxypropyl group, 3-methacryloxypropyl group, etc. And ethylenically unsaturated group-containing siloxy groups such as acrylic group, vinyldimethylsiloxy group, allyldimethylsiloxy group, vinyldiphenylsiloxy group, allyldiphenylsiloxy group, and the like.

（式中、Ｒ²⁰は置換又は非置換の炭素数１〜１０の１価炭化水素基であり、Ｒ²¹は炭素数１〜２０の置換又は非置換の１価炭化水素基であり、互いに同一でも異なっていてもよく、Ｒ²²は、Ｒ²¹又は（ＯＳｉＲ²¹ ₂）_sＲ²¹（ｓは０〜２０の整数）で表されるシロキシ基であり、互いに同一であっても異なっていてもよい。ｑは１〜１００の整数であり、ｒは２又は３であり、ｔは０〜１０の整数である。） X is a linear, branched or monocyclic oligosiloxane group, and examples thereof include a group represented by the following formula. In this case, the oligosiloxane group preferably has 5 or less silicon atoms.
-(SiR ²¹ ₂ O) _q SiR ²¹ ₃
-Si (OSiR ²² ₃ ) _r R ²⁰ _3-r

(In the formula, R ²⁰ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ²¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which are identical to each other. However, they may be different, and R ²² is a siloxy group represented by R ²¹ or (OSiR ²¹ ₂ ) _s R ²¹ (s is an integer of 0 to 20), and may be the same or different from each other. Q is an integer from 1 to 100, r is 2 or 3, and t is an integer from 0 to 10.

（式中、Ｒ¹〜Ｒ¹⁶、ｍは上記と同様である。）
で表されるノルボルネン系モノマーを、開環メタセシス反応触媒を用いて反応させることによって製造することができる。 The norbornene-based resin of the above formula (1) is represented by the following general formula (2)
CH ₂ = CR ¹⁷ (R ¹⁸ ) X (2)
(Wherein R ¹⁷ , R ¹⁸ and X are the same as above)
In the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated group represented by the following general formula (3)

(Wherein R ^{1 to} R ¹⁶ and m are the same as above).
Can be produced by reacting using a ring-opening metathesis reaction catalyst.

  Further, the hydrogenated norbornene resin of the general formula (4) is obtained by performing a hydrogenation reaction of the resin of the general formula (1) in the presence of a hydrogenation catalyst, that is, the ethylenic resin represented by the general formula (2). In the presence of a linear, branched or monocyclic oligosiloxane compound having an unsaturated bond, the norbornene monomer represented by the general formula (3) is subjected to a ring-opening metathesis polymerization reaction using a metathesis catalyst, It can manufacture by performing a hydrogenation reaction in presence.

（式中、Ｒ¹⁷、Ｒ¹⁸及びＲ²¹は上記と同様であり、Ｒ²¹は互いに同一でも異なっていてもよい。ｔは０〜１０の整数である。）
で表される化合物であることが好ましい。 Here, as the oligosiloxane compound having an ethylenically unsaturated bond represented by the above formula (2), linear oligosiloxane, branched oligosiloxane, or cyclic oligosiloxane can be used. As the linear oligosiloxane, the following general formula (5)
CH ₂ = CR ¹⁷ (R ¹⁸ ) (SiR ²¹ ₂ O) _q SiR ²¹ ₃ (5)
(Wherein R ¹⁷ and R ¹⁸ are the same as above, R ²¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other. Q is 1) It is an integer of ~ 100.)
The branched oligosiloxane is a compound represented by the following general formula (6):
CH ₂ = CR ¹⁷ (R ¹⁸ ) Si (OSiR ²² ₃ ) _r R ²⁰ _3-r (6)
Wherein R ¹⁷ , R ¹⁸ and R ²⁰ are the same as above, and R ²² is R ²¹ or (OSiR ²¹ ₂ ) _s R ²¹ (R ²¹ is the same as above). And may be the same or different from each other, r is 2 or 3, and s is an integer of 0 to 20.)
In addition, the monocyclic oligosiloxane is represented by the following general formula (7):

(In the formula, R ¹⁷ , R ¹⁸ and R ²¹ are the same as above, and R ²¹ may be the same as or different from each other. T is an integer of 0 to 10.)
It is preferable that it is a compound represented by these.

Here, specific examples of R ¹⁷ , R ¹⁸ and CH ₂ = CR ¹⁷ (R ¹⁸ ) are as described above. R ²¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group. , Sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group, n-decyl group, n-octadecyl group and other alkyl groups, cyclopentyl group, cyclohexyl group, cyclooctyl group and other cycloalkyl groups, Alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups and o-tolyl groups, aralkyl groups such as benzyl groups and phenylethyl groups, halogen-substituted alkyl groups such as 3,3,3-trifluoropropyl groups, etc. Is mentioned. R ²¹ is preferably a methyl group, an ethyl group, a phenyl group, or a 3,3,3-trifluoropropyl group. n is an integer of 1 to 100, preferably n is 1 to 20, more preferably 1 to 4.

  Specific examples of the compound represented by the general formula (5) include 1,1,1,3,3-pentamethyl-3-vinyldisiloxane, 1,1,1,3,3,5,5- Heptamethyl-5-vinyltrisiloxane, 1,1,1,3,3,5,5,7,7-nonamethyl-7-vinyltetrasiloxane, 1,1,1,3,3,5,5,7, 7,9,9-undecamethyl-9-vinylpentasiloxane, 1,1,1,3,3,5,5,7,7,9,9,11,11-tridecamethyl-11-hexasiloxane, 1,1 , 3,3-tetramethyl-1-vinyldisiloxane, 1,1,1,3,3-pentaethyl-3-vinyldisiloxane, 1,1,1,3,3,5,5-heptaethyl-5 Vinyltrisiloxane, 1,1,1,3,3,5,5,7,7-nonethyl- -Vinyltetrasiloxane, 1,1,1,3,3,5,5,7,7,9,9-undecaethyl-9-vinylpentasiloxane, 1,1,1,3,3-pentaphenyl-3- Vinyldisiloxane, 1,1,1,3,3,5,5-heptaphenyl-5-vinyltrisiloxane, 1,1,1,3,3,5,5,7,7-nonaphenyl-7-vinyl Tetrasiloxane, 1,1,1,3,3,5,5,7,7,9,9-undecaethyl-9-vinylpentasiloxane, 1-allyl-1,1,3,3,3-pentamethyldi Siloxane, 1-allyl-1,1,3,3,5,5,5-heptamethyltrisiloxane, 1-allyl-1,1,3,3,5,5,7,7,7-nonamethyltetra Siloxane, 1-allyl-1,1,3,3,5,5,7,7,9,9, Undecamethylpentasiloxane, 1-allyl-1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane, 1-allyl-1,1 , 3,3-tetraethyldisiloxane, 1-allyl-1,1,3,3,3-pentaethyldisiloxane, 1-allyl-1,1,3,3,5,5,5-heptaethyltrisiloxane 1-allyl-1,1,3,3,5,5,7,7,7-nonaethyltetrasiloxane, 1-allyl-1,1,3,3,5,5,7,7,9, 9,9-undecaethylpentasiloxane, 1-allyl-1,1,3,3,3-pentaphenyldisiloxane, 1-allyl-1,1,3,3,5,5,5-heptaphenyltrisiloxane Siloxane, 1-allyl-1,1,3,3,5,5,7,7,7-nonafe Nyltetrasiloxane, 1-allyl-1,1,3,3,5,5,7,7,9,9,9-undecaphenylpentasiloxane, 1- (3-butenyl) -1,1,3 3,3-pentamethyldisiloxane, 1- (3-butenyl) -1,1,3,3,5,5,5-heptamethyltrisiloxane, 1- (3-butenyl) -1,1,3 3,5,5,7,7,7-nonamethyltetrasiloxane, 1- (3-butenyl) -1,1,3,3,5,5,7,7,9,9,9-undecamethyl Pentasiloxane, 1- (3-butenyl) -1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane, 1- (3-butenyl) -1,1,3,3-tetraethyldisiloxane, 1- (3-butenyl) -1,1,3,3,3-penta Tildisiloxane, 1- (3-butenyl) -1,1,3,3,5,5,5-heptaethyltrisiloxane, 1- (3-butenyl) -1,1,3,3,5,5 , 7,7,7-nonaethyltetrasiloxane, 1- (3-butenyl) -1,1,3,3,5,5,7,7,9,9,9-undecaethylpentasiloxane, 1- (3-butenyl) -1,1,3,3,3-pentaphenyldisiloxane, 1- (3-butenyl) -1,1,3,3,5,5,5-heptaphenyltrisiloxane, (3-butenyl) -1,1,3,3,5,5,7,7,7-nonaphenyltetrasiloxane, 1- (3-butenyl) -1,1,3,3,5,5,7 , 7,9,9,9-undecaphenylpentasiloxane, 1- (5-hexenyl) -1,1,3,3,3-pe Tamethyldisiloxane, 1- (5-hexenyl) -1,1,3,3,5,5,5-heptamethyltrisiloxane, 1- (5-hexenyl) -1,1,3,3,5, 5,7,7,7-nonamethyltetrasiloxane, 1- (5-hexenyl) -1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane, -(5-hexenyl) -1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane, 1- (5-hexenyl) -1,1 , 3,3-tetraethyldisiloxane, 1- (5-hexenyl) -1,1,3,3,3-pentaethyldisiloxane, 1- (5-hexenyl) -1,1,3,3,5, 5,5-heptaethyltrisiloxane, 1- (5-hexenyl) -1,1,3,3,5,5 , 7,7,7-nonaethyltetrasiloxane, 1- (5-hexenyl) -1,1,3,3,5,5,7,7,9,9,9-undecaethylpentasiloxane, 1- (5-hexenyl) -1,1,3,3,3-pentaphenyldisiloxane, 1- (5-hexenyl) -1,1,3,3,5,5,5-heptaphenyltrisiloxane, 1- (5-hexenyl) -1,1,3,3,5,5,7,7,7-nonaphenyltetrasiloxane, 1- (5-hexenyl) -1,1,3,3,5,5,7 , 7,9,9,9-undecaphenylpentasiloxane, 1- (4-vinylphenyl) -1,1,3,3,3-pentamethyldisiloxane, 1- (4-vinylphenyl) -1, 1,3,3,5,5,5-heptamethyltrisiloxane, 1- (4-vinylphenol 1) -1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxane, 1- (4-vinylphenyl) -1,1,3,3,5,5,7,7 , 9,9,9-undecamethylpentasiloxane, 1- (4-vinylphenyl) -1,1,3,3,5,5,7,7,9,9,11,11,11-trideca Methyl hexasiloxane, 1- (4-vinylphenyl) -1,1,3,3-tetraethyldisiloxane, 1- (4-vinylphenyl) -1,1,3,3,3-pentaethyldisiloxane, 1 -(4-vinylphenyl) -1,1,3,3,5,5,5-heptaethyltrisiloxane, 1- (4-vinylphenyl) -1,1,3,3,5,5,7, 7,7-nonaethyltetrasiloxane, 1- (4-vinylphenyl) -1,1,3,3,5,5,5 , 7,9,9,9-undecaethylpentasiloxane, 1- (4-vinylphenyl) -1,1,3,3,3-pentaphenyldisiloxane, 1- (4-vinylphenyl) -1, 1,3,3,5,5,5-heptaphenyltrisiloxane, 1- (4-vinylphenyl) -1,1,3,3,5,5,7,7,7-nonaphenyltetrasiloxane, -(4-vinylphenyl) -1,1,3,3,5,5,7,7,9,9,9-undecaphenylpentasiloxane, 1- (3-methacryloxypropyl) -1,1, 3,3,3-pentamethyldisiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,5,5,5-heptamethyltrisiloxane, 1- (3-methacryloxypropyl)- 1,1,3,3,5,5,7,7,7-nonamechi Rutetrasiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,5,5,7,7,9,9,9-undecamethylpentasiloxane, 1- (3-methacryloxypropyl) ) -1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane, 1- (3-methacryloxypropyl) -1,1,3 3-tetraethyldisiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,3-pentaethyldisiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,5 , 5,5-heptaethyltrisiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,5,5,7,7,7-nonaethyltetrasiloxane, 1- (3-methacryloxy Propyl) -1,1,3,3,5 , 7,7,9,9,9-undecaethylpentasiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,3-pentaphenyldisiloxane, 1- (3-methacryloxypropyl) ) -1,1,3,3,5,5,5-heptaphenyltrisiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,5,5,7,7,7-nona Phenyltetrasiloxane, 1- (3-methacryloxypropyl) -1,1,3,3,5,5,7,7,9,9,9-undecaphenylpentasiloxane, 1- (3-acryloxypropyl) ) -1,1,3,3,3-pentamethyldisiloxane, 1- (3-acryloxypropyl) -1,1,3,3,5,5,5-heptamethyltrisiloxane, 1- (3 -Acryloxypropyl) -1,1,3 , 5,5,7,7,7-nonamethyltetrasiloxane, 1- (3-acryloxypropyl) -1,1,3,3,5,5,7,7,9,9,9-undeca Methylpentasiloxane, 1- (3-acryloxypropyl) -1,1,3,3,5,5,7,7,9,9,11,11,11-tridecamethylhexasiloxane, 1- (3 -Acryloxypropyl) -1,1,3,3-tetraethyldisiloxane, 1- (3-acryloxypropyl) -1,1,3,3,3-pentaethyldisiloxane, 1- (3-acryloxy Propyl) -1,1,3,3,5,5,5-heptaethyltrisiloxane, 1- (3-acryloxypropyl) -1,1,3,3,5,5,7,7,7- Nonaethyltetrasiloxane, 1- (3-acryloxypropyl) -1, 1,3,3,5,5,7,7,9,9,7,9-undecaethylpentasiloxane, 1- (3-acryloxypropyl) -1,1,3,3,3-pentaphenyl Disiloxane, 1- (3-acryloxypropyl) -1,1,3,3,5,5,5-heptaphenyltrisiloxane, 1- (3-acryloxypropyl) -1,1,3,3 5,5,7,7-nonaphenyltetrasiloxane, 1- (3-acryloxypropyl) -1,1,3,3,5,5,7,7,9,9,9-undecaphenylpentasiloxane Etc.

In the above formula (6), R ¹⁷ and R ¹⁸ are the same as above, R ²² is a siloxy group represented by R ²¹ or (OSiR ²¹ ₂ ) _r R ²¹ , and s is an integer of 0 to 20 Preferably, it is 0-5, More preferably, it is 0. r is 2 or 3; Specific examples of R ²² include the substituents described above as R ²¹ and a trimethylsiloxy group. R ²⁰ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include the same monovalent hydrocarbon groups as R ^{1 to} R ¹⁶ .

  Specific examples of the compound represented by the above formula (6) include bis (trimethylsiloxy) methylvinylsilane, bis (dimethylsiloxy) methylvinylsilane, bis (trimethylsiloxy) ethylvinylsilane, bis (trimethylsiloxy) propylvinylsilane, bis (Trimethylsiloxy) phenylvinylsilane, bis (dimethylsiloxy) methylvinylsilane, bis (triethylsiloxy) methylvinylsilane, bis (triethylsiloxy) ethylvinylsilane, bis (triethylsiloxy) propylvinylsilane, bis (triethylsiloxy) phenylvinylsilane, bis (tri Phenylsiloxy) methylvinylsilane, bis (triphenylsiloxy) ethylvinylsilane, bis (triphenylsiloxy) propylvinylsilane, bis (to Phenylsiloxy) phenylvinylsilane, tris (trimethylsiloxy) vinylsilane, tris (dimethylsiloxy) vinylsilane, tris (triethylsiloxy) vinylsilane, tris (triphenylsiloxy) vinylsilane, allylbis (trimethylsiloxy) methylsilane, allylbis (dimethylsiloxy) methylsilane, allylbis (Trimethylsiloxy) ethylsilane, allylbis (trimethylsiloxy) propylsilane, allylbis (trimethylsiloxy) phenylsilane, allylbis (triethylsiloxy) methylsilane, allylbis (triethylsiloxy) ethylsilane, allylbis (triethylsiloxy) propylsilane, allylbis (triethylsiloxy) phenyl Silane, allylbis (triphenylsiloxy) Silane, allylbis (triphenylsiloxy) ethylsilane, allylbis (triphenylsiloxy) propylsilane, allylbis (triphenylsiloxy) phenylsilane, allyltris (trimethylsiloxy) silane, allyltris (dimethylsiloxy) silane, allyltris (triethylsiloxy) silane, allyltris (Triphenylsiloxy) silane, (3-butenyl) bis (trimethylsiloxy) methylsilane, (3-butenyl) bis (dimethylsiloxy) methylsilane, (3-butenyl) bis (trimethylsiloxy) ethylsilane, (3-butenyl) bis ( Trimethylsiloxy) propylsilane, (3-butenyl) bis (trimethylsiloxy) phenylsilane, (3-butenyl) bis (triethylsiloxy) methylsilane, ( 3-butenyl) bis (triethylsiloxy) ethylsilane, (3-butenyl) bis (triethylsiloxy) propylsilane, (3-butenyl) bis (triethylsiloxy) phenylsilane, (3-butenyl) bis (triphenylsiloxy) methylsilane, (3-butenyl) bis (triphenylsiloxy) ethylsilane, (3-butenyl) bis (triphenylsiloxy) propylsilane, (3-butenyl) bis (triphenylsiloxy) phenylsilane, (3-butenyl) tris (trimethylsiloxy) ) Silane, (3-butenyl) tris (dimethylsiloxy) silane, (3-butenyl) tris (triethylsiloxy) silane, (3-butenyl) tris (triphenylsiloxy) silane, (4-vinylphenyl) bis (trimethylsiloxy) ) Mechi Silane, (4-vinylphenyl) bis (dimethylsiloxy) methylsilane, (4-vinylphenyl) bis (trimethylsiloxy) ethylsilane, (4-vinylphenyl) bis (trimethylsiloxy) propylsilane, (4-vinylphenyl) bis ( Trimethylsiloxy) phenylsilane, (4-vinylphenyl) bis (triethylsiloxy) methylsilane, (4-vinylphenyl) bis (triethylsiloxy) ethylsilane, (4-vinylphenyl) bis (triethylsiloxy) propylsilane, (4-vinyl Phenyl) bis (triethylsiloxy) phenylsilane, (4-vinylphenyl) bis (triphenylsiloxy) methylsilane, (4-vinylphenyl) bis (triphenylsiloxy) ethylsilane, (4-vinylphenyl) bis (Triphenylsiloxy) propylsilane, (4-vinylphenyl) bis (triphenylsiloxy) phenylsilane, (4-vinylphenyl) tris (trimethylsiloxy) silane, (4-vinylphenyl) tris (dimethylsiloxy) silane, (4 -Vinylphenyl) tris (triethylsiloxy) silane, (4-vinylphenyl) tris (triphenylsiloxy) silane, (5-hexenyl) bis (trimethylsiloxy) methylsilane, (5-hexenyl) bis (dimethylsiloxy) methylsilane, 5-hexenyl) bis (trimethylsiloxy) ethylsilane, (5-hexenyl) bis (trimethylsiloxy) propylsilane, (5-hexenyl) bis (trimethylsiloxy) phenylsilane, (5-hexenyl) bis (triethylsilo) Xyl) methylsilane, (5-hexenyl) bis (triethylsiloxy) ethylsilane, (5-hexenyl) bis (triethylsiloxy) propylsilane, (5-hexenyl) bis (triethylsiloxy) phenylsilane, (5-hexenyl) bis (tri Phenylsiloxy) methylsilane, (5-hexenyl) bis (triphenylsiloxy) ethylsilane, (5-hexenyl) bis (triphenylsiloxy) propylsilane, (5-hexenyl) bis (triphenylsiloxy) phenylsilane, (5-hexenyl) ) Tris (trimethylsiloxy) silane, (5-hexenyl) tris (dimethylsiloxy) silane, (5-hexenyl) tris (triethylsiloxy) silane, (5-hexenyl) tris (triphenylsiloxy) silane, (3-mes (Acryloxypropyl) bis (trimethylsiloxy) methylsilane, (3-methacryloxypropyl) bis (dimethylsiloxy) methylsilane, (3-methacryloxypropyl) bis (trimethylsiloxy) ethylsilane, (3-methacryloxypropyl) bis (trimethylsiloxy) ) Propylsilane, (3-methacryloxypropyl) bis (trimethylsiloxy) phenylsilane, (3-methacryloxypropyl) bis (triethylsiloxy) methylsilane, (3-methacryloxypropyl) bis (triethylsiloxy) ethylsilane, (3- (Methacryloxypropyl) bis (triethylsiloxy) propylsilane, (3-methacryloxypropyl) bis (triethylsiloxy) phenylsilane, (3-methacryloxypropyl) bis (to Phenylsiloxy) methylsilane, (3-methacryloxypropyl) bis (triphenylsiloxy) ethylsilane, (3-methacryloxypropyl) bis (triphenylsiloxy) propylsilane, (3-methacryloxypropyl) bis (triphenylsiloxy) phenyl Silane, (3-methacryloxypropyl) tris (trimethylsiloxy) silane, (3-methacryloxypropyl) tris (dimethylsiloxy) silane, (3-methacryloxypropyl) tris (triethylsiloxy) silane, (3-methacryloxypropyl) ) Tris (triphenylsiloxy) silane, (3-acryloxypropyl) bis (trimethylsiloxy) methylsilane, (3-acryloxypropyl) bis (dimethylsiloxy) methylsilane, (3-acryloxy) Cypropyl) bis (trimethylsiloxy) ethylsilane, (3-acryloxypropyl) bis (trimethylsiloxy) propylsilane, (3-acryloxypropyl) bis (trimethylsiloxy) phenylsilane, (3-acryloxypropyl) bis (triethylsiloxy) ) Methylsilane, (3-acryloxypropyl) bis (triethylsiloxy) ethylsilane, (3-acryloxypropyl) bis (triethylsiloxy) propylsilane, (3-acryloxypropyl) bis (triethylsiloxy) phenylsilane, (3- (Acryloxypropyl) bis (triphenylsiloxy) methylsilane, (3-acryloxypropyl) bis (triphenylsiloxy) ethylsilane, (3-acryloxypropyl) bis (triphenylsiloxy) propyl Pyrsilane, (3-acryloxypropyl) bis (triphenylsiloxy) phenylsilane, (3-acryloxypropyl) tris (trimethylsiloxy) silane, (3-acryloxypropyl) tris (dimethylsiloxy) silane, (3-acrylic) Roxypropyl) tris (triethylsiloxy) silane, (3-acryloxypropyl) tris (triphenylsiloxy) silane, and the like.

R ¹⁷ , R ¹⁸ and R ^{21 in the} above formula (7) are the same as above, and t is an integer of 0 to 10, preferably 0 to 5, more preferably 1 to 2.

Specific examples of the compound represented by the above formula (7) include 1,1,3,3,5-pentamethyl-5-vinylcyclotrisiloxane, 1,1,3,3,5,5,7- Heptamethyl-7-vinylcyclotetrasiloxane, 1,1,3,3,5,5,7,7,9-nonamethyl-9-vinylcyclopentasiloxane, 1,1,3,3,5,5,7, 7,9,9,11-undecamethyl-11-vinylcyclohexasiloxane, 1,1,3,3,5-pentaethyl-5-vinylcyclotrisiloxane, 1,1,3,3,5,5,7- Heptaethyl-7-vinylcyclotetrasiloxane, 1,1,3,3,5,5,7,7,9-nonaethyl-9-vinylcyclopentasiloxane, 1,1,3,3,5,5,7, 7,9,9,11-Undecaethyl-11-vini Cyclohexasiloxane, 1,1,3,3,5-pentaphenyl-5-vinylcyclotrisiloxane, 1,1,3,3,5,5,7-heptaphenyl-7-vinylcyclotetrasiloxane, 1, 1,3,3,5,5,7,7,9-nonaphenyl-9-vinylcyclopentasiloxane, 1,1,3,3,5,5,7,7,9,9,11-undecaphenyl -11-vinylcyclohexasiloxane, 1,1,3,3,5-pentakis (3,3,3-trifluoropropyl) -5-vinylcyclotrisiloxane, 1,1,3,3,5,5, 7-heptakis (3,3,3-trifluoropropyl) -7-vinylcyclotetrasiloxane, 1,1,3,3,5,5,7,7,9-nonakis (3,3,3-trifluoro Propyl) -9-vinylcyclope Tasiloxane, 1,1,3,3,5,5,7,7,9,9,11-undecakis (3,3,3-trifluoropropyl) -11-vinylcyclohexasiloxane, 1-allyl-1 , 3,3,5,5-pentamethylcyclotrisiloxane, 1-allyl-1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1-allyl-1,3,3,5 , 5,7,7,9-nonamethylcyclopentasiloxane, 1-allyl-1,3,3,5,5,7,7,9,9,11,11-undecamethylcyclohexasiloxane, Allyl-1,3,3,5,5-pentaethylcyclotrisiloxane, 1-allyl-1,3,3,5,5,7,7-heptaethylcyclotetrasiloxane, 1-allyl-1,3, 3,5,5,7,7,9,9-nonethyl ethyl Clopentasiloxane, 1-allyl-1,3,3,5,5,7,7,9,9,11,11-undecaethylcyclohexasiloxane, 1-allyl-1,3,3,5,5 -Pentaphenylcyclotrisiloxane, 1-allyl-1,3,3,5,5,7,7-heptaphenylcyclotetrasiloxane, 1-allyl-1,3,3,5,5,7,7,9 , 9-nonaphenylcyclopentasiloxane, 1-allyl-1,3,3,5,5,7,7,9,9,11,11-undecaphenylcyclohexasiloxane, 1-allyl-1,3, 3,5,5-pentakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 1-allyl-1,3,3,5,5,7,7-heptakis (3,3,3-trifluoro Propyl) cyclotetrasiloxane, 1-a 1,3,3,5,5,7,7,9,9-nonakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 1-allyl-1,3,3,5,5 7,7,9,9,11,11-undecakis (3,3,3-trifluoropropyl) cyclohexasiloxane, 1- (3-butenyl) -1,3,3,5,5-pentamethylcyclotri Siloxane, 1- (3-butenyl) -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1- (3-butenyl) -1,3,3,5,5,7, 7,9,9-nonamethylcyclopentasiloxane, 1- (3-butenyl) -1,3,3,5,5,7,7,9,9,11,11-undecamethylcyclohexasiloxane, -(3-Butenyl) -1,3,3,5,5-pentaethylcycloto Siloxane, 1- (3-butenyl) -1,3,3,5,5,7,7-heptaethylcyclotetrasiloxane, 1- (3-butenyl) -1,3,3,5,5,7, 7,9,9-nonaethylcyclopentasiloxane, 1- (3-butenyl) -1,3,3,5,5,7,7,9,9,11,11-undecaethylcyclohexasiloxane, -(3-butenyl) -1,3,3,5,5-pentaphenylcyclotrisiloxane, 1- (3-butenyl) -1,3,3,5,5,7,7-heptaphenylcyclotetrasiloxane 1- (3-butenyl) -1,3,3,5,5,7,7,9,9-nonaphenylcyclopentasiloxane, 1- (3-butenyl) -1,3,3,5,5 , 7,7,9,9,11,11-undecaphenylcyclohexasiloxane 1- (3-butenyl) -1,3,3,5,5-pentakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 1- (3-butenyl) -1,3,3,5 , 5,7,7-heptakis (3,3,3-trifluoropropyl) cyclotetrasiloxane, 1- (3-butenyl) -1,3,3,5,5,7,7,9,9-nonakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 1- (3-butenyl) -1,3,3,5,5,7,7,9,9,11,11-undecakis (3,3 , 3-trifluoropropyl) cyclohexasiloxane, 1- (5-hexenyl) -1,3,3,5,5-pentamethylcyclotrisiloxane, 1- (5-hexenyl) -1,3,3,5 , 5,7,7-heptamethylcyclotetrasiloxane, -(5-hexenyl) -1,3,3,5,5,7,7,9,9-nonamethylcyclopentasiloxane, 1- (5-hexenyl) -1,3,3,5,5,7 , 7,9,9,11,11-undecamethylcyclohexasiloxane, 1- (5-hexenyl) -1,3,3,5,5-pentaethylcyclotrisiloxane, 1- (5-hexenyl)- 1,3,3,5,5,7,7-heptaethylcyclotetrasiloxane, 1- (5-hexenyl) -1,3,3,5,5,7,7,9,9-nonaethylcyclopenta Siloxane, 1- (5-hexenyl) -1,3,3,5,5,7,7,9,9,11,11-undecaethylcyclohexasiloxane, 1- (5-hexenyl) -1,3 , 3,5,5-pentaphenylcyclotrisiloxane, 1- (5-he Senyl) -1,3,3,5,5,7,7-heptaphenylcyclotetrasiloxane, 1- (5-hexenyl) -1,3,3,5,5,7,7,9,9-nona Phenylcyclopentasiloxane, 1- (5-hexenyl) -1,3,3,5,5,7,7,9,9,11,11-undecaphenylcyclohexasiloxane, 1- (5-hexenyl)- 1,3,3,5,5-pentakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 1- (5-hexenyl) -1,3,3,5,5,7,7-heptakis ( 3,3,3-trifluoropropyl) cyclotetrasiloxane, 1- (5-hexenyl) -1,3,3,5,5,7,7,9,9-nonakis (3,3,3-trifluoro Propyl) cyclopentasiloxane, 1- (5-hexenyl) ) -1,3,3,5,5,7,7,9,9,11,11-undecakis (3,3,3-trifluoropropyl) cyclohexasiloxane, 1- (4-vinylphenyl) -1 , 3,3,5,5-pentamethylcyclotrisiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1- (4-vinyl Phenyl) -1,3,3,5,5,7,7,9,9-nonamethylcyclopentasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7, 9,9,11,11-undecamethylcyclohexasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5-pentaethylcyclotrisiloxane, 1- (4-vinylphenyl) -1 , 3,3,5,5,7,7-heptaethylcyclo Torasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7,9,9-nonaethylcyclopentasiloxane, 1- (4-vinylphenyl) -1,3,3 , 5,5,7,7,9,9,11,11-undecaethylcyclohexasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5-pentaphenylcyclotrisiloxane, -(4-vinylphenyl) -1,3,3,5,5,7,7-heptaphenylcyclotetrasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7 , 9,9-nonaphenylcyclopentasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7,9,9,11,11-undecaphenylcyclohexasiloxane, -(4-vinylphenyl) -1,3,3,5 5-pentakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7-heptakis (3,3,3-tri Fluoropropyl) cyclotetrasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7,9,9-nonakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 1- (4-vinylphenyl) -1,3,3,5,5,7,7,9,9,11,11-undecakis (3,3,3-trifluoropropyl) cyclohexasiloxane, 1- ( 3-methacryloxypropyl) -1,3,3,5,5-pentamethylcyclotrisiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5,7,7-heptamethylcyclo Tetrasiloxane 1- (3-methacryloxypropyl) -1,3,3,5,5,7,7,9,9-nonamethylcyclopentasiloxane, 1- (3-methacryloxypropyl) -1,3,3 , 5,5,7,7,9,9,11,11-undecamethylcyclohexasiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5-pentaethylcyclotrisiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5,7,7-heptaethylcyclotetrasiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5, 7,7,9,9-nonaethylcyclopentasiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5,7,7,9,9,11,11-undecaethylcyclohex Sasiloxane, 1- (3-methacrylic Xylpropyl) -1,3,3,5,5-pentaphenylcyclotrisiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5,7,7-heptaphenylcyclotetrasiloxane, 1 -(3-methacryloxypropyl) -1,3,3,5,5,7,7,9,9-nonaphenylcyclopentasiloxane, 1- (3-methacryloxypropyl) -1,3,3,5 , 5,7,7,9,9,11,11-undecaphenylcyclohexasiloxane, 1- (3-methacryloxypropyl) -1,3,3,5,5-pentakis (3,3,3- Trifluoropropyl) cyclotrisiloxane,
1- (3-Methacryloxypropyl) -1,3,3,5,5,7,7-heptakis (3,3,3-trifluoropropyl) cyclotetrasiloxane, 1- (3-methacryloxypropyl)- 1,3,3,5,5,7,7,9,9-nonakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 1- (3-methacryloxypropyl) -1,3,3 5,5,7,7,9,9,11,11-Undecakis (3,3,3-trifluoropropyl) cyclohexasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5 , 5-Pentamethylcyclotrisiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 1- (3-Atacryloxypropyl) -1,3,3 5,5,7,7,9,9-nonamethylcyclopentasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5,7,7,9,9,11,11 -Undecamethylcyclohexasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5-pentaethylcyclotrisiloxane, 1- (3-Atacryloxypropyl) -1,3 3,5,5,7,7-heptaethylcyclotetrasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5,7,7,9,9-nonaethylcyclopentasiloxane 1- (3-Atacryloxypropyl) -1,3,3,5,5,7,7,9,9,11,11-undecaethylcyclohexasiloxane, 1- (3-Atacryloxypropyl) ) -1,3,3,5,5-pentafe Lucyclotrisiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5,7,7-heptaphenylcyclotetrasiloxane, 1- (3-Atacryloxypropyl) -1,3 3,5,5,7,7,9,9-nonaphenylcyclopentasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5,7,7,9,9,11 , 11-Undecaphenylcyclohexasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5-pentakis (3,3,3-trifluoropropyl) cyclotrisiloxane, 1- ( 3-Athacryloxypropyl) -1,3,3,5,5,7,7-heptakis (3,3,3-trifluoropropyl) cyclotetrasiloxane, 1- (3-Athacryloxypropyl) -1 , 3,3,5 , 5,7,7,9,9-nonakis (3,3,3-trifluoropropyl) cyclopentasiloxane, 1- (3-Atacryloxypropyl) -1,3,3,5,5,7, Examples include 7,9,9,11,11-undecakis (3,3,3-trifluoropropyl) cyclohexasiloxane.

  These linear, branched or monocyclic oligosiloxane compounds having an ethylenically unsaturated bond can be used alone, but have an ethylenically unsaturated bond in which two or more of these are mixed. It can also be used as a mixture of oligosiloxane compounds.

  The amount of the linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond is preferably 0.0001 to 1.0 mol, more preferably 0.001 with respect to 1 mol of the norbornene monomer. ˜0.5 mol, particularly preferably 0.005 to 0.2 mol. In order to obtain a polymer having a desired molecular weight, the amount of the linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond can be adjusted.

  The norbornene-based monomer used in the present invention is represented by the above formula (3), and examples include norbornenes, dicyclopentadiene, tetracyclododecenes and the like.

Specific examples of norbornene-based monomers include 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, and 5-decyl-2. -Norbornene, 5-trimethoxysilyl-2-norbornene, 5-triethoxysilyl-2-norbornene, 5-tris (trimethylsiloxy) silyl-2-norbornene, 5-bis (trimethylsiloxy) methylsilyl-2-norbornene, 1 -(5-norbornen-2-yl) -1,3,3,5,5,7,7-heptamethylcyclotetrasiloxane, 5- (2-trimethoxysilylethyl) -2-norbornene, 5- (2 -Triethoxysilylethyl) -2-norbornene, 5- [2-tris (trimethylsiloxy) silane Ruethyl] -2-norbornene, 5- [2-bis (trimethylsiloxy) methylsilylethyl] -2-norbornene, 5-cyclopentyl-2-norbornene, 5-cyclohexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-phenyl-2-norbornene, 5-norbornene-2-cambonic acid Methyl, ethyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornen-2-yl acetate, 5-norbornen-2-yl acrylate, 5-norbornene methacrylate -2-yl, 5-norbornene-2-carvone 5-norbornene-2,3-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methanol, 5-norbornene-2,3-dimethanol, 5-norbornene-2- Norbornenes such as ol, dicyclopentadiene, methyldicyclopentadiene, dicyclopentadiene such as tricyclo [5.2.1.0 ^2,6 ] dec-8-ene, tetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclopentyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-propenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-en-4-ol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carbonitrile, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carbaldehyde, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxamide, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic imide, 4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-triethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-tris (trimethylsiloxy) silyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-bis (trimethylsiloxy) silyltetracyclo [6.2.1.1 ^3,6 . ^{Tetracyclododecenes} such as 0 ^2,7 ] dodec-9-ene, 7-oxa-2-norbornene, 5-methyl-7-oxa-2-norbornene, 5-ethyl-7-oxa-2-norbornene, 5-butyl-7-oxa-2-norbornene, 5-hexyl-7-oxa-2-norbornene, 5-cyclopentyl-7-oxa-2-norbornene, 5-cyclohexyl-7-oxa-2-norbornene, 5- And oxanorbornenes such as phenyl-7-oxa-2-norbornene.

  These norbornene monomers can be used alone, but can also be used as a mixture of norbornene monomers obtained by mixing two or more of these norbornene monomers.

  In the present invention, a monocyclic cycloolefin such as cyclobutene, cyclopentene, cyclooctene, cyclododecene, and 1,5-cyclooctadiene and derivatives thereof may be added to a norbornene monomer and used as a norbornene monomer mixture. it can.

  The metathesis polymerization catalyst used in the present invention is not particularly limited as long as the norbornene-based monomer can be subjected to metathesis ring-opening polymerization.

Examples of the metathesis polymerization catalyst include (i) a periodic table group 4-8 transition metal carbene complex catalyst, and (ii) a ring-opening metathesis polymerization catalyst based on a combination of a transition metal compound and an alkylating agent or a Lewis acid that functions as a promoter. Can be mentioned. Among these, since the catalytic activity is high, it is preferable to use a group 4-8 transition metal carbene complex catalyst of the periodic table, and it is particularly preferable to use a ruthenium carbene complex catalyst.
These are exemplified below, but in the following formulae, Me represents a methyl group, i-Pr represents an isopropyl group, t-Bu represents a tert-butyl group, and Ph represents a phenyl group.

The 4-8 transition metal carbene complex catalyst periodic table, as the tungsten alkylidene complexes, in particular W (N-2,6-i- Pr 2 C 6 H 3) (CH-t-Bu) (O _{-t-Bu) 2, W (} N-2,6-i-Pr 2 C 6 H 3) (CH-t-Bu) (OCMe 2 CF 3) 2, W (N-2,6-i-Pr _{2 C 6 H 3) (CH} -t-Bu) (OCMe (CF 3) 2) 2, W (N-2,6-i-Pr 2 C 6 H 3) (CHCMe 2 Ph) (O-t- _{Bu) 2, W (N-} 2,6-i-Pr 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W (N-2,6-i-Pr 2 C 6 H 3 ) (CHCMe ₂ Ph)) OCMe (CF ₃ ) ₂ ) _{2 and the} like.

The 4-8 transition metal carbene complex catalyst periodic table, as a molybdenum alkylidene complexes, in particular Mo (N-2,6-i- Pr 2 C 6 H 3) (CH-t-Bu) (O _{-t-Bu) 2, Mo (} N-2,6-i-Pr 2 C 6 H 3) (CH-t-Bu) (OCMe 2 CF 3) 2, Mo (N-2,6-i-Pr _{2 C 6 H 3) (CH} -t-Bu) (OCMe (CF 3) 2) 2, Mo (N-2,6-i-Pr 2 C 6 H 3) (CHCMe 2 Ph) (O-t- _{Bu) 2, Mo (N-} 2,6-i-Pr 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo (N-2,6-i-Pr 2 C 6 H 3 ) (CHCMe ₂ Ph)) OCMe (CF ₃ ) ₂ ) ₂ , Mo (N-2,6-i-Pr ₂ C ₆ H ₃ ) (BIPHEN), Mo (N-2,6-i-Pr ₂ C) ₆ H ₃ ) (BINO) (THF: tetrahydrofuran) and the like.

In the periodic table group 4-8 transition metal carbene complex catalyst, as the rhenium alkylidene complex, specifically, Re (Ct-Bu) (CH-t-Bu) (O-2,6-i-Pr _{2). C 6 H 3) 2, Re} (C-t-Bu) (CH-t-Bu) (O-2-t-BuC 6 H 4) 2, Re (C-t-Bu) (CH-t-Bu _{) (OCMe 2 CF 3) 2} , Re (C-t-Bu) (CH-t-Bu) (O-2,6-Me 2 C 6 H 3) 2 and the like.

  In the periodic table group 4-8 transition metal carbene complex catalyst, as the ruthenium carbene complex catalyst, specifically, benzylidenebis (tricyclohexylphosphine) ruthenium dichloride, (3-methyl-2-buten-1-ylidene) bis ( Tricyclopentylphosphine) ruthenium dichloride, benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride, benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride, benzylidene (1,3 -Dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) Tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloctahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazo Lysine-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1 , 3,4-Triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydro Limidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityloimidazolidine-2-ylidene) pyridine ruthenium dichloride, (1,3-dimesityloimidazolidine-2 -Ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1,3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3- Dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylideneruthenium dichloride, 1,3-bis (mesityl-2-imidazolidinylidene) (o-isopropoxyphenylmethylene) ruthenium dichloride, etc. Is mentioned.

On the other hand, as a transition metal compound in a catalyst by a combination of a transition metal compound and an alkyl agent or a Lewis acid, MoCl ₄ , MoBr ₂ , MoBr ₃ , MoBr ₄ , WCl ₂ , WBr ₂ , WCl ₄ , WBr ₄ , WCl ₅ , WBr ₅ etc. are mentioned. Examples of the alkylating agent that functions as a co-catalyst include methyl lithium, ethyl lithium, n-butyl lithium methyl magnesium chloride, methyl magnesium bromide, and the like. Examples of Lewis acids include trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tetra Examples include methyl tin, tetraethyl tin, tetrabutyl tin and the like.

  The amount of the ring-opening metathesis polymerization catalyst used is preferably 0.1 to 0.0000001 mol, more preferably 0.01 to 0.0000005 mol, and particularly preferably 0.001 to 0.000001 mol with respect to 1 mol of the norbornene monomer. . If the amount of the catalyst is larger than this, it may be difficult to remove the catalyst, and if it is less than this, sufficient polymerization activity may not be obtained.

  The polymerization reaction of the norbornene monomer in the presence of the oligosiloxane compound having an ethylenically unsaturated bond can be carried out with or without using a solvent. Examples of the solvent used in this polymerization reaction include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane, cyclopentane, cyclohexane, methylcyclohexane, decahydronaphthalene, bicycloheptane, hexahydroindene, and cyclooctane. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, propionitrile and benzonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, acetone, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, and esters such as methyl acetate, ethyl acetate, and ethyl propionate. Of these, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, and ketones are preferably used.

  The amount of the solvent used is preferably such that the concentration of the total amount of the linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond and the norbornene-based monomer is 1 to 50% by mass. Is 3 to 40% by mass, particularly preferably 5 to 35% by mass. If it is less than 1% by mass, the productivity is poor, and if it exceeds 50% by mass, the viscosity after polymerization becomes high and handling may be difficult.

  The reaction temperature is preferably −30 ° C. to 200 ° C., more preferably −10 ° C. to 180 ° C., particularly preferably 0 to 150 ° C. When it is lower than −30 ° C., the reaction rate is slow, and when it is higher than 200 ° C., side reactions may occur.

  The method for adding the ring-opening metathesis polymerization catalyst is not particularly limited, and it may be dissolved in a solvent and added to the reaction system, or may be added without dissolving. In the case of dissolving in a solvent, a solvent similar to the solvent used in the polymerization reaction can be used.

  The hydrogenated norbornene resin in which the polymer terminal of the present invention is modified with a linear, branched or monocyclic oligosiloxane is a carbon-carbon double of the norbornene resin in which the polymer terminal of the present invention is modified with an oligosiloxane. The bond is hydrogenated. In the hydrogenated norbornene resin whose polymer terminal is modified with oligosiloxane, the hydrogenation rate of the carbon-carbon double bond is 50% or more, preferably 80% or more, particularly preferably 90% or more.

  The hydrogenation reaction of a norbornene resin modified with a linear, branched or monocyclic oligosiloxane at the polymer end is performed using hydrogen gas in the presence of a hydrogenation catalyst, and the polymer end is linear, branched or This is performed by converting a carbon-carbon double bond in a norbornene-based resin modified with a monocyclic oligosiloxane into a single bond.

  The catalyst used for the hydrogenation reaction is not particularly limited, such as a heterogeneous catalyst or a homogeneous catalyst, and a catalyst generally used for a hydrogenation reaction of an olefin compound can be used.

  Examples of the heterogeneous catalyst include a catalyst in which a metal such as palladium, platinum, rhodium, ruthenium, or nickel is supported on activated carbon, silica, alumina, or the like. Specific examples include palladium / activated carbon, palladium / silica, palladium / alumina, platinum / activated carbon, platinum / alumina, rhodium / activated carbon, ruthenium / activated carbon, nickel / silica, and the like.

  Examples of the homogeneous catalyst include dichlorotris (triphenylphosphine) rhodium, the ruthenium carbene complex described as the catalyst used in the ring-opening metathesis polymerization, JP-A-7-2929, JP-A-7-149823, and JP-A-11. Ruthenium complex catalysts described in JP-A Nos. 158256, 11-193323, 11-209460, and the like.

  Among these, it is preferable to use a palladium-supported catalyst such as a rhodium complex catalyst, a ruthenium complex catalyst, and palladium / activated carbon because a carbon-carbon double bond can be selectively hydrogenated without causing a side reaction.

  When a ruthenium carbene complex is used as a catalyst for ring-opening metathesis polymerization of a norbornene-based monomer, the hydrogenation reaction can be carried out continuously as it is. In the case of performing the reaction continuously, a method of adding a vinyl compound such as ethyl vinyl ether or a base such as α-olefin, triethylamine, N, N-dimethylacetamide to improve the activity of the catalyst is preferable.

  The hydrogenation reaction is usually performed in an organic solvent. The organic solvent to be used is selected from those in which the hydride to be generated is dissolved, and a solvent similar to the solvent used for the ring-opening metathesis polymerization can be used. Therefore, after the polymerization reaction, the ring-opening metathesis polymerization catalyst used can be removed, and the hydrogenation catalyst can be added to carry out the reaction. Further, the reaction can be carried out by adding a hydrogenation catalyst without removing the ring-opening metathesis polymerization catalyst used.

  The conditions for the hydrogenation reaction can be appropriately selected depending on the hydrogenation catalyst used. The amount of the hydrogenation catalyst used is preferably 0.0001 to 30% by mass, more preferably 0.0005 to 10% by mass, and particularly preferably 0.001 to 5% by mass with respect to the resin obtained by ring-opening metathesis polymerization. %. The reaction temperature is preferably −20 ° C. to 250 ° C., more preferably −10 ° C. to 200 ° C., and particularly preferably 0 to 180 ° C. When it is lower than −20 ° C., the reaction rate is slow, and when it is higher than 250 ° C., side reaction may occur. The hydrogen pressure to be used is preferably 0.01 to 10.0 MPa, more preferably 0.05 to 7.0 MPa, and particularly preferably 0.1 to 5.0 MPa. If it is less than 0.01 MPa, the reaction rate is slow, and if it is higher than 10.0 MPa, a special reactor may be required. The reaction time of the hydrogenation reaction is appropriately selected depending on the hydrogenation rate. The reaction time is usually 0.1 to 10 hours, preferably 0.5 to 5 hours.

  The norbornene-based resin or hydrogenated norbornene-based resin of the present invention obtained as described above has a polystyrene-reduced weight average molecular weight of 1,000 to 5,000,000 by gel permeation chromatography (GPC), In particular, it is preferably 3,000 to 1,000,000.

  This norbornene-based resin in which the polymer terminal is modified with oligosiloxane has a good releasability and enables precision processing of various products. In the following examples, Me represents a methyl group.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example.
In addition, a weight average molecular weight (Mw) melt | dissolves a ring-opening metathesis polymer in THF, measures by gel permeation chromatography (GPC), and calculates | requires it in polystyrene conversion.

[Example 1]
A 300 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Into this flask, 7.2 g (76.4 mmol) of 2-norbornene and 0.63 g (1.9 mmol) of tris (trimethylsiloxy) vinylsilane were added and dissolved by adding 150 g of THF. Heated with an oil bath, added a catalyst solution in which 3.6 mg of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride dissolved in 2.25 g of THF was added under reflux. The mixture was stirred for 3 hours to obtain a polymer solution. The polymer solution was dropped into 1,750 ml of methanol to precipitate a solid content. The solid content was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 7.3 g of a polymer. The weight average molecular weight (Mw) of the obtained polymer was 71,900, and it was confirmed by analysis by ¹ H-NMR that a tris (trimethylsiloxy) silyl group was introduced.
A chart of ¹ H-NMR (deuterated chloroform solvent) is shown in FIG.
The obtained polymer is as follows.

[Example 2]
A 300 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. To this flask, 7.2 g (76.4 mmol) of 2-norbornene and 0.65 g (1.9 mmol) of allyltris (trimethylsiloxy) silane were charged, and 150 g of THF was added and dissolved. Heated with an oil bath, added a catalyst solution in which 3.6 mg of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride dissolved in 2.25 g of THF was added under reflux. The mixture was stirred for 3 hours to obtain a polymer solution. The polymer solution was dropped into 1,750 ml of methanol to precipitate a solid content. The solid content was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 7.0 g of a polymer. The weight average molecular weight (Mw) of the obtained polymer was 15,300, and it was confirmed by analysis by ¹ H-NMR that a tris (trimethylsiloxy) silyl group was introduced.
A chart of ¹ H-NMR (deuterated chloroform solvent) is shown in FIG.
The obtained polymer is as follows.

[Example 3]
A 300 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. To this flask, 7.2 g (76.4 mmol) of 2-norbornene and 0.60 g (1.9 mmol) of 1,3,3,5,5,7,7-heptamethyl-1-vinylcyclotetrasiloxane were charged, and 150 g of THF was charged. Was added and dissolved. Heated with an oil bath, added a catalyst solution in which 3.6 mg of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride dissolved in 2.25 g of THF was added under reflux. Under stirring for 3 hours, a polymer solution was obtained. The polymer solution was dropped into 1,750 ml of methanol to precipitate a solid content. The solid content was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 7.0 g of a polymer. The weight average molecular weight (Mw) of the obtained polymer was 360,740, and it was confirmed by analysis by ¹ H-NMR that a heptamethylcyclotetrasiloxane group was introduced.
A chart of ¹ H-NMR (deuterated chloroform solvent) is shown in FIG.
The obtained polymer is as follows.

[Example 4]
A 300 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. To this flask, 7.2 g (76.4 mmol) of 2-norbornene and 1,3,5,7-tetramethyl-1,3,5-tris (3,3,3-trifluoropropyl) -7-vinylcyclo 1.08 g (1.9 mmol) of tetrasiloxane was charged, and 150 g of THF was added and dissolved. Heated with an oil bath, added a catalyst solution in which 3.6 mg of benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride dissolved in 2.25 g of THF was added under reflux. Under stirring for 3 hours, a polymer solution was obtained. The polymer solution was dropped into 1,750 ml of isopropanol to precipitate a solid content. The solid content was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 7.0 g of a polymer. The weight average molecular weight (Mw) of the obtained polymer was 220,330, and it was confirmed by analysis by ¹ H-NMR that a cyclotetrasiloxane group was introduced.
A chart of ¹ H-NMR (deuterated chloroform solvent) is shown in FIG.
The obtained polymer is as follows.

2 is a nuclear magnetic resonance spectrum chart of the compound obtained in Example 1. FIG. 2 is a nuclear magnetic resonance spectrum chart of the compound obtained in Example 2. FIG. 2 is a chart of a nuclear magnetic resonance spectrum of the compound obtained in Example 3. 2 is a chart of a nuclear magnetic resonance spectrum of the compound obtained in Example 4.

Claims (8)

  A norbornene obtained by ring-opening metathesis polymerization of a monomer containing a single or two or more types of norbornene-based monomers and having a polymer terminal modified with a linear, branched or monocyclic oligosiloxane group Resin.   A ring-opening metathesis polymerization reaction of a monomer containing a single or two or more types of norbornene monomers in the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond, using a metathesis catalyst. A method for producing a norbornene-based resin in which a polymer terminal is modified with a linear, branched, or monocyclic oligosiloxane. The following general formula (1)

(Wherein R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and 2 carbon atoms. 10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, organo group having 1 to 10 carbon atoms, or _{^{O (SiR 20 2 O) p}} SiR 20 3 (R 20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0-20 integer And may be the same or different from each other, and two of R ^{1 to} R ¹⁶ may form an acid anhydride group. R ¹⁷ is a monovalent hydrocarbon group hydrogen atom or a C1-10, R ¹⁸ represents a single bond or The valence of the organic radical, X is a linear, branched or monocyclic oligosiloxane groups .m is 0, 1 or 2, n is an integer of 10 to 1,000,000.)
The norbornene-type resin by which the polymer terminal represented by this was modified | denatured by the linear, branched or monocyclic oligosiloxane group. The following general formula (2)
CH ₂ = CR ¹⁷ (R ¹⁸ ) X (2)
(Wherein R ¹⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁸ is a single bond or a divalent organic group, and X is a linear, branched or monocyclic oligosiloxane. Group.)
In the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond represented by the following general formula (3)

(Wherein R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and 2 carbon atoms. 10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, organo group having 1 to 10 carbon atoms, or _{^{O (SiR 20 2 O) p}} SiR 20 3 (R 20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0-20 integer And may be the same or different from each other, and two of R ^{1 to} R ¹⁶ may form an acid anhydride group. m is 0, 1 or 2.)
The polymer terminal represented by the general formula (1) according to claim 3 is linear, branched, or monocyclic, wherein the norbornene-based monomer represented by the formula is subjected to ring-opening metathesis polymerization reaction using a metathesis catalyst. Of a norbornene-based resin modified with an oligosiloxane group. The following general formula (4) obtained by hydrogenating a norbornene-based resin in which the polymer terminal represented by the general formula (1) according to claim 3 is modified with a linear, branched or monocyclic oligosiloxane.

(Wherein R ^{1 to} R ¹⁶ are a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an acyloxy group having 1 to 10 carbon atoms, and 2 carbon atoms. 10 organo oxycarbonyl group, an alkoxyl group having 1 to 10 carbon atoms, a cyano group, an amide group, an imide group, or a SiR ¹⁹ ₃ group (R ¹⁹ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, organo group having 1 to 10 carbon atoms, or _{^{O (SiR 20 2 O) p}} SiR 20 3 (R 20 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, p is 0-20 integer And may be the same or different from each other, and two of R ^{1 to} R ¹⁶ may form an acid anhydride group. R ¹⁷ is a monovalent hydrocarbon group hydrogen atom or a C1-10, R ¹⁸ represents a single bond or X is a linear, branched or monocyclic oligosiloxane group, m is 0, 1 or 2, and n is an integer of 10 to 1,000,000. The bond represented by the solid line and the dotted line in the formula may be a single bond or a double bond, but at least a part is a single bond.)
A hydrogenated norbornene resin in which a polymer terminal represented by the formula is modified with a linear, branched, or monocyclic oligosiloxane.   The norbornene system represented by the general formula (3) in the presence of a linear, branched or monocyclic oligosiloxane compound having an ethylenically unsaturated bond represented by the general formula (2) according to claim 4 The polymer terminal represented by the general formula (4) according to claim 5, wherein the monomer is subjected to a ring-opening metathesis polymerization reaction with a metathesis catalyst, and then a hydrogenation reaction is performed in the presence of the catalyst. A method for producing a hydrogenated norbornene resin modified with a branched or monocyclic oligosiloxane.   The linear, branched or monocyclic oligo of claim 1, 3 or 5, wherein the linear, branched or monocyclic oligosiloxane group has 5 or less silicon atoms. Norbornene resin modified with siloxane. The linear, branched or monocyclic oligo of claim 2, 4 or 6, wherein the linear, branched or monocyclic oligosiloxane compound has 5 or less silicon atoms. A method for producing a norbornene resin modified with siloxane.

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