WO2016143148A1 - シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物 - Google Patents
シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物 Download PDFInfo
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- SBUPKNISIFDUKT-UHFFFAOYSA-N CC1C(C)C2C3C1C23 Chemical compound CC1C(C)C2C3C1C23 SBUPKNISIFDUKT-UHFFFAOYSA-N 0.000 description 1
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- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/70—Post-treatment
- C08G2261/72—Derivatisation
- C08G2261/724—Hydrogenation
Definitions
- the present invention provides a syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride having a high melting point and excellent heat resistance, and excellent in solution stability after polymerization reaction, and the hydride is obtained by hydrogenation reaction.
- the present invention relates to a syndiotactic dicyclopentadiene ring-opening polymer which can be converted into a ring, and a production method thereof.
- a ring-opening polymer hydride of norbornene-based monomers such as dicyclopentadiene is a kind of so-called cycloolefin polymer, and is excellent in transparency, low birefringence, molding processability, etc. It is used as a material applicable to various uses.
- the ring-opening polymer hydride of dicyclopentadiene is generally obtained as an amorphous polymer having an atactic structure.
- an amorphous dicyclopentadiene ring-opening polymer hydride having an atactic structure may have insufficient heat resistance, mechanical strength, solvent resistance, and the like depending on its use. Therefore, as a method for improving these performances, by producing a ring-opening polymer hydride of dicyclopentadiene having stereoregularity in the main chain, a ring-opening polymer hydride of dicyclopentadiene having crystallinity is obtained. Proposed.
- Patent Document 1 discloses ring opening of dicyclopentadiene using a polymerization catalyst mainly composed of a periodic table Group 6 transition metal compound having a specific substituent, such as a tungsten phenylimide tetrachloride diethyl ether complex.
- a dicyclopentadiene ring-opening polymer having a cis-syndioregularity that is soluble in a hydrocarbon solvent such as cyclohexane at room temperature is obtained. Further, a carbon-carbon double bond in the ring-opening polymer is obtained.
- Patent Document 2 uses a polymerization catalyst such as a tungsten phenylimide bisbiphenolate complex, which mainly contains a transition metal compound of Groups 4 to 6 of the periodic table having a specific aromatic dioxy group as a ligand.
- ring-opening polymerization of dicyclopentadiene yields a dicyclopentadiene ring-opening polymer having crystallinity and cis-iso regularity that is insoluble in a hydrocarbon solvent such as cyclohexane at room temperature.
- a hydrocarbon solvent such as cyclohexane at room temperature.
- the isotactic crystalline dicyclopentadiene ring-opened polymer hydride specifically described in Patent Document 2 has an isotacticity of 100% within the measurement accuracy range of the analyzer, and its melting point is It is around 295 ° C. and has a very high melting point.
- the dicyclopentadiene ring-opening polymer having a cis-isotactic structure is insoluble in a hydrocarbon solvent such as cyclohexane at room temperature, it has been difficult to produce on an industrial production scale.
- the present invention has a sufficiently high melting point, excellent heat resistance, advantageous for industrial production, syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride, and excellent solution stability after polymerization reaction, and hydrogenation. It aims at providing the syndiotactic dicyclopentadiene ring-opening polymer which can be converted into the said hydride by reaction, and those efficient manufacturing methods.
- the present inventor conducted a ring-opening polymerization of dicyclopentadiene using a polymerization catalyst containing a tungsten compound having a specific structure.
- a pentadiene ring-opening polymer is obtained, and a syndiotactic crystalline dicyclopentadiene ring-opening polymer having an extremely high melting point is obtained by hydrogenating a carbon-carbon double bond present in the dicyclopentadiene ring-opening polymer. It was found that a hydride was obtained.
- the present invention has been completed based on this finding.
- syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride (1) syndiotactic dicyclopentadiene ring-opened polymer (2), and syndiotactic (3) Method for producing tic dicyclopentadiene ring-opening polymer, (4) method for producing syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride, and (5) syndiotactic crystalline dicyclopentadiene ring-opening polymer
- a hydride molded body and a method for producing the molded body of (6) are provided.
- Syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride having a melting point of 280 ° C. or higher and a syndiotacticity higher than 90%.
- Syndiotactic dicyclopentadiene opening having a syndiotacticity higher than 90%, which can generate a syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride according to [1] by hydrogenation reaction. Ring polymer.
- W represents a tungsten atom
- R 1 and R 2 may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a substituent.
- L 1 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent.
- L 2 represents a conjugated heterocyclic group having 5 to 15 ring members having at least one nitrogen atom, and the conjugated heterocyclic group may have a substituent
- L 3 represents an alkoxy group represented by O-R 3
- R 3 is an alkyl group of from 1 to 12 carbon atoms which may have a substituent
- carbon atoms, which may have a substituent Represents a group selected from 6 to 30 aryl groups
- L 4 represents a neutral conjugated heterocyclic ligand having at least two nitrogen atoms and having 12 to 24 ring members, and the conjugated heterocyclic ligand may have a substituent.
- a syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride having a melting point as high as 280 ° C. or higher and a syndiotacticity higher than 90% is provided.
- the present invention relates to a syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride having a melting point of 280 ° C. or higher and a syndiotacticity of more than 90% (hereinafter referred to as “crystalline dicyclopentadiene ring-opening polymer of the present invention”). Hydride ”).
- the crystalline dicyclopentadiene ring-opening polymer hydride of the present invention contains a repeating unit of hydrogenated poly (endo-dicyclopentadiene) represented by the following formula (2).
- the melting point of the crystalline dicyclopentadiene ring-opening polymer hydride of the present invention is 280 ° C. or higher, preferably 282 ° C. or higher.
- the melting point is a melting point measured after the crystalline dicyclopentadiene ring-opening polymer hydride is sufficiently melted and then sufficiently crystallized.
- the upper limit of the melting point is not particularly limited, but is generally 310 ° C.
- fusing point can be measured in accordance with the method as described in the below-mentioned Example.
- the melting start temperature of the crystalline dicyclopentadiene ring-opening polymer hydride of the present invention is preferably 260 ° C. or higher, more preferably 265 ° C. or higher.
- the upper limit of the melting start temperature is not particularly limited, but is generally 310 ° C. and below the melting point. Since the crystalline dicyclopentadiene ring-opened polymer hydride of the present invention has a very high melting start temperature, it is excellent in processability such as solder reflow resistance.
- the crystalline dicyclopentadiene ring-opened polymer hydride of the present invention since the carbon represented by (1, 4) in the above formula (2) is an asymmetric carbon (indicated by *), (Tacty City) exists.
- the crystalline dicyclopentadiene ring-opening polymer hydride of the present invention has syndiotactic stereoregularity, and syndiotacticity, ie, meso diad and racemo duplex in the configuration.
- a polymer having a ratio of racemo diads in the total of racemo diads hereinafter sometimes simply referred to as a ratio of racemo diads
- the proportion of racemo diads is preferably higher than 91%, more preferably higher than 92%.
- the ratio of racemo diads is 90% or less, the crystallinity of the syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride is greatly lowered, and characteristics such as a high melting point and workability are impaired.
- the syndiotacticity can be determined by the formula I: [(Rasemo Duplicate) / (Meso Duplicate + Racemo Duplicate) ⁇ 100 (%)].
- the ratio of racemo diads can be calculated by analyzing the 13 C-NMR spectrum of the syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride. Specifically, it is determined by quantifying the spectrum of the carbon atom represented by (5, 9) in the above formula (2) of the syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride of the present invention. it can.
- the crystalline dicyclopentadiene ring-opening polymer hydride and dicyclopentadiene ring-opening polymer of the present invention have a repeating unit derived from dicyclopentadiene represented by the following formula (3).
- the syndiotactic dicyclopentadiene ring-opened polymer of the present invention (hereinafter sometimes referred to as “dicyclopentadiene ring-opened polymer”) and the crystalline dicyclopentadiene ring-opened polymer hydride are the heat resistant hydride. From the viewpoint of particularly improving the properties and increasing the crystallization rate, it is preferable to use those containing a large number of repeating units derived from dicyclopentadiene.
- the proportion of the repeating units derived from dicyclopentadiene in the total repeating units in the crystalline dicyclopentadiene ring-opening polymer hydride and dicyclopentadiene ring-opening polymer of the present invention is not particularly limited, but is 90% by weight or more. It is preferably 95% by weight or more, more preferably 97% by weight or more.
- the crystalline dicyclopentadiene ring-opened polymer hydride of the present invention contains dicyclopentadiene or dicyclopentadiene and another cyclic olefin monomer in the presence of a specific ring-opening polymerization catalyst.
- a monomer mixture (hereinafter, these may be collectively referred to as “dicyclopentadiene, etc.”) is subjected to ring-opening polymerization to obtain a dicyclopentadiene ring-opening polymer, and then hydrogenated to obtain an efficiency. Can get well.
- dicyclopentadiene there are stereoisomers of endo and exo, both of which can be used as monomers, and either isomer may be used alone, or endo and It is also possible to use an isomer mixture in which an exo isomer is present in an arbitrary ratio. From the viewpoint of increasing the crystallinity of the crystalline dicyclopentadiene ring-opening polymer hydride and making its heat resistance particularly favorable, it is preferable to increase the ratio of one stereoisomer.
- the dicyclopentadiene used preferably has an endo or exo ratio of 90% or more, more preferably 95% or more, and particularly preferably 99% or more.
- the stereoisomer which makes a ratio high is an end body from a viewpoint of synthetic
- dicyclopentadiene can be used in combination with another cyclic olefin monomer.
- the amount of the other cyclic olefin monomer used is less than 10% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, based on the total amount of dicyclopentadiene and the other cyclic olefin monomer. .
- dicyclopentadiene such as unda-3-ene
- Norbornene having an unsubstituted or alkyl group as a substituent such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, 5-cyclopentylnorbornenekind
- Norbornenes having an alkenyl group as a substituent such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene, 5-cyclopentenyl norbornene
- Norbornenes having an aromatic ring as a substituent such as 5-phenylnorbornene
- alkyl such as 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, 8-cyclopentyltetracyclododecene, etc.
- Tetracyclododecenes having a group as a substituent 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8-cyclopentenyltetracyclododecene Tetracyclododecenes having a double bond outside the ring, such as Tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxycarbonyltetracyclododecene, 8-methyl-8-methoxycarbonyltetracyclodecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododec
- Hexacycloheptadecenes include unsubstituted or non-substituted hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, 12-cyclopentylhexacycloheptadecene, etc.
- Hexacycloheptadecenes having an alkyl group as a substituent 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12-cyclopentenylhexacycloheptadecene Hexacycloheptadecenes having a double bond outside the ring, etc .; Hexacycloheptadecenes having an aromatic group as a substituent, such as 12-phenylhexacycloheptadecene;
- the number average molecular weight (Mn) of the crystalline dicyclopentadiene ring-opening polymer hydride of the present invention is usually 500 to 1,000,000, preferably 1000 to 600,000, more preferably 2000 to 400,000. . If Mn is too low, the mechanical strength may decrease, and if Mn is too high, molding tends to be difficult.
- the number average molecular weight of the syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride is substantially equal to the number average molecular weight of the dicyclopentadiene ring-opened polymer before the hydrogenation step.
- the glass transition point (Tg) of the crystalline dicyclopentadiene ring-opening polymer hydride of the present invention is preferably 80 ° C. or higher, more preferably 85 ° C. or higher. If the glass transition point is within such a range, the heat resistance is good, for example, the deflection temperature under load is high, which is preferable.
- the upper limit of the glass transition point is not particularly limited, but is approximately 120 ° C.
- the dicyclopentadiene ring-opening polymer of the present invention can be obtained by subjecting dicyclopentadiene or the like to ring-opening polymerization using a polymerization catalyst containing a tungsten compound represented by the following formula (1).
- W represents a tungsten atom.
- R 1 and R 2 may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a substituent.
- L 1 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent.
- the nitrogen atom which may have the substituent selected from is represented.
- L 2 represents a conjugated heterocyclic group having 5 to 15 ring members having at least one nitrogen atom, and the conjugated heterocyclic group may have a substituent.
- L 3 represents an alkoxy group represented by O-R 3
- R 3 is an alkyl group of from 1 to 12 carbon atoms which may have a substituent, and carbon atoms, which may have a substituent Represents a group selected from 6 to 30 aryl groups.
- L 4 represents a neutral conjugated heterocyclic ligand having at least two nitrogen atoms and having 12 to 24 ring members, and the conjugated heterocyclic ligand may have a substituent.
- the tungsten compound represented by the above formula (1) is used as a polymerization active component of a polymerization catalyst for ring-opening polymerization of dicyclopentadiene or the like.
- W is a tungsten atom.
- R 1 and R 2 are each independently a hydrogen atom; an alkyl group having 1 to 12 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group; A cycloalkyl group having 3 to 20 carbon atoms which may have a substituent such as a cyclopropyl group, a cyclopentyl group or a cyclohexyl group; or an aryl group having 6 to 12 carbon atoms which may have a substituent; Represents.
- Examples of the aryl group of the aryl group which may have a substituent include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- Examples of the substituent for the cycloalkyl group and the aryl group include alkyl groups having 1 to 12 carbon atoms such as a methyl group and an ethyl group; halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; a methoxy group, an ethoxy group, An alkoxy group having 1 to 12 carbon atoms such as a propoxy group; a haloalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group; a haloalkoxy group having 1 to 12 carbon atoms such as a trifluoromethoxy group; a phenyl group, 4-methyl And an aryl group having 6 to 12 carbon atoms which may have
- L 1 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms which may have a substituent, and a cycloalkyl group having 3 to 20 carbon atoms which may have a substituent.
- the nitrogen atom which may have the substituent selected from is represented.
- the alkyl group having 1 to 12 carbon atoms which the nitrogen atom of L 1 has may be either linear or branched. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group and the like.
- Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
- Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group and the like.
- the substituent that the nitrogen atom of L 1 may have in the cycloalkyl group having 3 to 20 carbon atoms and the aryl group having 6 to 12 carbon atoms is not particularly limited.
- an alkyl group having 1 to 12 carbon atoms such as a methyl group or an ethyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group or an isopropoxy group
- a haloalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group; a haloalkoxy group having 1 to 12 carbon atoms such as a trifluoromethoxy group; a phenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, 2
- An aryl group having 6 to 12 carbon atoms which may have a
- aryl group having 6 to 12 carbon atoms which may have a substituent include a phenyl group, 2-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, pentafluoro A phenyl group etc. are mentioned.
- L 2 represents a conjugated heterocyclic group which has at least one nitrogen atom and has 5 to 15 ring members and may have a substituent.
- the conjugated heterocyclic group of L 2 include 5-membered conjugated heterocyclic groups such as pyrrolyl, imidazolyl, pyrazolyl, oxazolyl and thiazolyl groups; pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like 6-membered ring conjugated heterocyclic group; condensed ring conjugated heterocyclic group such as quinazolinyl group, phthalazinyl group, pyrrolopyridyl group; and the like.
- the substituent that the conjugated heterocyclic group may have is not particularly limited.
- an alkyl group having 1 to 12 carbon atoms such as a methyl group or an ethyl group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group or an isopropoxy group
- a haloalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group; a haloalkoxy group having 1 to 12 carbon atoms such as a trifluoromethoxy group; a phenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, 2
- An aryl group having 6 to 12 carbon atoms which may have a substituent such as a chlorophenyl group or a 3-methoxyphenyl group; an amino group; a mono
- L 3 is a group represented by —O—R 3 .
- R 3 is a group selected from an alkyl group having 1 to 12 carbon atoms which may have a substituent and an aryl group having 6 to 30 carbon atoms which may have a substituent.
- alkyl group having 1 to 12 carbon atoms of the alkyl group having 1 to 12 carbon atoms which may have a substituent of R 3 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t- A butyl group, a pentyl group, etc. are mentioned.
- the substituent that the alkyl group having 1 to 12 carbon atoms of R 3 can have is not particularly limited.
- a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom
- an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group or an isopropoxy group
- a haloalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group
- a haloalkoxy group having 1 to 12 carbon atoms such as a trifluoromethoxy group
- having a substituent such as a phenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2-chlorophenyl group, a 3-methoxyphenyl group
- an aryl group having 6 to 12 carbon atoms an amino group; a mono-substituted amino group such as a methylamino group;
- Examples of the aryl group having 6 to 30 carbon atoms which may have a substituent include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and an adamantyl group.
- the substituent that the aryl group having 6 to 30 carbon atoms of R 3 can have is not particularly limited.
- halogen atoms such as fluorine atom, chlorine atom and bromine atom
- alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group, isopropyl group and t-butyl group
- an alkoxy group having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group
- a haloalkyl group having 1 to 12 carbon atoms such as a trifluoromethyl group
- a haloalkoxy group having 1 to 12 carbon atoms which may have a substituent such as phenyl group, 4-methylphenyl
- L 3 include 1,1,1,3,3,3-hexafluorofluoro-2-propoxy group, 2-methyl-2-propoxy group, 1,1,1-trifluoro-2- Methyl-2-propoxy group, 1,1,1-trifluoro-2-trifluoromethyl-2-propoxy group, 2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy group, etc.
- R 3 is an optionally substituted alkyl group having 1 to 12 carbon atoms; 2,6-bis (2,4,6-trimethylphenyl) phenoxy group, 2,6-bis (2, 4, 6-triisopropylphenyl) phenoxy group, 2,4,6-trimethylphenoxy group, 2,3,5,6-tetraphenylphenoxy group, etc., and R 3 may have a substituent carbon number Groups that are 6-30 aryl groups And the like.
- L 4 is a neutral conjugated heterocyclic ligand having at least 2 nitrogen atoms and having 12 to 24 ring members.
- Specific examples of the ligand include 2,2′-bipyridyl, 5,5′-dimethyl-2,2′-bipyridyl, 4,4′-dimethyl-2,2′-bipyridyl, 4,4′- Examples include dibromo-2,2′-bipyridyl, 2,2′-biquinoline, 1,10-phenanthroline, and terpyridine.
- conjugated heterocyclic group of L 4 may have a substituent.
- substituents include those listed as substituents that the conjugated heterocyclic group of L 2 may have.
- tungsten compound used in the present invention include (2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy) 2,6-dimethylphenylimidotungsten (VI) (2,5-dimethyl).
- Pyrrolide (neophylidene) (1,10-phenanthroline), (2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy) phenylimidotungsten (VI) (2,5-dimethylpyrrolide) (Neophylidene) (1,10-phenanthroline), (2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy) 2,6-dimethylphenylimidotungsten (VI) (2,5-dimethylpyrrole) D) (Neophylidene) (2,2'-bipyridine), (2-trifluoromethyl-2- Examples include, but are not limited to, phenyl-1,1,1-trifluoroethoxy) phenylimidotungsten (VI) (2,5-dimethylpyrrolide) (neophylidene) (2,2′-bipyridine) is not.
- the tungsten compound used as a polymerization catalyst has a neutral conjugated heterocyclic ligand, but a metal salt compound may be used in combination to increase the rate of ring-opening polymerization of dicyclopentadiene.
- a metal salt compound By using a metal salt compound in combination, the neutral conjugated heterocyclic ligand can be eliminated from the Group 6 transition metal compound of the periodic table, and a highly active catalyst species can be obtained.
- the metal atom constituting the metal salt zinc, tin, copper, titanium, rare earth and the like are suitable. Specific examples of metal salts that can be used include zinc chloride, copper chloride, tin chloride, titanium chloride, scandium chloride, yttrium chloride, and the like.
- Group 6 transition metal compounds of the periodic table can be produced, for example, by the method described in JP-T-2014-520103 (International Publication No. 2012/167171). Moreover, what is marketed as a periodic table group 6 transition metal compound can also be refine
- dicyclopentadiene or the like and a polymerization catalyst may be mixed in order to perform ring-opening polymerization of dicyclopentadiene or the like.
- the amount of the polymerization catalyst used relative to dicyclopentadiene is not particularly limited, but the molar ratio of tungsten compound: dicyclopentadiene, etc. in the polymerization catalyst is 1:10 to 1: 2,000,000. A range is preferred, a range of 1: 200 to 1,000,000 is more preferred, and a range of 1: 500 to 1: 500,000 is particularly preferred. If the amount of the polymerization catalyst used is too large, it may be difficult to remove the polymerization catalyst, and if it is too small, sufficient polymerization activity may not be obtained.
- the polymerization reaction can be carried out in a solventless system, but it is preferably carried out in an organic solvent from the viewpoint of controlling the reaction well.
- the organic solvent used in this case is not particularly limited as long as it can dissolve or disperse the produced ring-opening polymer and does not adversely affect the polymerization reaction.
- organic solvents that can be used include aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, Alicyclic hydrocarbons such as tricyclodecane, hexahydroindenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene Halogen-containing aromatic hydrocarbons such as dichlorobenzene; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzen
- the concentration of the monomer in the reaction system is not particularly limited, but is preferably 1 to 50% by weight, and preferably 2 to 45% by weight. More preferred is 3 to 40% by weight. If the concentration of the monomer is too low, the productivity may be deteriorated. If it is too high, the viscosity of the reaction solution after the polymerization reaction becomes too high, and the subsequent hydrogenation reaction may be difficult.
- the polymerization temperature is not particularly limited, but is usually ⁇ 30 ° C. to + 200 ° C., preferably 0 ° C. to 180 ° C.
- the polymerization time is not particularly limited, but is usually selected in the range of 1 minute to 100 hours.
- a vinyl compound or a diene compound may be added to the polymerization reaction system for the purpose of adjusting the molecular weight of the resulting dicyclopentadiene ring-opened polymer.
- the vinyl compound used for the purpose of adjusting the molecular weight is not particularly limited as long as it is an organic compound having a vinyl group.
- ⁇ -olefins such as 1-butene, 1-pentene, 1-hexene and 1-octene; styrenes such as styrene and vinyltoluene; ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether; allyl Halogen-containing vinyl compounds such as chloride; oxygen-containing vinyl compounds such as allyl acetate, allyl alcohol and glycidyl methacrylate; nitrogen-containing vinyl compounds such as acrylamide; silicon-containing vinyl compounds such as vinyltrimethylsilane, allyltrimethylsilane and vinyltrimethoxysilane; Can be used.
- styrenes such as styrene and vinyltoluene
- ethers such as ethyl vinyl ether, i-butyl vinyl ether and allyl glycidyl ether
- allyl Halogen-containing vinyl compounds such as
- the diene compound used for the purpose of adjusting the molecular weight is not particularly limited.
- Conjugated dienes; conjugated dienes such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. are used. be able to.
- the amount of vinyl compound or diene compound to be added may be determined according to the target molecular weight, but is usually in the range of 0.1 to 10 moles per 100 moles of dicyclopentadiene or the like used as a monomer. Selected.
- the syndiotactic stereoregulation is carried out by carrying out the ring-opening polymerization reaction of dicyclopentadiene under the conditions as described above using the polymerization catalyst comprising the tungsten compound represented by the above formula (1).
- a dicyclopentadiene ring-opening polymer having properties can be obtained.
- syndiotactic crystalline dicyclopentadiene opening having syndiotactic stereoregularity and crystallinity is obtained.
- a ring polymer hydride can be obtained.
- the dicyclopentadiene ring-opening polymer may be recovered from the reaction solution and used for the hydrogenation reaction, but the reaction solution containing the dicyclopentadiene ring-opening polymer can be used for the hydrogenation reaction as it is.
- the number average molecular weight (Mn) measured by 1 H-NMR of the dicyclopentadiene ring-opening polymer subjected to the hydrogenation reaction is not particularly limited, but is preferably 1,000 to 1,000,000. More preferably, it is from 1,000,000 to 800,000.
- Mn The number average molecular weight measured by 1 H-NMR of the dicyclopentadiene ring-opening polymer subjected to the hydrogenation reaction.
- the cis content measured by 1 H-NMR of the dicyclopentadiene ring-opening polymer subjected to the hydrogenation reaction is preferably higher than 50%, more preferably higher than 70%, and particularly higher than 90%. preferable.
- the ratio of racemo diads is preferably higher than 90%, more preferably higher than 91%, and particularly preferably higher than 92%.
- the solubility of the dicyclopentadiene ring-opening polymer in an organic solvent increases, and the reaction includes the dicyclopentadiene ring-opening polymer.
- a production process in which the liquid is directly subjected to a hydrogenation reaction is advantageous, which is preferable.
- the dicyclopentadiene ring-opened polymer of the present invention which can be used as an intermediate of the syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride of the present invention, is dissolved in an organic solvent at room temperature.
- an organic solvent inert to hydrogenation it can be dissolved in an organic solvent inert to hydrogenation. preferable.
- Solvents for dissolving the dicyclopentadiene ring-opening polymer of the present invention include cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydro Cycloaliphatic hydrocarbons such as indenecyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; halogens such as chlorobenzene and dichlorobenzene System aromatic hydrocarbons; ethers such as diethyl ether and tetrahydrofuran; aromatic ether
- a hydrogenating agent is added to the system in which the dicyclopentadiene ring-opening polymer obtained as described above exists, Then by heating and reacting, or (b) by adding a hydrogenation catalyst and then adding hydrogen to hydrogenate the carbon-carbon double bonds present in the dicyclopentadiene ring-opening polymer.
- a syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride is obtained.
- a hydrazine-containing compound as a hydrogenating agent for a hydrogen transfer hydrogenation reaction is used.
- the carbon-carbon double bond contained in the dicyclopentadiene ring-opening polymer is preferably hydrogenated.
- the compound used as a hydrogenating agent for the hydrogen transfer hydrogenation reaction is not particularly limited.
- the compound used as a hydrogenating agent for the dicyclopentadiene ring-opening polymer hydride may be used as a hydrogenation catalyst.
- Specific examples of the hydrogenating agent include hydrazine and paratoluenesulfonyl hydrazide.
- a conventionally known catalyst can be used as a hydrogenation catalyst for a ring-opening polymer.
- Specific examples thereof include RuHCl (CO) (PPh 3 ) 3 , RuHCl (CO) [P (p-Me-Ph) 3 ] 3 , RuHCl (CO) (PCy 3 ) 2 , RuHCl (CO) [P ( n-Bu) 3 ] 3 , RuHCl (CO) [P (i-Pr) 3 ] 2 , RuH 2 (CO) (PPh 3 ) 3 , RuH 2 (CO) [P (p-Me-Ph) 3 ] 3 , RuH 2 (CO) (PCy 3 ) 3 , RuH 2 (CO) [P (n-Bu) 3 ] 3 RuH (OCOCH 3 ) (CO) (PPh 3 ) 2 , RuH (OCOPh) (CO) (CO) ( PPh 3 ) 2 , RuH (CO) (PPh 3 ) 2 , Ru
- the hydrogenation reaction is usually performed in an inert organic solvent.
- inert organic solvents that can be used include cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane.
- Alicyclic hydrocarbons such as benzene, toluene and xylene; Halogenous aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Halogenous aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Diethyl And ethers such as ether and tetrahydrofuran; aromatic ethers such as anisole and phenetole; and the like.
- the method for producing a crystalline dicyclopentadiene ring-opening polymer hydride of the present invention preferably, by adding hydrogen to a system in which a dicyclopentadiene ring-opening polymer and a hydrogenation catalyst are present,
- the carbon-carbon double bond existing in the norbornene-based ring-opening polymer is hydrogenated.
- the suitable conditions for the hydrogenation reaction vary depending on the hydrogenation catalyst system used, but the reaction temperature is usually -20 ° C to + 250 ° C, preferably -10 ° C to + 220 ° C, more preferably 0 ° C to 200 ° C. . If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, side reactions may occur.
- the hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required.
- the reaction time is not particularly limited as long as the desired hydrogenation rate can be obtained, but is usually 0.1 to 10 hours.
- the target crystalline norbornene-based ring-opening polymer hydride may be recovered according to a conventional method, and in recovering the polymer, the catalyst residue can be removed by a technique such as filtration.
- the hydrogenation rate (ratio of hydrogenated main chain double bonds) in the hydrogenation reaction of the ring-opening polymer is not particularly limited, but is preferably 98% or more, more preferably 99% or more, and particularly preferably 99.99. 5% or more.
- the stereoregularity of the syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride is such that the hydride has crystallinity (that is, the melting point is 280 ° C. or higher) and syndiotactic (racemo diads). As long as the ratio of racemo diads to the repeating unit of dicyclopentadiene is higher than 91%, the ratio may be higher than 91%.
- the syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride obtained by the production method of the present invention has a high melting point and melting start temperature. Therefore, it can be said that this syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride exhibits excellent heat resistance even after being molded by melt molding. Can be used particularly preferably.
- the said molded object can be manufactured in accordance with a well-known method.
- the use of the molded product is not particularly limited, and examples thereof include a light reflector, an insulating material, an optical film, a connector, a food packaging material, a bottle, a pipe, gears, a fiber / nonwoven fabric, and the like. it can.
- Example 1 The (2-trifluoromethyl-2-phenyl-1,1,1-trifluoroethoxy) -2,6-dimethylphenylimidotungsten (VI) (2,5) obtained in Synthesis Example 1 was placed in a glass reactor equipped with a stirrer.
- This hydrogenation reaction solution was poured into a large amount of methanol to completely precipitate the produced dicyclopentadiene ring-opening polymer hydride, and after filtration and washing, it was dried under reduced pressure at 40 ° C. for 24 hours.
- the hydrogenation rate of the obtained ring-opened polymer hydride was 99% or more, and the ratio of racemo diads was 92%.
- the melting point of the hydride was measured, the melting point was 282 ° C., the heat of fusion was 53 J / g, and the melting start temperature was 275 ° C.
- solder immersion evaluation and the measurement of the curl value were performed. The results are shown in Table 1.
- Example 2 1.75 g of a polymerization mixture of the dicyclopentadiene ring-opening polymer obtained in Example 1 and 47 g of cyclohexane were added to an autoclave equipped with a stirrer. Then, a solution obtained by dispersing 0.00157 g of RuHCl (CO) (PPh 3 ) 3 in 10 ml of cyclohexane was further added, and a hydrogenation reaction was performed at a hydrogen pressure of 4.0 MPa and 160 ° C. for 8 hours. This hydrogenation reaction liquid was poured into a large amount of acetone to completely precipitate a hydrogenated ring-opening polymer, which was washed by filtration and dried under reduced pressure at 40 ° C.
- RuHCl (CO) (PPh 3 ) 3 10 ml of cyclohexane
- the hydrogenation rate of the obtained ring-opened polymer hydride was 99% or more, and the ratio of racemo diads was 92%.
- the melting point of the hydride was measured, the melting point was 284 ° C., the heat of fusion was 52 J / g, and the melting start temperature was 274 ° C.
- solder immersion evaluation and the measurement of the curl value were performed. The results are shown in Table 1.
- the syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride of the present invention has a high melting point and high melting start temperature, excellent heat resistance, and does not thermally deform even when contacted with solder. It was a material that can be mounted such as reflow (Examples 1 and 2). Therefore, according to the present invention, there is obtained a syndiotactic crystalline dicyclopentadiene ring-opened polymer hydride having a high melting point and melting start temperature, excellent heat resistance after melting, and not thermally deformed even when contacting with solder. Can be said.
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Abstract
Description
一方で、特許文献2に具体的に記載されたアイソタクチック結晶性ジシクロペンタジエン開環重合体水素化物は、そのアイソタクティシティーは分析装置の測定精度の範囲で100%であり、その融点は295℃前後であり極めて高い融点を有するものである。しかしながら、シス‐アイソタクチック構造を有するジシクロペンタジエン開環重合体はシクロヘキサン等の炭化水素溶媒に室温で不溶であるため、工業的な生産規模での製造が困難なものであった。
〔2〕水素化反応により、前記〔1〕に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物を生じうる、シンジオタクティシティーが90%より高い、シンジオタクチックジシクロペンタジエン開環重合体。
〔3〕下記の式(1)で表されるタングステン化合物を含んでなる重合触媒を用いて、ジシクロペンタジエンを開環重合する工程を有する、前記〔2〕に記載のシンジオタクチックジシクロペンタジエン開環重合体の製造方法。
R1及びR2は、それぞれ独立に、水素原子、炭素数1~12のアルキル基、置換基を有していてもよい炭素数6~12のアリール基、及び置換基を有していてもよい炭素数3~20のシクロアルキル基から選択される基を表し、
L1は、炭素数1~12のアルキル基、置換基を有していてもよい炭素数6~12のアリール基、及び置換基を有していてもよい炭素数3~20のシクロアルキル基から選択される置換基を有していてもよい窒素原子を表し、
L2は、少なくとも1個の窒素原子を有してなる環員数が5~15の共役複素環基を表し、該共役複素環基は置換基を有していてもよく、
L3は、O-R3で示されるアルコキシ基を表し、R3は、置換基を有していてもよい炭素数1~12のアルキル基、及び置換基を有していてもよい炭素数6~30のアリール基から選択される基を表し、
L4は、少なくとも2個の窒素原子を有する環員数が12~24の中性の共役複素環配位子を表し、該共役複素環配位子は置換基を有していてもよい。)
〔4〕前記〔2〕に記載のシンジオタクチックジシクロペンタジエン開環重合体を水素化反応に供する工程を有する、前記〔1〕に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物の製造方法。
〔5〕前記〔1〕に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物からなる成形体。
〔6〕前記〔1〕に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物を成形する工程を有する、前記〔5〕に記載の成形体の製造方法。
本明細書において、「置換基を有していてもよい」とは、「無置換又は置換基を有する」を意味する。
本発明の結晶性ジシクロペンタジエン開環重合体水素化物は、シンジオタクチックな立体規則性を有し、シンジオタクティシティー、すなわち、立体配置における、メソ二連子(meso diad)とラセモ二連子(racemo diad)の合計中のラセモ二連子の割合(以下、単にラセモ二連子の割合という場合がある。)が90%より高い高分子である。本発明の結晶性ジシクロペンタジエン開環重合体水素化物においては、ラセモ二連子の割合は、91%より高いことが好ましく、92%より高いことがより好ましい。
ラセモ二連子の割合が90%以下になると、シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物の結晶性が大きく低下し、高い融点と加工性等の特徴が損なわれる。
シクロペンテン、シクロヘキセン、シクロへプタン等のシクロアルケン類;
ジシクロペンタジエン又はジシクロペンタジエンの5員環部分の二重結合を飽和させたトリシクロ[4.3.12,5.0]デカ-3-エン、トリシクロ[4.4.12,5.0]ウンダ-3-エン等のジシクロペンタジエン類;
ノルボルネン、5-メチルノルボルネン、5-エチルノルボルネン、5-ブチルノルボルネン、5-ヘキシルノルボルネン、5-デシルノルボルネン、5-シクロヘキシルノルボルネン、5-シクロペンチルノルボルネン等の、無置換又はアルキル基を置換基として有するノルボルネン類;
5-エチリデンノルボルネン、5-ビニルノルボルネン、5-プロペニルノルボルネン、5-シクロヘキセニルノルボルネン、5-シクロペンテニルノルボルネン等の、アルケニル基を置換基として有するノルボルネン類;
5-フェニルノルボルネン等の、芳香環を置換基として有するノルボルネン類;
5-シアノノルボルネン、ノルボルネン-5,6-ジカルボン酸イミド等の、窒素原子を含む極性基を有するノルボルネン類;
8-メチリデンテトラシクロドデセン、8-エチリデンテトラシクロドデセン、8-ビニルテトラシクロドデセン、8-プロペニルテトラシクロドデセン、8-シクロヘキセニルテトラシクロドデセン、8-シクロペンテニルテトラシクロドデセン等の、環外に二重結合を有するテトラシクロドデセン類;
8-フェニルテトラシクロドデセン等の芳香環を有するテトラシクロドデセン類;
8-メトキシカルボニルテトラシクロドデセン、8-メチル-8-メトキシカルボニルテトラシクロドデセン、8-ヒドロキシメチルテトラシクロドデセン、8-カルボキシテトラシクロドデセン、テトラシクロドデセン-8,9-ジカルボン酸、テトラシクロドデセン-8,9-ジカルボン酸無水物等の、酸素原子を含む置換基を有するテトラシクロドデセン類;
8-シアノテトラシクロドデセン、テトラシクロドデセン-8,9-ジカルボン酸イミド等の窒素原子を含む置換基を有するテトラシクロドデセン類;
8-クロロテトラシクロドデセン等の、ハロゲン原子を含む置換基を有するテトラシクロドデセン類;
8-トリメトキシシリルテトラシクロドデセン等の、ケイ素原子を含む置換基を有するテトラシクロドデセン類;
12-メチリデンヘキサシクロヘプタデセン、12-エチリデンヘキサシクロヘプタデセン、12-ビニルヘキサシクロヘプタデセン、12-プロペニルヘキサシクロヘプタデセン、12-シクロヘキセニルヘキサシクロヘプタデセン、12-シクロペンテニルヘキサシクロヘプタデセン等の環外に二重結合を有するヘキサシクロヘプタデセン類;
12-フェニルヘキサシクロヘプタデセン等の、芳香族基を置換基として有するヘキサシクロヘプタデセン類;
12-シアノヘキサシクロヘプタデセン、ヘキサシクロヘプタデセン12,13-ジカルボン酸イミド等の窒素原子を含む置換基を有するヘキサシクロヘプタデセン類;
12-クロロヘキサシクロヘプタデセン等の、ハロゲン原子を含む置換基を有するヘキサシクロヘプタデセン類;
12-トリメトキシシリルヘキサシクロヘプタデセン等の、ケイ素原子を含む置換基を有するヘキサシクロヘプタデセン類;
R1及びR2は、それぞれ独立に、水素原子、炭素数1~12のアルキル基、置換基を有していてもよい炭素数6~12のアリール基、及び置換基を有していてもよい炭素数3~20のシクロアルキル基から選択される基を表す。
L1は、炭素数1~12のアルキル基、置換基を有していてもよい炭素数6~12のアリール基、及び置換基を有していてもよい炭素数3~20のシクロアルキル基から選択される置換基を有していてもよい窒素原子を表す。
L2は、少なくとも1個の窒素原子を有してなる環員数が5~15の共役複素環基を表し、該共役複素環基は置換基を有していてもよい。
L3は、O-R3で示されるアルコキシ基を表し、R3は、置換基を有していてもよい炭素数1~12のアルキル基、及び置換基を有していてもよい炭素数6~30のアリール基から選択される基を表す。
L4は、少なくとも2個の窒素原子を有する環員数が12~24の中性の共役複素環配位子を表し、該共役複素環配位子は置換基を有していてもよい。
R1及びR2はそれぞれ独立に、水素原子;メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基等の炭素数1~12のアルキル基;シクロプロピル基、シクロペンチル基、シクロヘキシル基等の、置換基を有していてもよい炭素数3~20のシクロアルキル基;又は置換基を有していてもよい炭素数6~12のアリール基;を表す。前記置換基を有していてもよいアリール基のアリール基としては、フェニル基、1-ナフチル基、2-ナフチル基等が挙げられる。また、シクロアルキル基及びアリール基の置換基としては、メチル基、エチル基等の炭素数1~12のアルキル基;フッ素原子、塩素原子、臭素原子等のハロゲン原子;メトキシ基、エトキシ基、イソプロポキシ基等の炭素数1~12のアルコキシ基;トリフルオロメチル基等の炭素数1~12のハロアルキル基;トリフルオロメトキシ基等の炭素数1~12のハロアルコキシ基;フェニル基、4-メチルフェニル基、2,4-ジメチルフェニル基、2-クロロフェニル基、3-メトキシフェニル基等の置換基を有していてもよい、炭素数6~12のアリール基;等が挙げられる。
炭素数6~12のアリール基としては、フェニル基、1-ナフチル基、2-ナフチル基等が挙げられる。
炭素数3~20のシクロアルキル基としては、シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基、アダマンチル基等が挙げられる。
置換基を有していてもよい炭素数6~12のアリール基の具体例としては、フェニル基、2-メチルフェニル基、2,6-ジメチルフェニル基、3,5-ジメチルフェニル基、ペンタフルオロフェニル基等が挙げられる。
L2の共役複素環基としては、ピロリル基、イミダゾリル基、ピラゾリル基、オキサゾリル基、チアゾリル基等の5員環共役複素環基;ピリジル基、ピリダジニル基、ピリミジニル基、ピラジニル基、トリアジニル基等の6員環共役複素環基;キナゾリニル基、フタラジニル基、ピロロピリジル基等の縮合環共役複素環基;等が挙げられる。
金属塩を構成する金属原子としては、亜鉛、錫、銅、チタン、希土類等が好適である。用いられうる金属塩の具体例としては、塩化亜鉛、塩化銅、塩化錫、塩化チタン、塩化スカンジウム、塩化イットリウム等が挙げられる。
この分子量調整の目的で用いるビニル化合物は、ビニル基を有する有機化合物であれば特に限定されない。例えば、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン等のα-オレフィン類;スチレン、ビニルトルエン等のスチレン類;エチルビニルエーテル、i-ブチルビニルエーテル、アリルグリシジルエーテル等のエーテル類;アリルクロライド等のハロゲン含有ビニル化合物;酢酸アリル、アリルアルコール、グリシジルメタクリレート等酸素含有ビニル化合物;アクリルアミド等の窒素含有ビニル化合物;ビニルトリメチルシラン、アリルトリメチルシラン、ビニルトリメトキシシラン等のケイ素含有ビニル化合物;等を用いることができる。
添加するビニル化合物またはジエン化合物の量は、目的とする分子量に応じて決定すればよいが、通常、単量体として用いるジシクロペンタジエン等100モルに対して、0.1~10モルの範囲で選択される。
なお、ジシクロペンタジエン開環重合体は、反応液中から回収して水素化反応に供してもよいが、ジシクロペンタジエン開環重合体を含む反応液をそのまま水素化反応に供することもできる。
(1)ジシクロペンタジエン開環重合体の数平均分子量
1H-NMR測定に基づき、重合体鎖末端に存在する水素原子の数と末端以外の重合体鎖中に存在する水素原子の数の比を求め、その比に基づいてジシクロペンタジエン開環重合体の数平均分子量を算出した。
(2)ジシクロペンタジエン開環重合体のシス/トランス含有率
1H-NMR測定に基づいて求めた。
(3)ジシクロペンタジエン開環重合体の水素化反応における水素化率
1H-NMR測定に基づいて求めた。
(4)シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物の融点及び融解開始温度
ジシクロペンタジエン開環重合体水素化物を320℃で10分間加熱して溶融させ、次いで10℃/分で降温して室温まで冷却させて結晶化させた後、示差走査熱量計を用いて、10℃/分で昇温して測定した。昇温測定時に観測される吸熱ピークにおいて、吸熱(結晶融解)熱量が最も大きくなる温度を融点とし、吸熱ピークの開始温度を融解開始温度として、求めた。
(5)シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物のラセモ二連子の割合
オルトジクロロベンゼン-d4/トリクロロベンゼン(混合比(重量基準)1/2)を溶媒として、200℃で13C-NMR測定を行い、メソ二連子由来の43.35ppmのシグナルのピーク面積値と、ラセモ二連子由来の43.43ppmのシグナルのピーク面積値と、に基づいて決定した。
(6)シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物のハンダ浸漬評価
試料となるシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物を320℃で10分間の加熱により加熱溶融して10mm×100mm×1mmの形状に成形し、次いで10℃/分で降温して室温まで冷却させて得たサンプル片を、260℃のハンダに20秒間浸漬し、その変形の有無を以下の基準に従って評価した。視認できる変形を生じさせないものは耐熱性に優れるといえる。
〔評価基準〕
○:視認できる変形なし
×:視認できる変形あり
(7)シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物のカール値
ハンダ浸漬評価を行ったサンプル片の端面を水平面に設置し、このサンプル片の長軸方向の逆側の端面と水平面との距離を測定し、その値をカール値とした。カール値が小さいものほど耐熱性に優れるといえる。
得られた固体の1H-NMR、13C-NMR、19F-NMRスペクトルにより、このものは、(2-トリフルオロメチル-2-フェニル-1,1,1-トリフルオロエトキシ)-2,6-ジメチルフェニルイミドタングステン(VI)(2,5-ジメチルピロリド)(ネオフィリデン)(1,10-フェナントロリン)と同定された。
攪拌機付きガラス反応器に、合成例1で得た(2-トリフルオロメチル-2-フェニル-1,1,1-トリフルオロエトキシ)-2,6-ジメチルフェニルイミドタングステン(VI)(2,5-ジメチルピロリド)(ネオフィリデン)(1,10-フェナントロリン)0.072g(1/500 モル/モル)、及びトルエン1gを添加し、次いで、ジシクロペンタジエン5.0g、シクロヘキサン20.0g及び1-ヘキセン0.21gを添加し、さらに無水塩化亜鉛0.0105gを1,4-ジオキサン5gに溶解したものを添加して、50℃において重合反応を行った。重合反応開始後、速やかに1,10-フェナントロリン亜鉛の白色の濁りが生成した。3時間反応させた後、重合反応液に大量のアセトンを注いで沈殿物を凝集させ、凝集物を濾別洗浄後、40℃で24時間減圧乾燥した。得られたジシクロペンタジエン開環重合体の収量は4.3gであり、数平均分子量は14,000で、シス含有率は97%であった。
次に、攪拌機付きガラス反応器に、得られたジシクロペンタジエン開環重合体2.5g及びパラトルエンスルホニルヒドラジド21gを加えた。そして、パラキシレン500mlを添加し、125℃で5時間水素化反応を行った。この水素化反応液を多量のメタノールに注いで、生成したジシクロペンタジエン開環重合体水素化物を完全に析出させ、濾別洗浄後、40℃で24時間減圧乾燥した。
得られた開環重合体水素化物の水素化率は99%以上であり、ラセモ二連子の割合は92%であった。当該水素化物の融点を測定したところ、融点は282℃であり、融解熱量は53J/gであり、融解開始温度は275℃であった。また、当該水素化物について、ハンダ浸漬評価及びカール値の測定を行った。それらの結果を表1に示す。
攪拌機付きオートクレーブに、実施例1で得られたジシクロペンタジエン開環重合体の重合混合物1.75g及びシクロヘキサン47gを加えた。そして、シクロヘキサン10mlにRuHCl(CO)(PPh3)30.00157gを分散させたものをさらに添加し、水素圧4.0MPa、160℃で8時間水素化反応を行った。この水素化反応液を多量のアセトンに注いで生成した開環重合体水素化物を完全に析出させ、濾別洗浄後、40℃で24時間減圧乾燥した。
得られた開環重合体水素化物の水素化率は99%以上であり、ラセモ二連子の割合は92%であった。当該水素化物の融点を測定したところ、融点は284℃であり、融解熱量は52J/gであり、融解開始温度は274℃であった。また、当該水素化物について、ハンダ浸漬評価及びカール値の測定を行った。それらの結果を表1に示す。
したがって、本発明によれば、融点と溶融開始温度が高く溶融後の耐熱性に優れ、ハンダに接触しても熱変形しない、シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物を得ることができるといえる。
Claims (6)
- 融点が280℃以上で、シンジオタクティシティーが90%より高い、シンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物。
- 水素化反応により、請求項1に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物を生じうる、シンジオタクティシティーが90%より高い、シンジオタクチックジシクロペンタジエン開環重合体。
- 下記の式(1)で表されるタングステン化合物を含んでなる重合触媒を用いて、ジシクロペンタジエンを開環重合する工程を有する、請求項2に記載のシンジオタクチックジシクロペンタジエン開環重合体の製造方法。
R1及びR2は、それぞれ独立に、水素原子、炭素数1~12のアルキル基、置換基を有していてもよい炭素数6~12のアリール基、及び置換基を有していてもよい炭素数3~20のシクロアルキル基から選択される基を表し、
L1は、炭素数1~12のアルキル基、置換基を有していてもよい炭素数6~12のアリール基、及び置換基を有していてもよい炭素数3~20のシクロアルキル基から選択される置換基を有していてもよい窒素原子を表し、
L2は、少なくとも1個の窒素原子を有してなる環員数が5~15の共役複素環基を表し、該共役複素環基は置換基を有していてもよく、
L3は、O-R3で示されるアルコキシ基を表し、R3は、置換基を有していてもよい炭素数1~12のアルキル基、及び置換基を有していてもよい炭素数6~30のアリール基から選択される基を表し、
L4は、少なくとも2個の窒素原子を有する環員数が12~24の中性の共役複素環配位子を表し、該共役複素環配位子は置換基を有していてもよい。) - 請求項2に記載のシンジオタクチックジシクロペンタジエン開環重合体を水素化反応に供する工程を有する、請求項1に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物の製造方法。
- 請求項1に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物からなる成形体。
- 請求項1に記載のシンジオタクチック結晶性ジシクロペンタジエン開環重合体水素化物を成形する工程を有する、請求項5に記載の成形体の製造方法。
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JPWO2018174029A1 (ja) * | 2017-03-21 | 2020-01-23 | 日本ゼオン株式会社 | 成形材料、樹脂成形体、化粧料容器、半導体容器、及び半導体容器の製造方法 |
EP3604377A4 (en) * | 2017-03-21 | 2020-12-30 | Zeon Corporation | MOLDING COMPOUNDS, RESIN MOLDED BODIES, COSMETIC CONTAINERS, SEMICONDUCTOR CONTAINERS AND MANUFACTURING METHODS FOR SEMICONDUCTOR CONTAINERS |
JP7115466B2 (ja) | 2017-03-21 | 2022-08-09 | 日本ゼオン株式会社 | 成形材料、樹脂成形体、化粧料容器、半導体容器、及び半導体容器の製造方法 |
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WO2016143424A1 (ja) | 2016-09-15 |
JPWO2016143424A1 (ja) | 2017-12-21 |
US20180044468A1 (en) | 2018-02-15 |
EP3269750A1 (en) | 2018-01-17 |
CN107406583B (zh) | 2019-11-01 |
US20180105636A1 (en) | 2018-04-19 |
EP3269750B1 (en) | 2023-10-18 |
EP3269750A4 (en) | 2018-12-19 |
EP3269751A4 (en) | 2018-12-19 |
US10590233B2 (en) | 2020-03-17 |
CN107428916A (zh) | 2017-12-01 |
EP3269751B1 (en) | 2023-08-09 |
US10611878B2 (en) | 2020-04-07 |
EP3269751A1 (en) | 2018-01-17 |
JP6760259B2 (ja) | 2020-09-23 |
CN107406583A (zh) | 2017-11-28 |
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