JP2005126372A - Norbornene-based compound having crosslinkable group and polymer derived therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a norbornene-based compound having crosslinkable olefin group, and to provide polymers derived therefrom. <P>SOLUTION: The norbornene-based compound is a norbornene derivative having crosslinkable olefin group that is obtained by producing norbornenemethanol by Diels-Alder reaction between an allyl compound and cyclopentadiene followed by introducing an olefin into the norbornenemethanol by ring-opening metathesis polymerization. Further, a series of block copolymers and their modified derivatives each obtained from the norbornene-based compound are provided. From any thereof, a polymeric material excellent in solubility and optical properties is prepared, and furthermore, a hybrid material narrow in molecular weight distribution with controlled molecular weight, having such properties as low refractive index and high transparency and also having such advantages as high heat resistance and chemical resistance is produced. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polynorbornene-based high-performance material, and particularly to a norbornene-based monomer having a functional group and a polymer derived therefrom.

Polynorbornene and its derivatives are products commercialized by ring-opening metathesis polymerization (ROMP) and are one of important elastic materials. Excellent transparency and impact resistance, wide range of usable temperatures, good mechanical properties and processability, shape memory polymer materials and lighting equipment, machinery, electronic components, pipe members, Widely used in food packaging. In addition, derivatives thereof such as acid and ester polymers are widely used as photoresists in the electronics industry.
The olefin metathesis polymerization method is a very important method in the synthesis of macromolecules, and is particularly induced by an organometallic catalyst to cause a living ring-opening metathesis polymerization reaction. That is, a ring-opening reaction with a cycloolefin-based derivative is performed using an organometallic catalyst, and the reaction is continued until the cycloolefin-based monomer is used up or the metal catalyst loses its activity. The advantage of such a polymerization reaction is that there are few by-products during the ring-opening polymerization reaction, and the physical properties that appear in the obtained polymers and copolymers can be changed by changing the type of organic catalyst or monomer substituent. Can be changed. Furthermore, it is possible to produce a functional block copolymer by utilizing the characteristics of active polymerization.
Research on ring-opening metathesis polymerization of a norbornene derivative containing a functional group has been emphasized for several years in order to obtain a polymer material having excellent characteristics, and in particular, a polymer material having a crosslinking group in the side chain is In addition to having excellent performance such as transparency and processability as described above, it is applied to reticulated cross-linked polymers, nonlinear optical materials, and materials having various heat resistance and chemical resistance.
Methyl methacrylate with crosslinkable side chains is most commonly used in such fields and can generate thermal or photochemical polymerization reactions with free radical initiators or photosensitizers, respectively. In the well-known technique, since the terminal functional group tends to cause a complex reaction with the organometallic catalyst, it is extremely difficult to synthesize a polymer having a crosslinking group in the side chain using a ring-opening metathesis polymerization reaction (ROMP). In known technology, in the case of a monomer containing a polyfunctional group, an insoluble gel or a cross-linked product is generated in the polymerization reaction. There were few things that could be obtained, and it was even more difficult to obtain crosslinkable polynorbornene.

  Grubbs et al., 1996 (Maughon, BR; Grubbs, RH Macromolecules 1996, 29, 5765.), ruthenium catalyst I using 5-methyl methacrylate-1-cyclooctene (5 -Methacryloyl-1-cyclooctene) was subjected to a ring-opening metathesis polymerization reaction, and it was found that a gelation phenomenon occurs when a methyl group inhibitor is not added during the polymerization reaction.

  In view of the above problems, the present invention provides a norbornene monomer having a crosslinkable olefin group, and a norbornene polymer having a side chain crosslinkable olefin group and a series of derivatives obtained by a ring-opening metathesis polymerization method. Is used to produce a polymer material with excellent solubility and optical characteristics, and further has controllable molecular weight, low refractive index, excellent transparency, etc., and a molecular weight distribution (PDI value). A polymer having a molecular weight of 2 or less is produced, and a reduction in birefringence required for an optical material is achieved. Moreover, the hybrid material which has the characteristic excellent in heat resistance and chemical resistance can be manufactured.

The norbornene monomer having a crosslinkable olefin group provided by the present invention is obtained by obtaining norbornene methanol by a Diels-Alder reaction between an allyl compound and cyclopentadiene, and further introducing olefin to form a crosslinkable olefin group. A norbornene derivative having Similarly, the present invention can also obtain norbornene derivatives having —OH by the following Diels-Alder reaction (see AI), and norbornene having norcrosslinkable olefin groups of the present invention represented by the formulas 1 and 2. System compounds and polymers thereof can be obtained.

In the formula, k is 50 ≦ k ≦ 1000, R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—, R ² is — (CH ₂ ) p—, and R ³ is — H or —CH ₃ , provided that 1 ≦ m, n, and p ≦ 4, and m, n, and p are each an integer. In particular, the present invention discloses norbornene compounds and polymers having a crosslinkable olefin group with excellent organic solubility, wherein R ² is — (CH ₂ ) p— and 1 ≦ p ≦ 4.
The main object of the present invention is to provide a norbornene monomer having a crosslinkable olefin group, to obtain a norbornene-based polymer having a olefin group having a crosslinkable side chain using a ring-opening metathesis polymerization method, and a series of Disclose copolymers and modified derivatives to produce polymer materials with excellent solubility and optical properties, narrow molecular weight distribution, control molecular weight, low refractive index, high transparency, etc. It is to produce a hybrid material having characteristics and excellent heat resistance and chemical resistance.
Another object of the present invention is to provide a norbornene monomer having a functional group and a polymer derived therefrom, and a polymer having a molecular weight distribution (PDI value) of 2 or less due to advantages such as easy control of the molecular weight. And achieving a reduction in the birefringence in the optical material.
Still another object of the present invention is to produce a functional norbornene block copolymer from a norbornene monomer containing a crosslinking group side chain and another norbornene monomer polymer.

有效量の（I）の化合物において、
Ｒ¹は-（ＣＨ₂）ｍ-または-Ｃ（Ｏ）Ｏ（ＣＨ₂）ｎ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈまたは-ＣＨ₃、
但し、１≦ｍ，ｎ，ｐ≦４でｍ、ｎ、ｐは整数である。
好適には、Ｒ¹は-（ＣＨ₂）ｍ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ、
但し、１≦ｍ，ｐ≦４でｍ、ｐは整数である。
好適には、ｍ＝１でｐ＝２。 In order to achieve the above object, in the first embodiment of the present invention, a norbornene compound having a crosslinkable olefin group having a structure represented by the following (I) is provided.

In an effective amount of compound (I),
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
Preferably, R ¹ is — (CH ₂ ) m—,
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
Preferably, m = 1 and p = 2.

有效量の（II）の化合物において、
kは 50≦ k ≦1000
Ｒ¹は-（ＣＨ₂）ｍ-または-Ｃ（Ｏ）Ｏ（ＣＨ₂）ｎ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈまたは-ＣＨ₃、
但し、１≦ｍ，ｎ，ｐ≦４でｍ、ｎ、ｐは整数である。
好適には、Ｒ１は-（ＣＨ₂）ｍ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ、
但し、１≦ｍ，ｐ≦４でｍ、ｐは整数である。
好適には、ｍ＝１でｐ＝２。 In a second embodiment of the present invention, a norbornene polymer having a structure represented by the following (II) and having a crosslinkable olefin group in the side chain is provided.

In an effective amount of compound (II),
k is 50 ≦ k ≦ 1000
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
Preferably, the R1 - (CH ₂₎ m-,
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
Preferably, m = 1 and p = 2.

有效量の（III）の化合物において、
jは 50≦ j ≦1000、kは 50≦ k ≦1000 、
Ｒ¹は-（ＣＨ₂）ｍ- または-Ｃ（Ｏ）Ｏ（ＣＨ₂）ｎ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈまたは-ＣＨ₃、
但し、１≦ｍ，ｎ，ｐ≦４でｍ，ｎ，ｐは整数である。
好適には、Ｒ¹は-（ＣＨ₂）ｍ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ、
但し、１≦ｍ，ｐ≦４でｍ、ｐは整数である。
好適には、ｍ＝１、ｐ＝２。 According to a third aspect of the present invention, there is provided a block copolymer having a structure represented by the following (III) and containing a carbazole group and a crosslinking group side chain.

In an effective amount of compound (III),
j is 50 ≦ j ≦ 1000, k is 50 ≦ k ≦ 1000,
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, 1 ≦ m, n, p ≦ 4, and m, n, and p are integers.
Preferably, R ¹ is — (CH ₂ ) m—,
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
Preferably, m = 1, p = 2.

但し、iは 50≦ i ≦1000、kは 50≦ k ≦1000 、
Ｒは-（ＣＨ₂）ｎ-、１≦ｎ≦４でｎは整数である。 According to a fourth aspect of the present invention, there is provided a block copolymer having a structure represented by the following (IV) and having different segment lengths containing a phthalamide group and an olefin group in the side chain.

However, i is 50 ≦ i ≦ 1000, k is 50 ≦ k ≦ 1000,
R is — (CH ₂ ) n—, 1 ≦ n ≦ 4, and n is an integer.

V式中、iは 50≦ i ≦1000、kは 50≦ k ≦1000 、
Ｒは-（ＣＨ₂）ｎ-，１≦ｎ≦４でｎは整数である。
さらに、本発明は架橋可能なオレフイン基を有するノルボルネン系モノマー及び他のノルボルネン系モノマーを重合して、機能的なノルボルネンブロック共重合体を製造できる。特にフタルアミド基及び架橋可能なオレフイン基を有するブロック共重合体は、加水分解によりアミノ基（-ＮＨ₂）及び架橋可能なオレフイン基を有するブロック共重合体が取得でき、前記アミノ基（-ＮＨ₂）は周知の技術で改性が可能である。強調しておきたいのは、改性された重合体は依然として架橋可能なオレフイン基を有し、且つ分子量が制御可能で分子量分布が狭いブロック共重合体であり、ナノ構造の自然形成に役立つことである。該ブロック共重合体は架橋可能なオレフイン基と改性可能なアミノ基を有し、且つ分子量は制御可能で分子量分布は狭いブロック共重合体である。また優れた有機可溶性を備える。
上記のアミノ基及び架橋基側鎖を含むブロック共重合体は、下記（VI）で表される構造を有する。

有效量の式VIの化合物において、
iは 50≦ i ≦1000、kは 50≦ k ≦1000 、
Ｒ¹は-（ＣＨ₂）ｍ- または-Ｃ（Ｏ）Ｏ（ＣＨ₂）ｎ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ または-ＣＨ₃、
但し、１≦ｍ，ｎ，ｐ≦４でｍ、ｎ、ｐは整数である。
好適には、Ｒ¹は-（ＣＨ₂）ｍ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ、
但し、１≦ｍ，ｐ≦４でｍ、ｐは整数である。
好適には、ｍ＝１でｐ＝２。 According to a fifth aspect of the present invention, there is provided a block saturated copolymer having a structure represented by the following (V) and containing a crosslinkable side chain.

In the formula V, i is 50 ≦ i ≦ 1000, k is 50 ≦ k ≦ 1000,
R is — (CH ₂ ) n—, 1 ≦ n ≦ 4, and n is an integer.
Furthermore, the present invention can produce a functional norbornene block copolymer by polymerizing a norbornene monomer having a crosslinkable olefin group and other norbornene monomers. In particular, a block copolymer having a phthalamide group and a crosslinkable olefin group can be obtained by hydrolysis to obtain a block copolymer having an amino group (—NH ₂ ) and a crosslinkable olefin group, and the amino group (—NH ₂ ) Can be modified by known techniques. It should be emphasized that the modified polymer is a block copolymer that still has crosslinkable olefin groups, has a controllable molecular weight and a narrow molecular weight distribution, and is useful for the spontaneous formation of nanostructures. It is. The block copolymer is a block copolymer having a crosslinkable olefin group and a modifiable amino group, having a controllable molecular weight and a narrow molecular weight distribution. It also has excellent organic solubility.
The block copolymer containing the amino group and the crosslinking group side chain has a structure represented by the following (VI).

In an effective amount of the compound of formula VI,
i is 50 ≦ i ≦ 1000, k is 50 ≦ k ≦ 1000,
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
Preferably, R ¹ is — (CH ₂ ) m—,
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
Preferably, m = 1 and p = 2.

有效量の式VIIの化合物において、
iは 50≦ i ≦1000、kは 50≦ k ≦1000 、
Ｒ¹は-（ＣＨ₂）ｍ-または-Ｃ（Ｏ）Ｏ（ＣＨ₂）ｎ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ または-ＣＨ₃、
但し、１≦ｍ，ｎ，ｐ≦４でｍ、ｎ、ｐは整数である。
好適には、Ｒ¹は-（ＣＨ₂）ｍ-、
Ｒ²は-（ＣＨ₂）ｐ-、
Ｒ³は-Ｈ、
但し、１≦ｍ，ｐ≦４でｍ、ｐは整数である。
好適には、ｍ＝１でｐ＝２。 Hydrochloric acid gas is introduced into the amino group in the side chain of the above block copolymer (VI) to produce an ammonium group, which is converted into a water-soluble polymer, and has excellent desired solubility and optical properties. A molecular material is obtained. Therefore, this block copolymer is reacted with a reducing agent to obtain a block copolymer having different segment lengths containing an olefin group and an amino group in the side chain, and further quaternizing the amino group to the side chain. Block copolymers having different segment lengths containing quaternized ammonium groups and olefin groups are obtained. Its structure is shown below in Formula VII.

In an effective amount of the compound of formula VII,
i is 50 ≦ i ≦ 1000, k is 50 ≦ k ≦ 1000,
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
Preferably, R ¹ is — (CH ₂ ) m—,
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
Preferably, m = 1 and p = 2.

The norbornene-based monomer of the present invention is produced at a high temperature of 180 ° C. in an autoclave using a Diels-Alder reaction. The Diels-Alder reaction is a reaction in which diolephine (diene) -based and olefin-based monomers are formed into new olefin-cyclized monomers. Of course, the method for obtaining the polymer in the present invention is not limited to the autoclave. Any method carried out in the Diels-Alder reaction in a well-known technique can be used in the present invention. In the present invention, a norbornene monomer including a norbornene monomer having an olefin group in the side chain is prepared, and then the monomer is polymerized by a ring-opening metathesis polymerization method (ROMP) to produce a new polymer, and the olefin group is selected. Used to react with other free radicals to produce a polymer.
The reaction conditions for the ring-opening metathesis polymerization reaction used in the present invention are as follows.
(1) Metathesis catalyst The tungsten- and molybdenum-based metathesis catalyst contains a halide, oxyhalide or oxyorganic compound of the metal and can be used for a ring-opening metathesis polymerization reaction. , Tungsten hexachloride, tungsten oxychloride, tungsten tetrachloride, molybdenum pentachloride and molybdenum oxide acetylacetoacetate. Others include ruthenium (Ru) metathesis catalysts, but in the present invention, the use of [Cl ₂ Ru (CHPh) [P (C ₆ H ₁₁ ) ₃ ] ₂ ] catalysts is preferred.

(2) Solvent The ring-opening metathesis polymerization of the norbornene monomer of the present invention can be carried out without using a solvent, but the reaction is usually carried out in an inert organic solvent.
As the organic solvent to be used, a hydrocarbon-based solvent is preferable, and a cyclic hydrocarbon-based solvent capable of producing an excellent soluble ring-opening polymer is optimal. Specifically, benzene, ethylbenzene, toluene and xylene aromatic hydrocarbons, n-pentane, hexane, heptane aliphatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, and other alicyclic hydrocarbons, dichloromethane , Halogenated hydrocarbons such as diethane, dichloroethylene, tetrachloroethane, chloroform, dichlorobenzene and trichlorobenzene. Two or more of these solvents may be mixed and used. The amount of the solvent used relative to the monomer is usually 1 to 20 parts by weight of solvent, and preferably 2 to 10 parts by weight of solvent with respect to 1 part by weight of monomer.
(3) Temperature Although there is no restriction | limiting in particular about the temperature conditions of ring-opening metathesis polymerization, Usually, it shall be -20 to 100 degreeC, 0 to 100 degreeC is preferable and 10 to 80 degreeC is the most preferable.
(4) Atmospheric gas of polymerization reaction Ring-opening metathesis polymerization is usually performed in an inert gas such as nitrogen or argon, but may be performed in a vacuum oxygen-free or air-free atmosphere.
(5) Ring-opening polymer The ring-opening metathesis polymer and its copolymer produced in the present invention have an average molecular weight (Mn) of 10,000 to 600,000 and a molecular weight distribution (Polydispersity Index, PDI = Mw / Mn). , Distribution degree of molecular weight of surface polymerization reaction, “PDI”) is 2 or less. When the produced ring-opening metathesis polymer is subjected to a hydrogenation reaction, an optical polymer material is further obtained, and these are usually used as optical materials such as an optical disk, an optical lens and a transparent film. As can be seen from the well-known technology, when the molecular weight distribution range is 3 or more, the birefringence increases, but the PDI of the polymer obtained in the present invention is 2 or less, and the birefringence in the optical material. Can be satisfied, and excellent optical characteristics can be obtained. For the measurement of the molecular weight and molecular weight distribution of the ring-opened polymer, tetrahydrofuran is used as a solvent by gel permeation chromatography (GPC).

In addition to the development of new norbornene monomers, the present invention can produce new copolymers using other norbornene monomers. The other norbornene-based monomers are norbornene and norbornene derivatives of alkyl, alkylene or aromatic substituents, such as 2-norbornene, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl. -2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-phenyl-2-norbornene, and the like. In addition, there are dicyclopentadiene, 2,3-dihydroxycyclopentadiene, and alkyl substituents such as methyl, ethyl, propyl and butyl.
These other norbornene monomers may be polar substituents or substituents containing metal atoms. Such substituents include, for example, halogen atoms such as chlorine, bromine and fluorine, ester residues such as methoxycarbonyl, ethoxycarbonyl and acetyloxy, cyan group and pyridine group.
The norbornene derivative is obtained by synthesis in an autoclave by Diels-Alder reaction. Dicyclopentadiene is mainly decomposed at high temperature to produce cyclopentadiene, and it is produced by reacting with an olefinic compound containing a functional group (for example, allyl alcohol). Norbornene methanol performs a Diels-Alder reaction at 180 ° C. using an allyl group compound and cyclopentadiene. Since cyclopentadiene has a boiling point of 41 ° C. and allyl alcohol has a boiling point of 97 ° C., the reaction is carried out in an autoclave. It is necessary to do in.
The reaction formulas and steps for synthesis are as follows.

本発明に係わる側鎖に架橋基を含むノルボルネン重合体[poly（NBMOAC）]は、上記本発明の新開発される末端にオレフイン基を含むノルボルネンモノマー（NBMOAC）を用いて、開環メタセシス重合反応により側鎖に架橋基を含むノルボルネン重合体[poly（NBMOAC）]が得られ、この側鎖に架橋可能なオレフイン基を有するノルボルネン系重合体[poly（NBMOAC）]の合成反応式及びステップは下記の通りである。

The norbornene monomer (NBMOAC) having an olefin group crosslinkable at the terminal according to the present invention is synthesized using the newly developed norbornene methanol of the present invention, and a norbornene compound having a olefin group crosslinkable at the terminal ( The synthesis reaction formula and steps of (NBMOAC) are as follows.

The norbornene polymer [poly (NBMOAC)] containing a crosslinking group in the side chain according to the present invention is a ring-opening metathesis polymerization reaction using a norbornene monomer (NBMOAC) containing an olefin group at the terminal of the present invention. To obtain a norbornene polymer [poly (NBMOAC)] having a crosslinking group in the side chain, and a synthesis reaction formula and steps of the norbornene polymer [poly (NBMOAC)] having an olefin group crosslinkable in the side chain are as follows: It is as follows.

A norbornene monomer (NBMOAC) having an olefin group crosslinkable at the terminal and an acrylate monomer are mixed, and an AB crosslinking reaction proceeds to obtain an AB crosslinked polymer hybrid material. For example, a norbornene polymer [Poly (NBMOAC)] having a crosslinkable olefin group in the side chain is mixed with methyl methacrylate monomer (MMA), and released when a heat induction initiator (for example, well-known BPO or AIBN) is added. A group is generated, and a double bond in the side chain of Poly (NBMOAC) is cross-linked with methyl methacrylate to generate a hybrid material of AB cross-linked polymer. This AB cross-linked polymer further improves the thermal stability and chemical resistance of a hybrid material derived from known methyl methacrylate (MMA). The preparation of this AB cross-linked polymer hybrid material and the thermophysical properties of the product at each stage are shown in the reaction path.

The block copolymer [poly (NBMPI-b-NBMOAC)] having different segment lengths containing a phthalamide group and an olefin group in the side chain according to the present invention contains a norbornene (NBMPI) containing a phthalamide group and an olefin group at the terminal. Two types of monomers, norbornene monomer (NBMOAC), are polymerized to obtain block copolymers having different segment lengths. The synthesis reaction formula and steps of the block copolymer [poly (NBMPI-b-NBMOAC), formula IV] having different segment lengths containing a phthalamide group and an olefin group in the side chain are as follows.

An object of the present invention is to prepare a polymer material having excellent solubility and optical properties. The block copolymer having a segment length containing a phthalamide group and an olefin group in the above side chain [poly (NBMPI-b-NBMOAC This is because the polynorbornene segment containing a phthalamide group of)] contains a phthalimide group having excellent thermal properties and solubility. Furthermore, this phthalimide group is converted into an amino group by a reducing agent, and is generated into a block copolymer [poly (NBMPI-b-NBMOAC)] having different segment lengths containing a phthalamide group and an olefin group in the side chain (general) Use hydrazine as the reducing agent). This amino group passes hydrochloric acid gas to produce an ammonium group, which is converted into a water-soluble polymer [poly (NQNMPI-b-NBMOAC)], and a polymer material with excellent solubility and optical properties is desired. can get. Therefore, block copolymers [poly (NBMPI-b-NBMOAC)] having different segment lengths containing phthalamide groups and olefin groups in the above side chains are reacted with a reducing agent to contain olefin groups and amino groups in the side chains. A block copolymer with different segment lengths [poly (NBAM-b-NBMOAC)] is obtained, and the segment length containing quaternized ammonium groups and olefin groups in the side chain is further quaternized with amino groups. Of different block copolymers [poly (NQNBAM-b-NBMOAC)]. The structural formulas of these derivatives are shown below.

In order to improve the thermal stability and chemical resistance of polymethyl methacrylate used as a normal optical material, block copolymers having different segment lengths containing phthalamide groups and olefin groups in the above side chains [poly (NBMPI-b-NBMOAC)] and adding methyl methacrylate to the methyl methacrylate (—C (CH ₃ ) ═CH ₂ ) double bond and methyl methacrylate on the norbornene side chain having an olefin group. Crosslinking polymerization is performed to produce an AB crosslinked polymer.
In addition, by polymerizing two monomers of the present invention, a norbornene monomer having a crosslinkable olefin group (NBMOAC) and a norbornene monomer having a carbazole group (CbzNB), the carbazole group having a different segment length and A norbornene block copolymer having crosslinkable olefin groups is obtained. A synthesis reaction formula and steps of a norbornene block copolymer (Poly (CbzNB-b-NBMOAC)) having a carbazole group having a different segment length and a crosslinkable olefin group are as follows.

According to an embodiment of the present invention, the present invention provides a norbornene monomer having a crosslinkable olefin group, and obtained by a ring-opening metathesis polymerization method. A series of derivatives is used to produce a polymer material with excellent solubility and optical characteristics, and the molecular weight can be controlled, the refractive index is small, the transparency is excellent, and the molecular weight distribution (PDI). A polymer having a value of 2 or less is produced, and a reduction in birefringence required for an optical material is achieved. Moreover, the hybrid material which has the characteristic excellent in heat resistance and chemical resistance can be manufactured.
The norbornene monomer having a crosslinkable olefin group provided by the present invention is obtained by obtaining norbornene methanol by a Diels-Alder reaction of an allyl compound and cyclopentadiene, and further introducing a norbornene derivative having a crosslinkable olefin group by introducing olefin. get. Similarly, according to the present invention, a norbornene derivative having —OH can be obtained by Diels-Alder reaction, and a norbornene-based compound having a crosslinkable olefin group with excellent organic solubility and a polymer thereof can be obtained.
Furthermore, the present invention can produce a functional norbornene block copolymer by polymerizing a norbornene monomer having a crosslinkable olefin group and other norbornene monomers. In particular, a block copolymer having a phthalamide group and a crosslinkable olefin group can be obtained by hydrolysis to obtain a block copolymer having an amino group (—NH ₂ ) and a crosslinkable olefin group, and the amino group (—NH ₂ ) Can be modified by known techniques. It should be emphasized that the modified polymer is a block copolymer that still has crosslinkable olefin groups, has a controllable molecular weight and a narrow molecular weight distribution, and is useful for the spontaneous formation of nanostructures. It is. The block copolymer is a block copolymer having a crosslinkable olefin group and a modifiable amino group, having a controllable molecular weight and a narrow molecular weight distribution. It also has excellent organic solubility.
Next, in order to further understand the object, technical contents, features, and effects of the present invention, the present invention will be described in detail with reference to specific examples.

(Synthesis Example 1) Synthesis of norbornene methanol 50 g of cyclopentadiene and 1 g of allyl alcohol and hydroquinone in an equivalent amount are charged into an autoclave and reacted at 180 ° C. for 8 hours. After extracting the unreacted cyclopentadiene and allyl alcohol from the obtained liquid by vacuum extraction at room temperature, the obtained solution was distilled under vacuum at a temperature of 92 to 95 ° C. and a pressure of 13 mmHg to obtain a norbornene derivative. To get. The derivative was exo / endo = 20/80.

1H NMR（CDCl₃）：δ（ppm）＝０.４４〜０.４６（H_n3n）、１.０６〜１.０８（H_x3x）、１.１４〜１.１６（H_n7a）、１.２２〜１.２４（H₃）、１.３３〜１.３５（H_n7s）、１.５９（H_x2n）、１.７０〜１.７４（H_n3x）、１.８３〜１.８９（H₁₀）、２.２７（H_n2x）、２.６０（H_x4）、２.７０〜２.７１（H_n4,H_x1）、２.７６（H_n1）、３.３９〜３.４０（H_n8）、３.５１〜３.５５（H₁₂）、３.７３〜３.７７（H₁₃）、４.１１〜４.１５（H_x8）、５.５０〜５.８５（H₁₁,C＝C）、５.９８（H_n6）、６.０１（H_x6,H_x5）、６.０４（H_n5）。
¹³C NMR（CDCl₃）：δ（ppm）＝１８.５３（C₁₀）、２９.２０（C_n3）、２９.７８（C_x3）、３８.４６（C_x2）、３９.５９（C_n2）、４０.３９（C₁₂）、４１.８８（C₁₃）、４２.５０（C_x1,C_n4）、４３.９０〜４４.１６（C_x4,C_n1）、４５.２５（C_x7）、４９.６６（C_n7）、６４.０１（C_n8）、６８.６９（C_x8）、１２６.２０（C₁₁）、１３２.５０（C_n6）、１３６.４６〜１３６.５１（C_x5,C_x6）、１３７.２１（C_n5）、１３７.７７（C₁₄）、１５７.０９（C₁₅）、１６７.５７（C₁₆）。
赤外線スペクトル分析装置を用いて、末端にオレフイン基を含むノルボルネンモノマー中の官能基を分析すると、スペクトル分析結果は次の通りであった。３３６０（υ_N-H）、３０５０（υ_C-H）、２９６０（υ_C-H）、１７１５（υ_C=O）、１６４０（υ_C=C）、１５４０（υ_C-H）、１３００（υ_C-O）。 Preparation of norbornene monomer containing olefin group at the end (NBMOAC) Using a two-necked flask, a small amount of hydroxylin was added to 12.2 g (0.1 mol) of norbornenemethanol obtained from Synthesis Example 1, and 20 ml of tetrahydrofuran was added. Dissolve, 15.0 g (0.1 molar slight excess) of methacryloxy isocyanate and 15 ml of tetrahydrofuran are mixed into the solution, and slowly dropped into the reaction flask at a speed of one drop per second with a funnel, and the mixture is stirred and refluxed at 50 ° C. for 6 hours. Then, when a small amount of methanol is added to completely react the remaining methacryloxy isocyanate, a transparent liquid is obtained. Furthermore, when the transparent liquid is rotary evaporated to remove the solvent, a slightly white liquid is obtained, and when left to stand, a white solid can be obtained.
Comparing the results of elemental analysis and theoretical distribution, the theoretical values (C ₁₅ H ₂₁ O ₄ N) of norbornene monomer (NBMOAC) containing an olefin group at the terminal are C = 64.52%, H = 7.52%, N = The actual measurement results were 5.02%, C = 64.07%, H = 7.50%, and N = 4.98%. The measurement results of the optical spectrum of nuclear magnetic resonance (NMR) of a norbornene monomer (NBMOAC) containing an olefin group at the end were as follows.

1H NMR (CDCl ₃ ): δ (ppm) = 0.44 to 0.46 (H _n3n ), 1.06 to 1.08 (H _x3x ), 1.14 to 1.16 (H _n7a ), 1. 22 to 1.24 (H ₃ ), 1.33 to 1.35 (H _n7s ), 1.59 (H _x2n ), 1.70 to 1.74 (H _n3x ), 1.83 to 1.89 ( _{H 10), 2.27 (H n2x} ), 2.60 (H x4), 2.70~2.71 (H n4, H x1), 2.76 (H n1), 3.39~3.40 (H _n8 ), 3.51 to 3.55 (H ₁₂ ), 3.73 to 3.77 (H ₁₃ ), 4.11 to 4.15 (H _x8 ), 5.50 to 5.85 (H ₁₁ , C = C), 5.98 (H _n6 ), 6.01 (H _x6 , H _x5 ), 6.04 (H _n5 ).
¹³ C NMR (CDCl ₃ ): δ (ppm) = 18.53 (C ₁₀ ), 29.20 (C _n3 ), 29.78 (C _x3 ), 38.46 (C _x2 ), 39.59 (C _{n2), 40.39 (C 12)} , 41.88 (C 13), 42.50 (C x1, C n4), 43.90~44.16 (C x4, C n1), 45.25 (C _{x7), 49.66 (C n7)} , 64.01 (C n8), 68.69 (C x8), 126.20 (C 11), 132.50 (C n6), 136.46~136.51 _{(C x5, C x6),} 137.21 (C n5), 137.77 (C 14), 157.09 (C 15), 167.57 (C 16).
When the functional group in the norbornene monomer containing an olefin group at the terminal was analyzed using an infrared spectrum analyzer, the spectrum analysis result was as follows. 3360 (v _NH ), 3050 (v _CH ), 2960 (v _CH ), 1715 (v _{C = O} ), 1640 (v _{C = C} ), 1540 (v _CH ), 1300 (v _CO ).

Preparation of Norbornene Polymer Containing Crosslinkable Olefin Group in Side Chain [poly (NBMOAC)] 0.339 g (1.215 mmol) of norbornene monomer (NBMOAC) having an olefin group at the terminal is dissolved in 5 ml of dichloromethane. Moisture and air are removed by repeatedly refrigeration-bleeding-thawing three times using a vacuum system. Ruthenium catalyst [Cl ₂ Ru (CHPh) [P (C ₆ H ₁₁ ) ₃ ] ₂ ] 0.001 g (0.001515 mmol) was dissolved in 0.5 ml of dichloromethane, and the catalyst solution was poured into the reactor at room temperature. The mixture was stirred and reacted for 2 hours, and then the mixture was precipitated using methanol to obtain the product of formula 2 [poly (NBMOAC)]. The yield was about 80%.

[Measurement of properties]
(1) Analysis of groups In the present invention, by synthesizing a norbornene monomer (NBMOAC) containing an olefin group at the terminal, [Cl ₂ Ru (CHPh) [P (C ₆ H] by a ring-opening metathesis polymerization method (ROMP). ₁₁ ) A norbornene polymer [Poly (NBMOAC)] containing an olefin group in the side chain is synthesized using ₃ ] ₂ ] as a catalyst. When the structure was analyzed by an IR optical spectrum analyzer and 1H NMR and ¹³ C NMR, the result showed that 1H NMR (CDCl ₃ ): δ = 5.55, 6.08 ppm showed a double bond to the side chain olefin group. Absorption was observed and the presence of double bonds in the main chain after ring-opening polymerization was observed at 5.16-5.30 ppm. ¹³ C NMR (CDC1 ₃ ): The presence of double bonds in the main chain after ring-opening polymerization was observed at δ = 129.30 ppm, and the absorption of double bonds of olefin groups was observed in the side chain at 125.98 ppm. .
(2) Solubility measurement: measuring solubility at various ratios of different [M] / [I] (monomer concentration to catalyst concentration) norbornene polymer containing olefin groups crosslinkable in the side chain [poly (NBMOAC )] Is dissolved in a general organic solvent, and its solubility is as shown in Table 1. Even if the molecular weight is 332,000, it can be dissolved in a general organic solvent, and has extremely excellent solubility and workability.

(3) Gel permeation Measurement with a chromatographic analyzer (GPC) Average molecular weight and molecular weight of norbornene polymer [Poly (NBMOAC)] containing olefin groups in side chains obtained at various [M] / [I] ratios The distribution is as shown in Table 2.

As can be seen from the above results, when the ratio of the monomer concentration to the catalyst concentration ([M] / [I]) is changed, high molecular weight polymers having different molecular weights are obtained and the [M] / [I] ratio is increased. As the molecular weight increases, the molecular weight distribution is still narrow. Even when the molecular weight is 332000, the molecular weight still shows a narrow distribution (PDI = 1.7).
(4) Measurement of norbornene monomer containing olefin group and polymer thereof by differential scanning calorimeter (DSC) When the melting point is measured using a differential scanning calorimeter (DSC), the terminal contains olefin group. The melting point of the norbornene monomer (NBMOAC) is 62 ° C., and the norbornene polymer [Poly (NBMOAC)] containing an olefin group in the side chain is measured at the glass transition temperature (Tg). (Exothermal peak) appeared. This phenomenon indicates that the side chain and the terminal have double bonds.

AB cross-linking reaction of norbornene polymer containing olefin group in side chain and methyl methacrylate Norbornene monomer (NBMOAC) containing olefin group at the terminal obtained from Example 2 was dissolved in 4 ml of dichloromethane, and the catalyst solution [Cl ₂ Ru (CHPh ) Add [P (C ₆ H ₁₁ ) ₃ ] ₂ ] and dissolve further. When the polymerization reaction is complete, all the solvent is evaporated under reduced pressure, and methyl methacrylate is injected into the reactor only in a fixed amount to form side chains. A norbornene polymer containing olefin groups [Poly (NBMOAC)] is dissolved in 1 to 5% by weight of the norbornene polymer and methyl methacrylate, and 1% benzoyl peroxide (BPO) is added to the polymer solution. Is added to form a free radical initiator, and the mixed solution is frozen, extracted and thawed to remove air, and then heated at 90 ° C. for 24 hours to obtain methyl methacrylate. Over preparative (MMA) is free radical polymerization, at the same time carry out the crosslinking reaction between the norbornene polymer containing a further cross-linking group. The AB crosslinked polymer obtained by the crosslinking reaction does not dissolve in benzene, toluene, chloroform and dichloromethane, but simple polymethyl methacrylate dissolves in the organic solvent. This indicates that a cross-linking reaction between norbornene polymer [Poly (NBMOAC)] having an olefin group in the side chain and methyl methacrylate surely occurs, which is useful for improving the chemical resistance of the polymer material.

[Analysis of thermal properties]
In order to prove the generation of the cross-linking reaction more prominently, measurement was performed with a differential scanning calorimeter (DSC) and a thermogravimetric analyzer (TGA). From the results of differential scanning calorimetry and thermogravimetric analysis, it was confirmed that the norbornene polymer [Poly (NBMOAC)] having an olefin group in the side chain shows an exothermic peak at a temperature of about 176 ° C. This indicates that it has the double bond property of a methyl methacrylate group. However, in the AB cross-linking system of norbornene polymer [Poly (NBMOAC)] having an olefin group in the side chain and methyl methacrylate, the double bond property of the terminal is lost, and other phase transitions are not observed. This indicates that the AB cross-linked polymer does not already have a methyl methacrylate double bond.
Such effects are shown in the decomposition temperature (Td) because the crosslinking reaction can usually improve the thermal stability of the polymer. As seen from the thermogravimetric analysis diagram, among the cross-linked materials, the norbornene polymer [Poly (NBMOAC)] containing an olefin group in the side chain disclosed by the present invention is thermally stable due to a change in the amount introduced into the cross-linked material. It turns out that sex is changed. Judging from the results of thermogravimetric analysis, thermal stability improves as the ratio of norbornene polymer [Poly (NBMOAC)] containing poly (olefin) in the side chain to polymethyl methacrylate increases. In comparison with simple polymethylmethacrylate, a norbornene polymer containing olefin groups in 1% of the side chains under nitrogen [Poly (NBMOAC)] increases thermal stability by 13.5 ° C. under 5% of the side chains. It can be seen that the norbornene polymer having an olefin group [Poly (NBMOAC)] increases the thermal stability by 20.5 ° C.

The norbornene polymer [Poly (NBMOAC)] having an olefin group in the side chain disclosed in the present invention is obtained by polymerizing a thermally initiated free radical at 60 ° C. using azobisisobutyronitrile (AIBN) as an initiator. To crosslink (see reaction path (B)). The obtained crosslinked hybrid material had a glass transition temperature (Tg) of 28 ° C. When heat treatment was further performed at a high temperature (220 ° C.), a crosslinked hybrid material having a high glass transition temperature was obtained, and the glass transition temperature was 197 ° C. (see reaction path (C)). The crosslinked hybrid material does not dissolve in a general organic solvent. The norbornene compound (NBMOAC) containing a crosslinkable olefin group disclosed in the present invention is also crosslinked by polymerizing a thermally initiated free radical at 60 ° C. using azobisisobutyronitrile (AIBN) as an initiator. Polymers [poly (MMANB)] containing possible norbornene side chains can be formed. In the ¹ H NMR spectrum of poly (MMANB), the double bond hydrogen (5.55 and 6.08 ppm) of the methacrylic acid group is completely lost by thermal polymerization, and the norbornene double bond hydrogen (5.95 And 6.16 ppm) are still pending. This indicates that a norbornene polymer [poly (MMANB)] containing a crosslinking group in the side chain was obtained. Acquired polymers [poly (MMANB)] are N, N-dimethylsulfoxide (N, N-dimethylsulfoxide (DMSO)), N, N-dimethylformamide (DMF), N, N- Dissolves in dimethylacetamide (N, N-dimethylacetamide (DMAc), tetrahydrofuran (tetrahydrofuran (THF)), pyridine (pyridine), dichloromethane, chloroform, benzene, toluene and xylene. The obtained polymer [poly (MMANB)] The glass transition temperature (Tg) was 115 ° C. [Refer to Reaction Path (D)] Further, when the norbornene double bond in the side chain was crosslinked at 30 ° C. by ring-opening metathesis reaction to form a crosslinked hybrid material, The glass transition temperature (Tg) was 180 ° C. (see reaction path (E)).
(Comparative Example 1)

An appropriate amount of newly synthesized norbornene monomers (NBMMAI and NBMM) containing olefin groups at the ends are dissolved in 5 ml of dichloromethane. In the vacuum system, refrigeration-bleeding-thawing is repeated three times to remove moisture and air. An appropriate amount of ruthenium catalyst [Cl ₂ Ru (CHPh) [P (C ₆ H ₁₁ ) ₃ ] ₂ ] is dissolved in 0.5 ml of dichloromethane, the catalyst solution is poured into the reactor, and the reactor is left at room temperature. When the mixture was stirred and reacted for 10 minutes, an insoluble gel was produced. An insoluble gel was produced even when the inhibitor p-methoxyphenol (MEHQ) was added during the polymerization. (See Table 3).

(A) Measurement conditions: monomer and ruthenium catalyst II in CH ₂ Cl ₂ , [M] / [cat] =
1000, temperature (30 ° C.), (b) molecular weight by GPC (polystyrene basis), (c) 5- (methacryloyloxyethylaminocarboxylmethyl) bicyclo [2.2.1] heptan-2-one (NBMOAC), 5- (Methylmethacryloylisocyanate) bicyclo [2.2.1] heptan-2-one (NBMMAI), 5- (methacryloylmethyl) bicyclo [2.2.1] heptan-2-one (NBMM), (d) MEHQ (p-methoxyphenol) = 20 mol%, (e) Gelation during polymerization

Preparation of block copolymer [poly (NBMPI-b-NBMOAC)] containing phthalamide groups and olefin groups in the side chain and having different segment lengths Reaction was performed by dissolving 0.3744 g of norbornene (NBMPI) containing phthalamide groups in 10 ml of dichloromethane. The flask was put into a flask, the reaction flask was connected to a high vacuum system, and freeze-vacuum extraction-sealed tube-thawing was repeated three times to remove moisture and air, thereby obtaining a cured monomer solution. Then, 0.01 g of the catalyst [Cl ₂ Ru (CHPh) [P (C ₆ H ₁₁ ) ₃ ] ₂ ] is taken out in a dry box containing argon gas and dissolved in 0.5 ml of dichloromethane. Then, the solution was placed in the cured monomer solution with a syringe, and vacuum extraction was performed. After bleeding for a while, the reaction flask was thawed at room temperature (about 25 ° C.) and further stirred for 2 hours to measure the molecular weight. Subsequently, 0.08 g of norbornene monomer (NBMOAC) containing an olefin group at the terminal was put into the reaction flask with a syringe and stirred continuously for 2 hours, and finally dissolved in 1000 ml of methanol and precipitated.
In the above process, block copolymers [poly (NBMPI-b-NBMOAC), which have different segment lengths containing phthalamide groups and olefin groups in the side chain, by changing the addition amounts of the two types of monomers, wherein formula IV (provided that , R = (CH ₂ ) ₂ —)] was produced by polymerization, and the resulting block polymer was analyzed by ¹ H NMR and ¹³ C NMR.

¹ H NMR (CDCl ₃ ): δ (ppm) = 0.8 to 3.0 (hydrogen formed on the alicyclic ring after opening of norbornene), 1.5 (H ₁₀ ), 3.4 to 3.5 (H _n8 ), 3.76 (H ₁₃ ), 3.95 (H ₁₂ ), 4.12 (H _x8 ), 5.0-5.3 (of the double bond on the main chain after opening of norbornene) Hcis), 5.37 (H _{trans of the} double bond on the main chain after ring opening of norbornene), 5.0, 6.04 (H1), 7.4 to 7.8 (H _4H ).
¹³ C NMR (CDC1 ₃ ): δ (ppm) = 19 (C ₁₀ ), 31-68 (C _n8 ), 36-46 (C formed on the alicyclic ring after opening of norbornene), 124, 132.5 , 134 (aromatic group), 120-136 (C of the double bond on the main chain after norbornene ring opening), 169 (C ₁₆ , ₁₇ ).

(1) Measurement by gel permeation chromatography (GPC) Obtained by polymerization according to various [M] / [I] ratios ([M]: molar concentration of monomer, [I]: molar concentration of catalyst) A block copolymer [Poly (NBMPI-b-NBMOAC)] containing phthalamide groups and olefin groups in various side chains was measured, and its number average molecular weight (Mn) and molecular weight distribution are shown in Table 3.

As can be seen from the results, [M] _NBMPI / [I] ([M]: molar concentration of NBMPI monomer, [I]: molar concentration of catalyst) vs. [M] _NBMOAC / [I] ([M]: NBMOAC monomer By changing the ratio of [M], [I]: molar concentration of catalyst), block copolymers having different crosslinks were obtained, and [(M] _NBMPI / [I]) / ([M] _NBMOAC / [ As the ratio of I]) increases, the molecular weight of the copolymer also increases, but the molecular weight distribution is still narrow, {weight average molecular weight (Mw) / number average molecular weight (Mn), ie PDI = 1.50-1 .67} shows a single peak molecular weight curve. This indicates that the block copolymer was reliably produced.

(2) Measurement of solubility By introducing a norbornene monomer (NBMOAC) containing an olefin group at the terminal, the polymer obtained has anti-benzene, anti-xylene and anti-dichlorobenzene properties, and tetrahydrofuran, N, N -Dissolve in dimethylacetoside, N, N-dimethylformamide, dichloromethane and chloroform. The solubility measurement results are shown in Table 5.

++: dissolved at room temperature, +: dissolved at 60 ° C., + −: partially dissolved at 60 ° C., −: not dissolved, in the table, THF: tetrahydrofuran, DMAc: N, N-dimethylacetamide, Pyridine: pyridine, DMSO: Dimethyl sulfoxide, 1,2-Dichloro benzene: Dichlorobenzene, Xylene: Xylene, Toluene: Toluene, CH ₂ Cl ₂ : Dichloromethane, CHCl ₃ : Methane trichloride, DMF: N, N-dimethylformamide.

Production of AB cross-linked polymer of cross-linked block copolymer and polymethyl methacrylate 0 wt%, 5 wt% and 10 wt% of block copolymer having different segment lengths containing phthalamide groups and olefin groups in side chains obtained from Example 4 Each of the combined [poly (NBMPI-b-NBMOAC)] and methyl methacrylate are added to the ampoule, and dibenzoyl peroxide (BPO) is added as an initiator. Connect to high vacuum system and repeat freeze-vacuum-sealed tube-thaw 3 times. The ampoule is then thawed at room temperature, heated to 80 ° C. and stirred for 8 hours. The ampoule was allowed to cool to room temperature, the solution was precipitated in 500 ml of methanol, and the crosslinked polymer thus obtained was filtered and vacuum dried at room temperature.
The obtained crosslinked block copolymer was measured for the thermal properties of the polymer with a differential scanning calorimeter and a thermogravimetric analyzer (TGA, DSC). From thermogravimetry results, the thermal stability increases with the ratio of poly (methacrylate) to block copolymer [poly (NBMPI-b-NBMOAC)] with different segment lengths containing phthalamide and olefin groups in the side chain. You can see that it changes. Compared with simple polymethylmethacrylate, a block copolymer [poly (NBMPI-b-NBMOAC] with different segment lengths containing a phthalamide group and an olefin group in the side chain of 5 wt% in a methyl methacrylate (MMA) polymerization system in a nitrogen atmosphere. )] Is added for crosslinking, the thermal stability increases by 5 ° C. In addition, when a block copolymer [poly (NBMPI-b-NBMOAC)] having a different segment length containing a phthalamide group and an olefin group is added to a side chain of 10 wt% to a methyl methacrylate (MMA) polymerization system, Thermal stability increases by 20 ° C. When the block copolymer [Poly (NBMPI-b-NBMOAC)] having a crosslinking group in the side chain was crosslinked alone, the obtained thermal stability was 65.6 ° C. higher than that of a single polymethyl methacrylate.

Preparation of norbornene block copolymer having carbazole group and crosslinkable olefin group having different segment lengths equimolar amounts of potassium hydroxide (KOH) 12g and carbazole 30g were charged into a reaction flask, and xylene 200ml Is added to remove water, and further xylene is removed to obtain a potassium salt containing a carbazole group. The potassium salt is then placed in N, N-dimethylformamide (DMF) and 25 g of norbornene methyl chloride is gradually added and refluxed for 12 hours. After the refluxed solution is extracted three times with water and ethyl acetate, the solvent is extracted with a rotary concentrator. An initial product of a norbornene monomer having a carbazole group is obtained by gel permeation chromatography, and further recrystallized using n-hexane to obtain a purified norbornene monomer (CbzNB) having a carbazole group. .
Further, 2.5 mmol of norbornene (CbzNB) having a carbazole group is dissolved in 4 ml of dichloromethane, charged into a reaction flask, connected to a high vacuum system, and freeze-vacuum extraction-sealed tube-thawing is repeated three times. Take 2 mg of the catalyst [Cl2Ru (CHPh) [P (C18H15)] 2] from a dry box containing argon gas, dissolve it in 1 ml of dichloromethane, and inject it into the cured monomer solution with a syringe. .
The reaction flask was then allowed to thaw at room temperature and stirred at room temperature (about 25 ° C.) for 30 minutes, then 0.5 mmol of norbornene monomer was injected into the reaction flask with a syringe while the color was still red for 12 hours. Continue to stir. Subsequently, 0.1 ml of ethyl olefin ether was added to terminate the polymerization reaction, and the solution was precipitated in 500 ml of methanol to have olefin groups crosslinkable with carbazole groups having different segment lengths. A norbornene block copolymer [Poly (CbzNB-b-NBMOAC), Formula III (where R = (CH2) 2-)] is obtained. The poly (CbzNB-b-NBMOAC) polymer thus obtained is dissolved in dichloromethane and precipitated in methanol, and this is repeated three times to obtain a purified polymer, which is then vacuum dried at room temperature.

Block copolymers with different segment lengths by changing the addition amount of the two types of monomer, carbazole group-containing norbornene monomer (CbzNB) and epoxy group-containing norbornene monomer (NBMOAC) [Poly (CbzNB-b-NBMOAC) ] Is polymerized. When the block copolymer [Poly (CbzNB-b-NBMOAC)] thus obtained was analyzed by 1H NMR, the position of hydrogen on the carbazole group was in the range of 7.05 to 8.00 ppm, that is, the range was carbazole group. It turns out that it is the characteristic position of the upper hydrogen. The hydrogen positions on the side chain olefin groups are 5.01 and 6.04. The hydrogen position on the double bond of the main chain is in the range of 5.08 to 5.50 ppm, and this range is the characteristic position of polynorbornene.
The block copolymer having a carbazole group and a crosslinkable olefin group in the side chain disclosed in the present invention emits fluorescence by excitation of ultraviolet rays or electricity, but has a crosslinkable olefin group, and thus can be widely applied. Have sex.
The features of the present invention have been described with reference to the embodiments. The purpose of the present invention is to enable an engineer familiar with the technology to understand and implement the present invention. It does not limit the range. Accordingly, changes and applications having equivalent effects without departing from the spirit disclosed by the present invention should still be included in the scope of the claims.

Claims (15)

A norbornene-based compound having a crosslinkable olefin group, comprising an effective amount of the compound represented by formula I.

In the formula I, R ¹ represents — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, m, n, and p are each an integer when 1 ≦ m, n, and p ≦ 4.
The norbornene-based compound according to claim 1,
R ¹ is — (CH ₂ ) m—
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
The norbornene-based compound according to claim 2, wherein m = 1 and p = 2.
A norbornene-based polymer having an olefin group crosslinkable in a side chain, containing an effective amount of the compound represented by formula II.

In the formula II, k is 50 ≦ k ≦ 1000, — (CH ₂ ) p—, R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
The norbornene-based polymer according to claim 4,
R ¹ is — (CH ₂ ) m—
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
6. The norbornene polymer according to claim 5, wherein m = 1 and p = 2. A block copolymer having an effective amount of a compound represented by formula III and having a carbazole group and a crosslinkable olefin group in the side chain.

In the formula III, j is 50 ≦ j ≦ 1000, k is 50 ≦ k ≦ 1000,
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
The block copolymer according to claim 7,
R ¹ is — (CH ₂ ) m—
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
The block copolymer according to claim 7, wherein m = 1 and p = 2.
A block copolymer having a segment length containing a phthalamide group and an olefin group in the side chain, containing an effective amount of the compound represented by formula IV.

In the formula IV, i is 50 ≦ i ≦ 1000, k is 50 ≦ k ≦ 1000,
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
The block copolymer according to claim 10, wherein
R ¹ is — (CH ₂ ) m—
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
The block copolymer according to claim 11, wherein m = 1 and p = 2.
A block saturated copolymer having crosslinkable side chains comprising an effective amount of a compound of formula V.

In Formula V, i is 50 ≦ i ≦ 1000, k is 50 ≦ k ≦ 1000,
R ¹ is — (CH ₂ ) m— or —C (O) O (CH ₂ ) n—,
R ² is — (CH ₂ ) p—,
R ³ is —H or —CH ₃ ,
However, when 1 ≦ m, n, p ≦ 4, m, n, and p are integers.
The block copolymer according to claim 13,
R ¹ is — (CH ₂ ) m—
R ² is — (CH ₂ ) p—,
R ³ is —H,
However, when 1 ≦ m and p ≦ 4, m and p are integers.
The block copolymer according to claim 14, wherein m = 1 and p = 2.