JP4945945B2 - Thermoplastic resin, method for producing the same, and molding material - Google Patents

Description

  The present invention relates to a thermoplastic resin excellent in transparency, heat resistance, and oil resistance obtained by bonding a crystalline segment to an amorphous polymer segment having a glass transition temperature (Tg) of 40 to 300 ° C., The present invention relates to a production method and a molding material containing the thermoplastic resin as a resin component.

  Conventionally, thermoplastic resins such as polystyrene, polymethacrylate, and cyclic olefin polymers are widely used as transparent plastic materials for molding because they are excellent in moldability such as injection molding and blow molding. However, these thermoplastic resins have a problem of insufficient mechanical strength and oil resistance.

  As a solution, several methods for introducing a crystalline polymer segment into these thermoplastic resins have been proposed. For example, Non-Patent Document 1 reports a block copolymer of cyclooctadiene and methyl methacrylate and a hydride thereof (ethylene-methyl methacrylate block copolymer). However, the copolymer described in this document has a crystalline segment of polyethylene and has insufficient heat resistance.

Non-Patent Document 2 reports a hydride of a metathesis ring-opening block copolymer of norbornene and ethylidene norbornene, and states that the norbornene ring-opening polymer hydride segment is crystalline. However, the ethylidene norbornene ring-opening polymer hydride segment is a rubbery polymer having a glass transition temperature (Tg) of room temperature or lower.
Therefore, development of a thermoplastic resin excellent in all of transparency, heat resistance, and oil resistance has been strongly desired.

Journal of American Chemical Society, 2000, Vol. 122, p. 12872-12873 Macromolecules, 2004, 37, 7278-7284.

  The present invention has been made in view of such a state of the art, and includes a thermoplastic resin excellent in transparency, heat resistance, and oil resistance, a production method thereof, and the thermoplastic resin as a resin component. It is an object to provide a molding material.

  As a result of intensive studies to solve the above problems, the present inventors have found that a norbornene-based ring-opening polymer segment (C) that becomes a crystalline polymer when hydrogenated and a glass transition temperature (Tg) of 40 to 40 when hydrogenated. A polymer segment (D), which becomes an amorphous polymer at 300 ° C., was bonded to obtain a copolymer, which was then hydrogenated to obtain a thermoplastic resin. The obtained thermoplastic resin forms a structure in which the crystalline norbornene-based ring-opening polymer hydride segment (A) is micro-dispersed in the resin, so that heat resistance and oil resistance are maintained while maintaining transparency. As a result, the present invention has been completed.

Thus, according to the first aspect of the present invention, a crystalline norbornene-based ring-opening polymer hydride segment (A) comprising a polydicyclopentadiene hydride and an amorphous polymer having a glass transition temperature (Tg) of 40 to 300 ° C. A thermoplastic resin which is a block copolymer or graft copolymer with the polymer segment (B), and the ratio of the crystalline norbornene ring-opening polymer hydride segment (A) to the total polymer is 1 to 50 A thermoplastic resin having a weight percent and a weight average molecular weight (Mw) of 5,000 to 1,000,000 is provided .

According to a second aspect of the present invention, there is provided a process for producing a thermoplastic resin according to the present invention, wherein a polydicyclo which forms a crystalline polymer when 80% or more of carbon-carbon double bonds in the main chain are hydrogenated. pentadiene and Tona Ru ring-opened norbornene polymer segment (C), the main carbon in the chain - amorphous Shitsukasane of hydrogenation of 80% or more carbon-carbon double bond a glass transition temperature (Tg) of 40 to 300 ° C. Provided is a method for producing a thermoplastic resin in which 80% or more of carbon-carbon double bonds in the main chain of a block copolymer or graft copolymer with a polymer segment (D) to be combined are hydrogenated.
According to the third aspect of the present invention, there is provided a molding material comprising the thermoplastic resin of the present invention as a resin component.

The thermoplastic resin of the present invention is excellent in transparency, heat resistance, and oil resistance.
According to the production method of the present invention, the thermoplastic resin of the present invention can be efficiently produced.
The molding material of the present invention can be suitably used for the production of molded products such as optical products, medical products, various packaging containers, and vehicles as a transparent plastic material excellent in moldability, heat resistance, and oil resistance.

Hereinafter, the present invention will be described in detail.
1) Thermoplastic Resin The thermoplastic resin of the present invention comprises a crystalline norbornene-based ring-opening polymer hydride segment (A) (hereinafter sometimes referred to as “segment (A)”) and a glass transition temperature (Tg). A crystalline norbornene-based ring-opening polymer, which is a thermoplastic resin formed by bonding with an amorphous polymer segment (B) (hereinafter sometimes referred to as “segment B”) having a temperature of 40 to 300 ° C. The ratio of the hydride segment (A) to the entire polymer is 1 to 50% by weight, and the weight average molecular weight (Mw) is 5,000 to 1,000,000.

(1) Segment (A)
The segment (A) used for the thermoplastic resin of the present invention is made of a crystalline norbornene-based ring-opening polymer hydride and has excellent heat resistance and imparts excellent oil resistance and heat resistance to the thermoplastic resin.
The segment (A) is not particularly limited as long as it is a polymer segment in which the carbon-carbon double bond in the main chain of the norbornene-based ring-opening polymer is hydrogenated and has crystallinity.

  In general, the hydride of a norbornene-based ring-opening polymer is obtained by subjecting a norbornene-based monomer to ring-opening polymerization to obtain a norbornene-based ring-opening polymer, and then the carbon in the main chain of the obtained ring-opening polymer. -It can be produced by hydrogenating carbon double bonds.

The norbornene-based monomer is a compound having a norbornene ring in the molecule.
Specific examples of the norbornene monomer 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-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-cyclohexenyl- 2-norbornene, 5-cyclopentenyl-2-norbornene, 5-phenyl-2-norbornene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydro-9H-fluorene), tetracyclo [10.2.1.0. ^2,11 . 0 ^4,9 ] pentadeca-4,6,8,13-tetraene (also referred to as 1,4-methano-1,4,4a, 9,9a, 10-hexahydroanthracene), dicyclopentadiene, methyldicyclo Bicyclo [2.2.1] hept-2- with unsubstituted or hydrocarbon substituents such as pentadiene and dihydrodicyclopentadiene (tricyclo [5.2.1.0 ^2,6 ] dec-8-ene) Ens;

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-cyclohexyltetracyclo [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-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-cyclohexenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, and 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-4-ene and the like or a tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enes;

Such as methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, and ethyl 2-methyl-5-norbornene-2-carboxylate Bicyclo [2.2.1] hept-2-enes having an alkoxycarbonyl group;
Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodec-9-ene-4-carboxylate, and 4-methyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an alkoxycarbonyl group such as methyl 0 ^2,7 ] dodec-9-ene-4-carboxylate. 0 ^2,7 ] dodec-9-enes;

Bicyclo [2.2] having a hydroxycarbonyl group or an acid anhydride group such as 5-norbornene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and 5-norbornene-2,3-dicarboxylic acid anhydride .1] hept-2-enes;
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-4,5-dicarboxylic acid, and tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydroxycarbonyl group or an acid anhydride group such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride. 0 ^2,7 ] dodec-9-enes;

5-hydroxy-2-norbornene, 5-hydroxymethyl-2-norbornene, 5,6-di (hydroxymethyl) -2-norbornene, 5,5-di (hydroxymethyl) -2-norbornene, 5- (2- Bicyclo [2.2.1] hept-2-enes having a hydroxyl group such as hydroxyethoxycarbonyl) -2-norbornene and 5-methyl-5- (2-hydroxyethoxycarbonyl) -2-norbornene; tetracyclo [ 6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol and tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydroxyl group such as 0 ^2,7 ] dodec-9-en-4-ol. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept-2-enes having a hydrocarbonyl group such as 5-norbornene-2-carbaldehyde;
Tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydrocarbonyl group such as 0 ^2,7 ] dodec-9-ene-4-carbaldehyde. 0 ^2,7 ] dodec-4-enes;

  Bicyclo [2.2.1] hept-2-enes having an alkoxylcarbonyl group and a hydroxycarbonyl group such as 3-methoxycarbonyl-5-norbornene-2-carboxylic acid;

Bicyclo having a carbonyloxy group such as 5-norbornen-2-yl acetate, 2-methyl-5-norbornen-2-yl acetate, 5-norbornen-2-yl acrylate, and 5-norbornen-2-yl methacrylate [2.2.1] hept-2-enes;

Acetic acid 9-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enyl, acetic acid 9-tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enyl, 9-tetracycloacrylic acid [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-enyl, and 9-tetracyclomethacrylic acid [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a carbonyloxy group such as 0 ^2,7 ] dodec-4-enyl. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept- having functional groups containing nitrogen atoms such as 5-norbornene-2-carbonitrile, 5-norbornene-2-carboxamide, and 5-norbornene-2,3-dicarboxylic imide 2-enes; 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-carboxamide, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a nitrogen atom such as 0 ^2,7 ] dodec-9-ene-4 and 5-dicarboxylic imide. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept-2-enes having a halogen atom such as 5-chloro-2-norbornene; 9-chlorotetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a halogen atom such as 0 ^2,7 ] dodec-4-ene. 0 ^2,7 ] dodec-4-enes;

Bicyclo [2.2.1] hept-2-enes having a functional group containing a silicon atom such as 5-trimethoxysilyl-2-norbornene and 5-triethoxysilyl-2-norbornene; 4-trimethoxysilyl Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene and 4-triethoxysilyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a silicon atom such as 0 ^2,7 ] dodec-9-ene. 0 ^2,7 ] dodec-4-enes; and the like.
These norbornene monomers can be used alone or in combination of two or more.

  The hydride of the norbornene ring-opening polymer is obtained by ring-opening copolymerizing a norbornene monomer and a monomer copolymerizable with the norbornene monomer to obtain a norbornene ring-opening copolymer. Further, it may be obtained by hydrogenating a carbon-carbon double bond in the main chain of the obtained ring-opening copolymer.

  Examples of the monomer copolymerizable with the norbornene monomer include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; styrene, α-methylstyrene, p- Styrenes such as methylstyrene, p-chlorostyrene, and indene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; methyl acrylate, ethyl acrylate, and 2- Acrylates such as ethyl hexyl acrylate; metal methacrylates such as methyl methacrylate and ethyl methacrylate;

  The segment (A) used for the thermoplastic resin of the present invention has crystallinity among the hydrogenated norbornene-based ring-opening polymer thus obtained.

  Specific examples of the segment (A) include a polynorbornene hydride; a syndiotactic poly (endo-dicyclopentadiene) hydride, and an isotactic poly (endo-diene) because a crystalline polymer is easily obtained. Polydicyclopentadiene hydrides such as cyclopentadiene) hydrides; polytetracyclododecene hydrides such as syndiotactic poly (tetracyclododecene) hydrides, and isotactic poly (tetracyclododecene) hydrides; etc. Is mentioned.

  These segments can be used alone or in combination of two or more as segment (A). Among these, polydicyclopentadiene hydride is preferable, and syndiotactic poly (endo-dicyclopentadiene) hydride and isotactic poly (endo-dicyclopentadiene) hydride have a good balance between heat resistance and moldability. Therefore, it is particularly preferable.

Whether it has crystallinity can be confirmed by observing a peak due to the heat of fusion of the crystal when measured with a differential scanning calorimeter (DSC).
The melting point of the segment (A) is usually 50 to 400 ° C, preferably 100 to 300 ° C. If it is lower than the above range, the heat resistance becomes insufficient, and if it is higher than the above range, molding becomes difficult.

  In the thermoplastic resin of the present invention, the abundance ratio of the segment (A) to the total polymer is 1 to 50% by weight, preferably 2 to 45% by weight, more preferably 3 to 40% by weight. If it is less than the said range, the effect which makes a segment (A) exist cannot be anticipated, and when more than the said range, there exists a possibility that the characteristic of the segment (B) mentioned later may not be expressed.

  The weight average molecular weight (Mw) of the segment (A) is usually 1,000 to 500,000, preferably 1,500 to 200,000, more preferably 2,000 to 100,000. If the weight average molecular weight of the segment (A) is too small, crystallization may not occur, and if the weight average molecular weight is too large, the characteristics of the segment (B) may not be expressed.

  As will be described later, the thermoplastic resin of the present invention usually undergoes a polymerization reaction using a norbornene-based ring-opening polymer segment (C) and a polymer segment (D), which are segments before hydrogenation. After the coalescence is obtained, it is produced by hydrogenating this. Therefore, the molecular weight of the segment (A) can be determined by measuring the molecular weight of the norbornene-based ring-opening polymer segment (C) before hydrogenation, or by hydrogenating the segment (C) alone.

(2) Segment (B)
The segment (B) used for the thermoplastic resin of the present invention has a specific glass transition temperature (Tg) and is an amorphous polymer. The segment (B) imparts the property of high moldability to the thermoplastic resin.

The segment (B) is not particularly limited as long as it has a specific glass transition temperature (Tg) and is an amorphous polymer.
The Tg of the segment (B) is 40 to 300 ° C, preferably 50 to 270 ° C, particularly preferably 60 to 250 ° C. If it is less than the above range, the heat resistance is insufficient.

  The weight average molecular weight (Mw) of the segment (B) is usually 4,000 to 1,000,000, preferably 5,000 to 800,000, more preferably 7,000 to 500,000. If the molecular weight is too small, the mechanical strength becomes weak, and if the molecular weight is too large, the melt viscosity becomes high and molding becomes difficult.

  Specific examples of the segment (B) include: (Ba) amorphous norbornene ring-opening polymer hydride, (Bb) styrene polymer or hydride thereof, (Bc) acrylate polymer Etc. These segments can be used as a segment (B) individually by 1 type or in combination of 2 or more types.

(Ba) Amorphous norbornene-based ring-opening polymer hydride The norbornene-based ring-opening polymer hydride is usually amorphous. Therefore, as the norbornene ring-opening polymer hydride, all the norbornene ring-opening polymer hydrides except the crystalline norbornene ring-opening polymer hydride of the segment (A) are amorphous norbornene ring-opening polymers. Included in polymer hydrides.

  As described above, the hydride of a norbornene-based ring-opening polymer is obtained by subjecting a norbornene-based monomer to ring-opening polymerization to obtain a norbornene-based ring-opening polymer, and then the carbon in the main chain of the obtained ring-opening polymer. -It can be produced by hydrogenating carbon double bonds. As the norbornene-based monomer, those listed in the section of the hydrogenated norbornene-based ring-opening polymer of the segment (A) can be used.

(Bb) Styrene polymer or hydride thereof As long as the styrene polymer is a polymer obtained by polymerizing styrenes, any polymer is included. Examples of styrenes include styrene, α-methyl styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, ethyl styrene, trimethyl styrene, t-butyl styrene, indene, chlorostyrene, bromomethyl styrene, acetoxymethyl styrene. Etc. Examples of the styrenic polymer include polymers obtained using one or more of these styrenes.
The hydride is a vinylcyclohexane polymer obtained by hydrogenating an aromatic double bond in these polymers.

  The styrene polymer or hydride thereof may be a copolymer of styrenes and a monomer copolymerizable with styrenes or a hydride thereof. Examples of the monomer copolymerizable with styrenes include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; and chain structures such as 1,3-butadiene and isoprene. Conjugated dienes; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; acrylates such as methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate;

(Bc) Acrylate polymer The acrylate polymer includes any polymer as long as it is a polymer obtained by polymerizing acrylates. Examples of acrylates include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and hydroxyethyl acrylate. Examples of the acrylate polymer include polymers obtained using one or more of these acrylates.

  The acrylate polymer may be a copolymer of acrylates and a monomer copolymerizable with acrylates. Examples of monomers copolymerizable with acrylates include styrenes such as styrene, α-methylstyrene, and p-methylstyrene; α- such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene. Olefins; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether;

  The thermoplastic resin of the present invention is one in which the segment (A) is bonded to the segment (B) in an amount of 1 to 50% by weight based on the total polymer. Specifically, a block copolymer or graft copolymer of segment (A) and segment (B) is preferable. The block copolymer includes a diblock copolymer and a multiblock copolymer. The graft copolymer may be one obtained by grafting a plurality of segments (B) on the segment (A), or may be one obtained by grafting a plurality of segments (A) on the segment (B).

  The weight average molecular weight (Mw) of the thermoplastic resin of the present invention is 5,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 15,000 to 800,000, and particularly preferably 20. , 000 to 500,000. When the Mw is smaller than the above range, the mechanical strength is poor, and when it is larger than the above range, the viscosity is high and handling becomes difficult, which is not preferable.

2) Production method of thermoplastic resin The production method of the thermoplastic resin of the present invention is a norbornene-based ring-opening polymer which becomes a crystalline polymer when 80% or more of carbon-carbon double bonds in the main chain are hydrogenated. Hydrogenation of segment (C) (hereinafter referred to as “segment (C)”) and 80% or more of the carbon-carbon double bonds in the main chain results in an amorphous material having a glass transition temperature (Tg) of 40 to 300 ° C. 80% or more of the carbon-carbon double bonds in the main chain of the block copolymer or graft copolymer with the polymer segment (D) (hereinafter referred to as “segment (D)”) to be a crystalline polymer Is characterized by hydrogenation.

  The segment (C) is a norbornene-based ring-opening polymer segment that becomes a crystalline polymer when 80% or more of the carbon-carbon double bonds in the main chain are hydrogenated, that is, the carbon-carbon double bond in the main chain. It is a norbornene-based ring-opening polymer segment that becomes a segment (A) when 80% or more of the bonds are hydrogenated.

Specific examples of the segment (C) include: polynorbornene; polydicyclopentadiene such as syndiotactic poly (endo-dicyclopentadiene) and isotactic poly (endo-dicyclopentadiene); syndiotactic poly (tetracyclo Dodecene), and polytetracyclododecene such as isotactic poly (tetracyclododecene); and the like.
These segments can be used individually by 1 type or in combination of 2 or more types. Among these, polydicyclopentadiene is preferable, and syndiotactic poly (endo-dicyclopentadiene) and isotactic poly (endo-dicyclopentadiene) are particularly preferable.

  The segment (D) is a polymer segment that becomes a polymer having a glass transition temperature (Tg) of 40 to 300 ° C. when 80% or more of carbon-carbon double bonds in the main chain are hydrogenated, that is, in the main chain. It is a polymer segment which becomes a segment (B) when 80% or more of carbon-carbon double bonds are hydrogenated.

  Specific examples of the segment (D) include (Da) amorphous norbornene-based ring-opening polymer, (Db) styrene-based polymer, (Dc) acrylate-based polymer, and the like. Here, as the (Da) amorphous norbornene-based ring-opening polymer, the ring-opening polymer before hydrogenation of the amorphous norbornene-based ring-opening polymer hydride of (Ba), (Db) The styrene polymer is a styrene polymer among the (Bb), and the (Dc) acrylate polymer is the same as the (Bc) acrylate polymer. Is mentioned. These segments can be used individually by 1 type or in combination of 2 or more types.

  There is no restriction | limiting in particular as a method of manufacturing the block copolymer or graft copolymer of a segment (C) and a segment (D). For example, the following methods can be mentioned, but the method is not limited thereto.

(1) Method for producing a block copolymer of segment (C) and (Da) amorphous norbornene-based ring-opening polymer (segment (Da)) In the presence of a metathesis polymerization catalyst in an organic solvent The block copolymer can be synthesized by alternately adding the norbornene monomer to be the segment (C) and the norbornene monomer to be the segment (Da). Diblock to multiblock can be made differently depending on the number of times of alternating addition. In addition, when the norbornene-type monomer used as the segment (C) is dicyclopentadiene or tetracyclododecene, a stereoregular polymerization catalyst is preferably used as the metathesis polymerization catalyst. Examples of the stereoregular polymerization catalyst include W and Mo catalysts described in WO2001 / 14446 pamphlet and JP-A-2005-89744.

  When a living polymerization catalyst is used as the metathesis polymerization catalyst, almost 100% of the block copolymer can be synthesized. On the other hand, when a metathesis polymerization catalyst that is not living polymerizable is used, not only a block copolymer but also a segment (C) and / or a segment (D-a) that are not copolymerized are produced. Even if these homopolymers are contained, if a block copolymer is present, the thermoplastic resin obtained later is excellent in transparency, heat resistance and oil resistance, so that it does not matter.

(2) Method for producing block copolymer or graft copolymer of segment (C) and (Db) styrenic polymer (segment (Db)) Segment (C) and segment (Db) ) And a block copolymer can be produced by the method described in the literature (Macromolecules, 2002, Vol. 35).
The graft copolymer of the segment (C) and the segment (Db) can be produced by the method described in the literature (Macromolecules, 1997, Vol. 30).
In addition, a block copolymer is produced by ring-opening polymerization of a norbornene monomer to be a segment (C) in the presence of a metathesis polymerization catalyst in the presence of a styrene polymer having a vinyl group at the terminal. Can do.

(3) Method for producing block copolymer of segment (C) and (Dc) acrylate polymer (segment (Dc)) Norbornene monomer to be segment (C) and segment (D -C) The block copolymer with the acrylate monomer is obtained by subjecting the norbornene monomer to ring-opening polymerization in the same manner as described in Non-Patent Document 1 and then radical polymerization. Can be manufactured.

  The metathesis polymerization catalyst used in the above (1) to (3) is not particularly limited, and is a halide, oxyhalide, alkoxyhalide, alkoxide, carboxylate of groups 4 to 8 of the periodic table. Oxy) acetylacetonate or a carbonyl complex and an alkylating agent or Lewis acid functioning as a co-catalyst in combination with a metathesis polymerization catalyst; Periodic Table Group 4 to Group 8 transition metal metal carbene complex catalyst; Periodic Table A conventionally well-known thing, such as a metallacyclobutane complex catalyst of a group 4-a group 8 transition metal, can be used.

  Examples of the living polymerizable ring-opening metathesis polymerization catalyst include a molybdenum or tungsten metal carbene complex catalyst called a Schrock type catalyst; a ruthenium carbene complex catalyst and a titanacyclobutane complex catalyst called a Grubbs type catalyst; and the like.

Preferable specific examples of the Schrock type catalyst include 2,6-diisopropylphenylimide neophylidene molybdenum (VI) bis (t-butoxide) and 2,6-diisopropylphenylimide neophylidene molybdenum (VI) bis (hexa). Fluoro-t-butoxide) and the like.
Preferable specific examples of the Grubbs type catalyst include bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride.

The polymerization reaction is performed by mixing the monomer to be the segment (C), the monomer to be the segment (D), and the metathesis polymerization catalyst.
The polymerization reaction temperature is not particularly limited, but is usually −30 ° C. to + 200 ° C., preferably 0 ° C. to + 180 ° C.
The polymerization reaction time is usually 1 minute to 100 hours, depending on the reaction scale.

  The polymerization reaction can be performed in a suitable solvent. Solvents used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, decahydronaphthalene, bicycloheptane, tri Cycloaliphatic hydrocarbons such as cyclodecane, hexahydroindene and cyclooctane; halogen-containing aliphatic solvents such as dichloromethane, chloroform and 1,2-dichloroethane; halogen-containing aromatic solvents such as chlorobenzene and dichlorobenzene; nitromethane, nitrobenzene, Nitrogen-containing solvents such as acetonitrile; aliphatic ethers such as diethyl ether and tetrahydrofuran; aromatic ethers such as anisole and phenetole; These solvents can be used alone or in combination of two or more. Among these, industrially versatile aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, aliphatic ethers, and aromatic ethers are preferred, aromatic hydrocarbons, aliphatic hydrocarbons, and An alicyclic hydrocarbon is more preferable.

  The concentration of all monomers used in the polymerization reaction in the solvent is usually 1 to 50% by weight, preferably 2 to 45% by weight, and particularly preferably 3 to 40% by weight. When it is smaller than the above range, the productivity is deteriorated, and when it is larger than the above range, the solution viscosity after polymerization becomes large and the subsequent process becomes difficult.

In the polymerization reaction, a molecular weight modifier can be added to adjust the molecular weight as desired. Examples of molecular weight regulators to be used include α-olefins such as 1-butene, 1-pentene, 1-hexane and 1-octene; aromatic vinyl compounds such as styrene and vinyltoluene; ethyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether, Oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; halogen-containing vinyl compounds such as allyl chloride; nitrogen-containing vinyl compounds such as acrylamide; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, Non-conjugated dienes such as 1,6-heptadiene, 2-methyl-1,4-pentadiene, 2,5-dimethyl-1,5-hexadiene; 1,3-butadiene, 2-methyl-1,3-butadiene, 1 , 3-pentadiene, 1,3-hexene Conjugated dienes such as a diene; and the like.
The addition amount of the molecular weight modifier can be arbitrarily selected within the range of 0.1 to 10 mol% with respect to the total monomers used.

The method for hydrogenating the carbon-carbon double bond in the main chain of the block copolymer or graft copolymer obtained as described above is not particularly limited. For example, hydrogen and a hydrogenation catalyst in a solvent. The method of hydrogenating in presence is mentioned.
At this time, the carbon-carbon double bonds in the side chain may be simultaneously hydrogenated. In the case of a polymer having an aromatic ring in the side chain as in the segment (Db), the aromatic ring may not be hydrogenated or may be hydrogenated to be cycloalkylated.

  The hydrogenation reaction can be performed after the ring-opening copolymer is once isolated, or can be continuously performed by adding a hydrogenation catalyst to the reaction solution obtained by the ring-opening copolymerization reaction. The latter is preferable from the viewpoint of production efficiency.

It does not specifically limit as a hydrogenation catalyst to be used, What is generally used for the hydrogenation reaction of an olefin compound can be used suitably. For example, combinations of transition metal compounds and alkali metal compounds, such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, tetrabutoxytitanate and dimethylmagnesium Ziegler catalyst comprising: noble metal complex catalyst such as dichlorotris (triphenylphosphine) rhodium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium; homogeneous catalyst such as nickel, palladium, platinum Metals such as rhodium and ruthenium; these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina and titanium oxide. It was supported heterogeneous catalyst; and the like.
These hydrogenation catalysts can be used alone or in combination of two or more.

Among these, a supported heterogeneous catalyst is preferable because the hydrogenation catalyst can be easily removed by filtering the reaction solution after the hydrogenation reaction.
Specific examples of the supported heterogeneous catalyst include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina.

  The amount of the hydrogenation catalyst used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.3 to 10 parts by weight, particularly preferably, per 100 parts by weight of the ring-opening copolymer. Is in the range of 0.5 to 2.0 parts by weight.

  The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent can be appropriately selected depending on the solubility of the hydride to be produced, but it is preferable to use an organic solvent similar to the organic solvent used in the ring-opening copolymerization reaction. This is because, after the ring-opening copolymerization reaction, the hydrogenation catalyst can be added and reacted as it is without replacing the solvent.

What is necessary is just to select hydrogenation reaction conditions suitably according to the kind of hydrogenation catalyst to be used.
The reaction temperature is usually -20 to + 250 ° C, preferably -10 to + 220 ° C, more preferably 0 to + 200 ° C. If it is less than the above range, the reaction rate becomes slow, while if it exceeds the above range, side reactions may occur.

  A hydrogen pressure is a gauge pressure, and is 0.01-20 Mpa normally, Preferably it is 0.05-15 Mpa, More preferably, it is 0.1-10 Mpa. If the hydrogen pressure is less than the above range, the hydrogenation rate is slow, and if it exceeds the above range, a high pressure reactor is required.

Although reaction time will not be specifically limited if it is time which can achieve a desired hydrogenation rate, Usually, it is the range of 0.1 to 10 hours.
The hydrogenation rate of the carbon-carbon double bond in the main chain of the copolymer is usually 80% or more, preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more.

  After completion of the reaction, the desired thermoplastic resin can be isolated by performing a normal post-treatment operation. For example, when a heterogeneous catalyst is used, after the hydrogenation reaction, the hydrogenation catalyst is removed by filtration, and then obtained by a solidification drying method or a direct drying method using a thin film dryer or the like. Can do. When a homogeneous catalyst is used as the hydrogenation catalyst, alcohol or water is added after the hydrogenation reaction to deactivate the catalyst, insolubilized in a solvent, and then filtered to remove the catalyst. The thermoplastic resin can be usually obtained in a powder form or a pellet form.

  The weight average molecular weight (Mw) of the thermoplastic resin of the present invention obtained as described above is 5,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 15,000 to 800. 1,000, particularly preferably 20,000 to 500,000. When the Mw is smaller than the above range, the mechanical strength is poor, and when it is larger than the above range, the viscosity is high and handling becomes difficult, which is not preferable.

The number average molecular weight (Mn) of the thermoplastic resin of the present invention is preferably 2,500 to 500,000, more preferably 5,000 to 400,000, and particularly preferably 7,500 to 250,000. .
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer can be measured by gel permeation chromatography (GPC) using tetrahydrofuran or chloroform as a solvent.

The thermoplastic resin of the present invention is excellent in transparency. When the thermoplastic resin of the present invention is molded into a plate having a thickness of 2.5 mm, the total light transmittance of the molded body is preferably 70% or more, more preferably 80% or more, and particularly preferably 85% or more. It is.
The total light transmittance of the molded product can be measured using a known spectrophotometer.

The glass transition temperature (Tg) of the thermoplastic resin of the present invention is usually 40 ° C to 300 ° C, preferably 50 ° C to 270 ° C, and the melting point (Tm) is usually 50 ° C to 400 ° C, preferably 100 ° C to 300 ° C. It has excellent heat resistance.
The glass transition temperature (Tg) and the melting point (Tm) can be measured using a differential scanning calorimeter (DSC).

The thermoplastic resin of the present invention is excellent in oil resistance.
The critical stress, which is an index of oil resistance, of the thermoplastic resin of the present invention is usually 70 kgf / cm ² or more, preferably 100 kgf / cm ² or more, particularly preferably 150 kgf / cm ² or more.

  The critical stress is a 10 mm × 100 mm × 1 mm polymer sample formed by hot pressing the thermoplastic resin of the present invention at 250 ° C. and then cooled, and the cross section is an ellipse having a major axis of 200 mm and a single diameter of 80 mm, and a height of 10 mm. The elliptical cylinder is fixed to the curved surface of a jig that is equally divided into four parts, immersed in salad oil for 1 hour at room temperature, and then the critical stress can be calculated from the position where the crack occurs.

  As will be described later, the thermoplastic resin of the present invention is useful as a resin component of the molding material of the present invention.

3) Molding material The molding material of the present invention is characterized by containing one or more of the thermoplastic resins of the present invention as a resin component.

Although the molding material of this invention contains the thermoplastic resin of this invention as a resin component, a well-known additive can be added in the range which does not impair the effect of this invention as needed.
Additives to be added include fillers, antioxidants, mold release materials, flame retardants, antibacterial agents, wood flour, coupling agents, plasticizers, colorants, lubricants, silicone oils, foaming agents, surfactants, and light stabilizers Agent, dispersion aid, heat stabilizer, UV absorber, antistatic agent, dispersant, chlorine scavenger, crystallization nucleating agent, antifogging agent, organic filler, neutralizer, decomposition agent, metal deactivation Agents, antifouling materials, thermoplastic elastomers and the like. These additives can be used alone or in combination of two or more.

  As a method for producing a molding material, a method for obtaining a pellet-shaped molding material by kneading the thermoplastic resin of the present invention and an additive to be added if necessary; the heat of the present invention in an appropriate solvent; Examples thereof include a method of obtaining a molding material by mixing a plastic resin and, if necessary, an additive to be added and removing the solvent.

  For kneading, a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder can be used. The kneading temperature is preferably in the range of 200 to 400 ° C, and more preferably in the range of 240 to 350 ° C. In addition, when kneading, the components may be added together and kneaded or may be kneaded while being added in several times.

  The molding material can be formed into a molded body using a known molding means such as an injection molding method, a compression molding method, an extrusion molding method and the like. The shape of the molded body can be appropriately selected depending on the application.

  Since the molding material of this invention contains the thermoplastic resin of this invention excellent in transparency as a resin component, the molding material of this invention is also excellent in transparency. Since the thermoplastic resin of the present invention has a crystalline segment, the molding material of the present invention is also excellent in oil resistance. In addition, in the thermoplastic resin of the present invention, when the Tm of the segment (A) is higher than the Tg of the segment (B), deformation is suppressed even at a temperature equal to or higher than Tg. Even better.

The molding material of the present invention can be molded by a conventionally known molding method to produce a molded body having an arbitrary shape.
As described above, since the molding material of the present invention is excellent in transparency, heat resistance, oil resistance and the like, the resulting molded body is also excellent in transparency, heat resistance, oil resistance and the like.

  Specific examples of the molded body include optical materials such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, and retardation films; liquids, powders Or solid medicine containers (liquid medicine containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed medicine bags, press-through packages, solid medicine containers, eye drops containers, etc.), sampling containers (for blood tests) Sampling test tubes, caps for chemical containers, blood collection tubes, specimen containers, etc.), medical instruments (such as syringes), sterile containers such as medical instruments (for scalpels, forceps, gauze, contact lenses, etc.), experimental and analytical instruments (Beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical components (plastic lenses for medical examinations, etc.) Medical equipment such as piping materials (medical infusion tubes, piping, fittings, valves, etc.), artificial organs and their components (tooth base, artificial heart, artificial tooth roots, etc.); bottles, returnable bottles, baby bottles, films, shrinks Food containers such as films; containers for processing or transfer (tanks, trays, carriers, cases, etc.), protective materials (carrier tapes, separation films, etc.), piping (pipes, tubes, valves, flow meters, filters, Pumps, etc.), liquid containers (sampling containers, bottles, ampoule bags, etc.), electronic parts processing equipment; covering materials (for electric wires, cables, etc.), consumer / industrial electronic equipment (copiers, computers) , Printer, TV, VCR, video camera, etc.), structural members (parabolic antenna structural members, flat Container structural members, such as a radar dome member) electrically insulating material such as;

  Circuit boards such as general circuit boards (rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc.), high frequency circuit boards (circuit boards for satellite communication devices, etc.); transparent conductive films (liquid crystal boards, optical memories, surface heating elements) Etc.) substrate; semiconductor encapsulant (transistor encapsulant, IC encapsulant, LSI encapsulant, LED encapsulant, etc.), electrical / electronic component encapsulant (motor encapsulant, capacitor encapsulant) Materials, switch sealing materials, sensor sealing materials, etc .; automotive interior materials such as room mirrors and meter covers; automotive exterior materials such as door mirrors, fender mirrors, beam lenses, and light covers; Is mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples. In the examples, parts and% are based on weight unless otherwise specified.
The tests and evaluations in the examples and comparative examples were performed by the following methods.

(1) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured as polystyrene converted values by gel permeation chromatography (GPC) using tetrahydrofuran or chloroform as a solvent.
(2) The copolymerization ratio and hydrogenation rate of the polymer were determined by ¹ H-NMR measurement.
(3) The melting point (Tm) and the glass transition temperature (Tg) were measured by raising the temperature at 10 ° C./min using a differential scanning calorimeter (DSC).
(4) The critical stress for fats and oils was measured by the following method. A 10 mm × 100 mm × 1 mm polymer sample molded by heat-pressing at 250 ° C. and then cooled down, and an elliptical column with a major axis of 200 mm and a single diameter of 80 mm, and an elliptical column with a height of 10 mm were equally divided into four equal parts. After being fixed on the curved surface of the tool and immersed in salad oil for 1 hour at room temperature, the critical stress was calculated from the position where the crack occurred.

(Reference Example 1)
In a glass reactor equipped with a stirrer, 0.060 part of tungsten (phenylimide) tetrachloride / diethyl ether and 1.0 part of cyclohexane were added, and 0.047 part of diethylaluminum ethoxide was added to 0.50 part of hexane. The dissolved solution was added and the whole volume was stirred at room temperature for 30 minutes. Thereto were added 7.5 parts of dicyclopentadiene, 27.0 parts of cyclohexane, and 5.0 parts of 1-octene, and the polymerization reaction was carried out at 50 ° C. As a result, the viscosity of the solution gradually increased. After the reaction for 3 hours, a large amount of isopropyl alcohol was poured into the reaction solution to aggregate the precipitate, and after washing by filtration, the precipitate was dried under reduced pressure at 40 ° C. for 24 hours to obtain 7.4 parts of the ring-opening polymer (1). Mn of the obtained ring-opening polymer (1) was 3,800, and Mw was 13,000. The cis / trans ratio of the carbon-carbon double bond in the ring-opening polymer main chain was 93/7.

Next, 5 parts of the ring-opening polymer (1) and 35 parts of cyclohexane are placed in an autoclave equipped with a stirrer, and 0.029 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.025 of ethyl vinyl ether are added thereto. A hydrogenation catalyst solution in which a part was dissolved in 5 parts of toluene was added, and a hydrogenation reaction was performed at hydrogen pressure of 0.9 MPa and 120 ° C. for 8 hours.
The hydrogenation reaction liquid was cloudy and the hydride was insoluble. The reaction mixture was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration, and then dried under reduced pressure at 40 ° C. for 24 hours to obtain 5 parts of a ring-opened polymer hydride (1).

In ¹ H-NMR measurement of the ring-opened polymer hydride (1), no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The ratio of racemo dyad in the ring-opened polymer hydride (1) was 80%.
Further, the ring-opened polymer hydride (1) was completely insoluble in cyclohexane or toluene heated to 100 ° C., the melting point (Tm) was 272 ° C., and the heat of fusion (ΔH) was 51 J / g.

Example 1
In a glass reactor with nitrogen inside,

After adding 0.28 part of the molybdenum compound represented by the formula, 28 parts of toluene was added and dissolved. Next, 1.5 parts of a 66 wt% dicyclopentadiene (DCPD; end product> 99%) / toluene solution was added, and the mixture was stirred at room temperature for 1 hour. When a part of the reaction solution was sampled and GPC measurement was performed, Mn of the obtained polymer was 2,800, Mw was 3,200, and Mw / Mn was 1.14.

  Next, 38.6 parts of 28.6% by weight of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (MTHF) / toluene solution was added to the reaction solution and left at room temperature for 1 day. The obtained polymerization reaction liquid is diluted with toluene, and then poured into a large amount of methanol to completely precipitate the polymer. After filtration and washing, the polymer is dried under reduced pressure at 40 ° C. for 24 hours to obtain a ring-opening copolymer (2). 10.5 parts were obtained. Mn of the obtained ring-opening copolymer (2) was 28,600, Mw was 34,100, and Mw / Mn was 1.19.

  Next, 5 parts of the ring-opening copolymer (2) and 35 parts of toluene are placed in an autoclave equipped with a stirrer, and 0.029 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0. A hydrogenation catalyst solution in which 025 parts were dissolved in 5 parts of toluene was added, and a hydrogenation reaction was carried out at 120 ° C. for 8 hours at a hydrogen pressure of 0.9 MPa. The reaction solution was poured into a large amount of methanol to completely precipitate the polymer, washed by filtration and then dried under reduced pressure at 40 ° C. for 24 hours to obtain 5 parts of a ring-opening copolymer hydride (2).

In ¹ H-NMR measurement of the ring-opening copolymer hydride (2), no peak derived from the carbon-carbon double bond in the polymer main chain was observed, and the main chain hydrogenation rate was 99% or more. . On the other hand, the aromatic ring derived from MTHF was completely maintained. The DCPD / MTHF ratio was 10/90 (w / w), and Mn = 28,800, Mw = 34,400, and Mw / Mn = 1.19.
Moreover, the ring-opening copolymer hydride (2) was easily dissolved in toluene at 100 ° C.

The ring-opening copolymer hydride (2) was hot-pressed at 250 ° C. and then slowly cooled to prepare a sample plate (2) having a thickness of 1 mm. The plate is transparent. As a result of DSC measurement, melting point (Tm) derived from DCPD ring-opening polymer hydride segment = 256 ° C., heat of fusion (ΔH) = 2.0 J / g, MTHF ring-opening polymer hydride segment The glass transition temperature (Tg) derived from the above was observed to be 135 ° C.
The critical stress of the sample plate (2) with respect to the salad oil was measured, but no crack was generated, and the critical stress was not less than the measurement limit (186 kgf / cm ² ).
Therefore, the ring-opening copolymer hydride (2) is a block copolymer of a crystalline DCPD ring-opening polymer hydride and an amorphous MTHF ring-opening polymer hydride, and has transparency, heat resistance, and It can be seen that the polymer is excellent in oil resistance.

(Example 2)
In a glass reactor equipped with a stirrer, 0.060 part of tungsten (phenylimide) tetrachloride / diethyl ether and 1.0 part of cyclohexane were added, and 0.047 part of diethylaluminum ethoxide was added to 0.50 part of hexane. The solution dissolved in was added and stirred at room temperature for 30 minutes. 7.5 parts of dicyclopentadiene, 27.0 parts of cyclohexane, and 5.0 parts of 1-octene were added to the obtained mixture, and a polymerization reaction was performed at 50 ° C. After the polymerization reaction started, the viscosity of the solution gradually increased. After stirring for 3 hours, a large amount of isopropyl alcohol was poured into the reaction solution to aggregate the precipitate, washed by filtration, and dried under reduced pressure at 40 ° C. for 24 hours to obtain 714 parts of a ring-opening polymer (3).

  Mn of the obtained ring-opening polymer (3) was 3,800, and Mw was 13,000. The cis / trans ratio of the carbon-carbon double bond in the ring-opening polymer main chain was 93/7.

  Then, 3 parts of the ring-opened polymer (3) obtained above, 24.0 parts of toluene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene 3.0 were added to a glass reactor with a stirrer. In this, 0.0039 part of benzylidene [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichlorotricyclohexylphosphine) ruthenium is dissolved in 0.1 part of toluene. The solution was added and a polymerization reaction was performed at 60 ° C. After the polymerization reaction started, the viscosity of the solution gradually increased. After reacting for 2 hours, a large amount of isopropyl alcohol was poured into the polymerization reaction solution to aggregate the precipitate, washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours to obtain 5.9 parts of the ring-opening copolymer (4). Obtained. Mn of the obtained ring-opening copolymer (4) was 6,600, and Mw was 18,000.

  In an autoclave equipped with a stirrer, 3 parts of the ring-opening copolymer (4) and 47 parts of toluene were added, and 0.0187 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 part of ethyl vinyl ether were added thereto. A hydrogenation catalyst solution dissolved in 10 ml of toluene was added, and a hydrogenation reaction was performed at a hydrogen pressure of 0.8 MPa and 160 ° C. for 8 hours. The hydrogenation reaction solution was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours to obtain 3 parts of a ring-opening copolymer hydride (5).

As a result of ¹ H-NMR measurement of the obtained ring-opening copolymer hydride (5), all peaks derived from aromatic double bonds remain, but derived from carbon-carbon double bonds in the main chain. No peak was observed, and the hydrogenation rate of the main chain double bond was 99% or more. The ring-opening copolymer hydride (5) was dissolved in toluene at 100 ° C.

The ring-opening copolymer hydride (5) was hot-pressed at 250 ° C. and then cooled to prepare a sample plate (5) having a thickness of 1 mm. The sample plate (5) is transparent. According to the 1st scan of DSC measurement, the glass transition temperatures (Tg) are 100 ° C. and 136 ° C., the melting point (Tm) is 241 ° C., and the heat of fusion (ΔH) is 11 J / g. Met.
Moreover, although the critical stress with respect to the salad oil of a sample board (5) was measured, a crack did not generate | occur | produce and the critical stress was more than a measurement limit (186 kgf / cm < ² >).
Therefore, the ring-opening copolymer hydride (5) is a block copolymer of a crystalline DCPD ring-opening polymer hydride and an amorphous MTHF ring-opening polymer hydride, and has transparency, heat resistance, and The polymer was found to be excellent in oil resistance.

(Example 3)
A glass reactor equipped with a stirrer was charged with 3 parts of the ring-opening polymer (3) obtained in Reference Example 1, 24.0 parts of cyclohexane, and 3.0 parts of 8-ethyltetracyclododecene, where benzylidene was added. [
1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium 0.0039 part dissolved in toluene 0.1 part toluene was added, The polymerization reaction was conducted in After the polymerization reaction started, the viscosity of the solution gradually increased. After the reaction for 2 hours, a large amount of isopropyl alcohol was poured into the polymerization reaction solution to aggregate the precipitate, and after washing by filtration, it was dried under reduced pressure at 40 ° C. for 24 hours to obtain 5.7 parts of the ring-opening copolymer (6). Obtained. Mn of the obtained ring-opening copolymer (6) was 7,400, and Mw was 30,000.

  In an autoclave equipped with a stirrer, 3 parts of the ring-opening copolymer (6) and 47 parts of cyclohexane are added, and 0.0187 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 part of ethyl vinyl ether are added to cyclohexane. A hydrogenation catalyst solution dissolved in 10 ml was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and 160 ° C. for 8 hours. The hydrogenation reaction solution was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours to obtain 3 parts of a ring-opening copolymer hydride (6).

As a result of ¹ H-NMR measurement of the obtained ring-opening copolymer hydride (6), no peak derived from a carbon-carbon double bond was observed, and the hydrogenation rate was 99% or more. The obtained ring-opening copolymer hydride (6) was dissolved in toluene at 100 ° C.

The ring-opening copolymer hydride (6) was hot-pressed at 250 ° C. and then cooled to prepare a sample plate (6) having a thickness of 1 mm. The sample plate (6) is transparent. According to the first scan of DSC measurement, the glass transition temperatures (Tg) are 100 ° C. and 144 ° C., the melting point (Tm) is 246 ° C., and the heat of fusion (ΔH) is 7 J / g. Met.
Moreover, although the limit stress with respect to the salad oil of a sample board (6) was measured, a crack did not generate | occur | produce and the limit stress was more than a measurement limit (186 kgf / cm < ² >).
Therefore, the ring-opening copolymer hydride (6) is a block copolymer of a crystalline DCPD ring-opening polymer hydride and an amorphous MTHF ring-opening polymer hydride, and has transparency, heat resistance, and The polymer was found to be excellent in oil resistance.

(Comparative Example 1)
In a glass reactor equipped with a stirrer, 17.0 parts of toluene, 7.5 parts of 1,4-methano-1,4,4a, 9a-tetrahydrofluorene and 0.043 parts of 1-hexene were placed. A solution of 0.0035 parts of benzylidene [1,3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] dichloro (tricyclohexylphosphine) ruthenium in 0.1 part of toluene, The polymerization reaction was performed at 60 ° C. After the polymerization reaction started, the viscosity of the solution gradually increased. After the reaction for 2 hours, a large amount of methanol was poured into the polymerization reaction solution to aggregate the precipitate. After washing by filtration, the precipitate was dried under reduced pressure at 40 ° C. for 24 hours to obtain 7.4 parts of a ring-opening copolymer (7). It was. Mn of the ring-opening copolymer (7) was 14,900, and Mw was 38,100.

  3 parts of the ring-opening copolymer (7) obtained above and 20 parts of toluene were added to an autoclave equipped with a stirrer. Next, a hydrogenation catalyst solution in which 0.0187 part of bis (tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride and 0.45 part of ethyl vinyl ether was dissolved in 10 ml of toluene was added, and the hydrogen pressure was increased to 0.8 MPa at 160 ° C. for 8 hours. The reaction was carried out. The hydrogenation reaction solution was poured into a large amount of isopropyl alcohol to completely precipitate the polymer, washed by filtration and dried under reduced pressure at 40 ° C. for 24 hours to obtain 3 parts of a ring-opening copolymer hydride (7).

As a result of ¹ H-NMR measurement of the obtained ring-opening copolymer hydride (7), all peaks derived from aromatic double bonds remain, but derived from carbon-carbon double bonds in the main chain. No peak was observed, and the hydrogenation rate of the main chain double bond was 99% or more. The obtained ring-opening copolymer hydride (7) was dissolved in toluene at room temperature.

The ring-opened copolymer hydride (7) was hot-pressed at 250 ° C. and then cooled to prepare a sample plate (7) having a thickness of 1 mm. The sample plate (7) was transparent, and the glass transition temperature (Tg) was 138 ° C. according to the first scan of DSC measurement. The limit stress on the salad oil of the sample plate (7) was 56 kgf / cm ² , which was inferior in heat resistance and oil resistance as compared with the ring-opened polymer hydrides obtained in Examples 1 to 3. .

Claims (3)

A crystalline norbornene-based ring-opening polymer hydride segment (A) comprising a polydicyclopentadiene hydride;
Amorphous polymer segment (B) having a glass transition temperature (Tg) of 40 to 300 ° C.
A thermoplastic resin which is a block copolymer or a graft copolymer ,
The presence ratio of the crystalline norbornene-based ring-opening polymer hydride segment (A) to the total polymer is 1 to 50% by weight, and
Weight average molecular weight (Mw) of 5,000 to 1,000,000
Is a thermoplastic resin. It is a manufacturing method of the thermoplastic resin of Claim 1, Comprising:
A norbornene-based ring-opening polymer segment (C) made of polydicyclopentadiene, which becomes a crystalline polymer when 80% or more of carbon-carbon double bonds in the main chain are hydrogenated;
A block copolymer with a polymer segment (D) that becomes an amorphous polymer having a glass transition temperature (Tg) of 40 to 300 ° C. when 80% or more of carbon-carbon double bonds in the main chain are hydrogenated or A method for producing a thermoplastic resin, wherein 80% or more of carbon-carbon double bonds in the main chain of the graft copolymer are hydrogenated. A molding material comprising the thermoplastic resin according to claim 1 as a resin component.