WO2014141957A1 - ノルボルネン系重合体溶液 - Google Patents

ノルボルネン系重合体溶液 Download PDF

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WO2014141957A1
WO2014141957A1 PCT/JP2014/055517 JP2014055517W WO2014141957A1 WO 2014141957 A1 WO2014141957 A1 WO 2014141957A1 JP 2014055517 W JP2014055517 W JP 2014055517W WO 2014141957 A1 WO2014141957 A1 WO 2014141957A1
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norbornene
polymer
solution
hydrocarbon solvent
polymer solution
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PCT/JP2014/055517
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English (en)
French (fr)
Japanese (ja)
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敬之 八重樫
桂一 加中
鈴木　健
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ポリプラスチックス株式会社
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Priority to CN201480013451.7A priority Critical patent/CN105008433B/zh
Priority to KR1020157013842A priority patent/KR101588368B1/ko
Priority to JP2014545030A priority patent/JP5721913B2/ja
Publication of WO2014141957A1 publication Critical patent/WO2014141957A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F32/04—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F132/02—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F132/04—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/25—Cycloolefine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2345/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers

Definitions

  • the present invention relates to a norbornene polymer solution.
  • Patent Document 1 discloses a method for producing a brightness enhancement film for a liquid crystal display device using a polynorbornene resin.
  • Patent Document 2 discloses a method for producing a retardation compensation film made of a polynorbornene resin.
  • Patent Document 3 a norbornene / ethylene addition copolymer having a glass transition temperature (Tg) of 150 ° C. or less, and a norbornene-based polymer obtained by ring-opening polymerization of a norbornene-based monomer and then hydrogenation reaction.
  • Patent Documents 4 and 5 are known.
  • Polynorbornene resins having a high proportion of structural units derived from bicyclo [2.2.1] hept-2-ene are particularly excellent in heat resistance, but have a glass transition temperature higher than the molding temperature. In the end, it becomes higher than the decomposition temperature of the polymer, so that it is generally difficult to melt-mold, unlike ordinary thermoplastic resins.
  • a conventional polynorbornene-based resin solution having a glass transition temperature of 170 ° C. or higher has a high viscosity and extremely low fluidity (for example, a glass transition temperature of 178 ° C. at a normal concentration used for producing cast films).
  • the present invention has been made to solve the above-mentioned problems, and the object thereof is to include a norbornene-based polymer having a high solution concentration suitable for producing a cast film and having a glass transition temperature of 170 ° C. or higher.
  • An object of the present invention is to provide a norbornene-based polymer solution having sufficient fluidity.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, the inventors have found that the above problems can be solved by adjusting the glass transition temperature, the weight average molecular weight, and the solution viscosity of the norbornene-based polymer within specific ranges, and have completed the present invention. More specifically, the present invention provides the following.
  • the norbornene-based polymer is a norbornene homopolymer or a copolymer of norbornene and an ⁇ -olefin, and the content of structural units derived from norbornene is 55 mol% or more and 100 mol% with respect to all structural units.
  • the norbornene-based polymer is a norbornene homopolymer or a copolymer of norbornene and substituted norbornene, and the content of structural units derived from norbornene is 20 mol% or more and 100 mol% or less with respect to all structural units.
  • the norbornene polymer is a norbornene polymer solution according to any one of (1) to (3), which is a norbornene homopolymer.
  • the aliphatic hydrocarbon solvent is at least one of cyclohexane, methylcyclohexane, p-menthane, and decahydronaphthalene, and the aromatic hydrocarbon solvent is at least one of toluene and xylene,
  • At least one of the above aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent, and halogenated hydrocarbon solvent is at least one of cyclohexane, methylcyclohexane, and toluene.
  • the norbornene-based polymer solution according to any one of the above.
  • Example and a comparative example it is a graph showing the result of having measured the glass transition temperature (Tg) by DSC method.
  • the arrow in the figure represents the glass transition temperature.
  • the norbornene polymer solution according to the present invention contains a norbornene polymer and a solvent.
  • This norbornene polymer solution has sufficient fluidity even if it contains the norbornene polymer at a high concentration suitable for the production of cast films. Therefore, a cast film having a sufficient thickness can be easily produced from this norbornene polymer solution using a known coating method.
  • the norbornene polymer contained in the norbornene polymer solution according to the present invention has a glass transition temperature of 170 ° C. or higher, and has a polystyrene equivalent weight average molecular weight of 5,000 or more and 250,000 measured by gel permeation chromatography. It is as follows. Further, when a 20 wt% solution obtained by dissolving this norbornene polymer in at least one of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, and a halogen hydrocarbon solvent is allowed to stand at 23 ° C. for 24 hours. The viscosity of the 20% by weight solution is 20,000 mPa ⁇ s or less.
  • a norbornene-type polymer can be used individually by 1 type or in combination of 2 or more types.
  • the glass transition temperature (Tg) of the norbornene-based polymer is usually 170 ° C. or higher, preferably 220 ° C. or higher, more preferably 260 ° C. or higher.
  • Tg glass transition temperature
  • the resin film obtained from the norbornene polymer solution according to the present invention tends to be inferior in heat resistance.
  • the glass transition temperature is 170 ° C. or higher, the resulting resin film has sufficient heat resistance, and can be suitably used, for example, as a substrate for ITO deposition.
  • the glass transition temperature is 260 ° C.
  • the resulting resin film has sufficient heat resistance, so that deformation, cracking, melting, etc., even when in contact with molten lead-free solder, for example, Since it does not easily occur, it can be suitably used as a lead-free solder member.
  • the glass transition temperature employ adopts the value measured on the conditions of the temperature increase rate of 20 degree-C / min by DSC method (method of JISK7121).
  • the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the norbornene polymer is usually 5,000 or more and 250,000 or less, preferably 10,000 or more and 200,000 or less. If the weight average molecular weight is less than 5,000, the glass transition temperature of the norbornene polymer may be too low. When the weight average molecular weight exceeds 250,000, the viscosity of the resulting norbornene polymer solution tends to be excessively high.
  • each of the said aliphatic hydrocarbon solvent, the said aromatic hydrocarbon solvent, and the said halogen-type hydrocarbon solvent can be used individually by 1 type or in combination of 2 or more types.
  • the norbornene-based polymer is not particularly limited as long as it has a structural unit derived from norbornene and the glass transition temperature, the weight average molecular weight, and the solution viscosity satisfy the above ranges, and is a norbornene homopolymer.
  • it may be a copolymer of norbornene and another monomer (a monomer that can be polymerized with norbornene). Examples of other monomers include ⁇ -olefins and substituted norbornene.
  • the norbornene polymer is a norbornene homopolymer or a copolymer of norbornene and an ⁇ -olefin, and the content of structural units derived from norbornene is 55 mol% or more and 100 mol% or less with respect to all structural units. Is preferred.
  • the norbornene-based polymer is a norbornene homopolymer or a copolymer of norbornene and substituted norbornene, and the content of structural units derived from norbornene is 20 mol% or more and 100 mol% or less with respect to all structural units. It is preferable.
  • the norbornene-based polymer is a copolymer of norbornene and an ⁇ -olefin or a substituted norbornene
  • 20% by weight obtained by dissolving the norbornene-based polymer in at least one of cyclohexane, methylcyclohexane, and toluene.
  • the viscosity of the 20 wt% solution tends to be low, and the resulting norbornene polymer solution tends to have excellent fluidity. This is presumably because the structural unit derived from ⁇ -olefin or substituted norbornene decreases the crystallinity of the norbornene polymer.
  • the ⁇ -olefin is not particularly limited, and examples thereof include ⁇ -olefins having 2 to 20 carbon atoms. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, Examples thereof include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. Of these, 1-octene is preferred.
  • the norbornene-based polymer is a norbornene homopolymer or a copolymer of norbornene and an ⁇ -olefin, particularly a random copolymer
  • the content of structural units derived from norbornene is 55 mol% or more based on the total structural units. It is preferable that it is 100 mol% or less.
  • the glass transition temperature of the norbornene polymer tends to be 170 ° C. or higher.
  • the substituted norbornene is not particularly limited, and examples of the substituent that the substituted norbornene has include a halogen atom, a monovalent or divalent hydrocarbon group.
  • Specific examples of the substituted norbornene include those represented by the following general formula (I). (Wherein R 1 to R 12 may be the same or different and are each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R 9 and R 10 , R 11 and R 12 may be integrated to form a divalent hydrocarbon group, R 9 or R 10 and R 11 or R 12 may form a ring with each other.
  • N represents 0 or a positive integer;
  • R 1 to R 12 in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
  • R 1 to R 8 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms, and these may be different from each other. , May be partially different or all may be the same.
  • R 9 to R 12 include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a phenyl group and tolyl Group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group and the like substituted or unsubstituted aromatic hydrocarbon group; benzyl group, phenethyl group, and other aralkyl groups in which an alkyl group is substituted with an aryl group These may be different from each other, may be partially different, or all may be the same.
  • R 9 and R 10 or R 11 and R 12 are integrated to form a divalent hydrocarbon group
  • alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.
  • the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge.
  • a ring having a double bond, or a ring composed of a combination of these rings may be used.
  • these rings may have a substituent such as a methyl group.
  • substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo [2.2.1] hept-2-ene, 5,5-dimethyl-bicyclo [2.2.1] hepta- 2-ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.
  • Tricyclo [4.3.0.1 2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 2,5 ] dec-3-ene; tricyclo [ 4.4.0.1 2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 2,5 ] undeca-3,8-diene or a partially hydrogenated product thereof (or cyclopentadiene) Tricyclo [4.4.0.1 2,5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2-ene A cyclic olefin of the ring;
  • Tetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene also simply referred to as tetracyclododecene
  • 8-methyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene 8-ethyltetracyclo [4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
  • 8-methylidenetetracyclo 4.4.0.1 2,5 . 1 7,10 ] dodec-3-ene
  • alkyl-substituted norbornene eg, bicyclo [2.2.1] hept-2-ene substituted with one or more alkyl groups
  • alkylidene-substituted norbornene eg, bicyclo substituted with one or more alkylidene groups
  • [2.2.1] hept-2-ene) preferably 5-ethylidene-bicyclo
  • hept-2-ene common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene Is particularly preferred.
  • the norbornene-based polymer is a norbornene homopolymer or a copolymer of norbornene and a substituted norbornene, particularly a random copolymer
  • the content of the structural unit derived from norbornene is 20 mol% or more to the total structural unit. It is preferable that it is below mol%.
  • the norbornene polymer tends to be uniform with a single glass transition temperature, and the norbornene polymer tends to have a glass transition temperature of 170 ° C. or higher.
  • the production method of the norbornene polymer is not particularly limited as long as it can obtain a norbornene polymer satisfying the above ranges of glass transition temperature, weight average molecular weight, and solution viscosity.
  • the polymerization temperature, polymerization pressure, polymerization time and the like are appropriately adjusted.
  • the form of polymerization is random copolymerization.
  • a metallocene catalyst can be particularly preferably used as the polymerization catalyst.
  • the content of the norbornene polymer is preferably 10% by weight or more and 100% by weight or less, and more preferably 30% by weight or more and 100% by weight or less with respect to the solid content in the norbornene polymer solution according to the present invention.
  • the solvent contained in the norbornene-based polymer solution according to the present invention is not particularly limited as long as it can dissolve the norbornene-based polymer.
  • a fat such as cyclohexane, methylcyclohexane, p-menthane, decahydronaphthalene, etc.
  • Aromatic hydrocarbon solvents such as aromatic hydrocarbon solvents, toluene and xylene, and halogenated hydrocarbon solvents such as dichloromethane, chloroform, and carbon tetrachloride. Among them, cyclohexane, methylcyclohexane, toluene, and xylene are preferable.
  • a solvent can be used individually by 1 type or in combination of 2 or more types.
  • the content of the solvent is preferably such that the solid content concentration of the norbornene polymer solution according to the present invention is 1% by weight to 50% by weight, and more preferably 5% by weight to 40% by weight.
  • the obtained norbornene polymer solution has sufficient fluidity, and therefore, using a known coating method, a cast having a sufficient thickness is obtained from this norbornene polymer solution.
  • a film can be manufactured easily.
  • a cast film containing a norbornene polymer can be obtained by applying the norbornene polymer solution according to the present invention on a support and removing the solvent from the applied norbornene polymer solution.
  • the coating method is not particularly limited, and examples thereof include known coating methods such as a micro gravure coating method, a die coating method, a comma coating method, and a spin coating method.
  • the cast film obtained from the norbornene-based polymer solution according to the present invention contains structural units derived from norbornene, it can be expected to be used as a high-frequency material utilizing low dielectric properties.
  • Nb Norbornene
  • ENb 5-ethylidene-2-norbornene
  • 1-octene catalyst (T-Butylamide) dimethyl-9-fluorenylsilane titanium dimethyl promoter: Modified methylaluminoxane (MMAO) Trisisobutylaluminum (TIBA) N, N-dimethylanilium tetrakis (pentafluorophenyl) borate (Borate) solvent: Toluene (super dewatering grade)
  • Nb ′ a structural unit derived from norbornene
  • ENb ′ a structural unit derived from 5-ethylidene-2-norbornene
  • 1-octene is represented by 1-Oct ′.
  • the amount of each component in the polymerization solution was as shown in Table 1, and the amount of the polymerization solution was 30 mL.
  • the polymerization solution was prepared and polymerized in a nitrogen atmosphere, and the system was stirred with a magnetic stirrer during the polymerization in order to make the system uniform.
  • the polymerization was stopped by adding a small amount of methanol to the polymerization solution.
  • the polymer was precipitated by adding the polymerization solution to 300 ml of a methanol solution containing about 1.5 vol% hydrochloric acid. The precipitated polymer was collected by filtration.
  • the recovered polymer was washed twice or more with methanol and acetone, respectively, and dried under reduced pressure at 40 ° C. for 10 hours or more to obtain a dried product of the polymer.
  • Glass transition temperature (Tg) Based on JIS K 7121, the glass transition temperature was measured from room temperature to 20 ° C./min with a differential scanning calorimeter (TA Instrument Q-1000). For Examples 1 to 6, the graph of the measurement results is shown in FIG.
  • metal proton in polymer means a methine proton contained in the ethylidene group of ENb ′ in the polymer
  • other protons in polymer means Nb ′ in the polymer. The sum of protons contained and protons other than methine protons contained in ENb ′ in the polymer. It was assumed that the ethylidene group in ENb was not consumed by polymerization.
  • Viscosity The obtained polymer was dissolved in toluene to obtain a 20 wt% solution. The viscosity of the 20% by weight solution left at 23 ° C. for 24 hours was measured. Viscosity is measured according to JIS K 7117-2, TVE-22HT viscometer manufactured by Toki Sangyo Co., Ltd. (rotary viscometer (cone-plate system), cone rotor: 3 ° ⁇ R17.65 (R17.65 is (Representing a radius of 17.65 mm).
  • the norbornene homopolymer of Comparative Example 1 had a weight average molecular weight exceeding 250,000, and the viscosity of a 20 wt% toluene solution far exceeded 20,000 mPa ⁇ s.
  • the norbornene homopolymer of Comparative Example 2 had a weight average molecular weight of 250,000 or less, but the viscosity of a 20 wt% toluene solution exceeded 20,000 mPa ⁇ s.
  • the norbornene homopolymer of Example 5 had a weight average molecular weight of 250,000 or less, and the viscosity of a 20 wt% toluene solution was 20,000 mPa ⁇ s or less.
  • the compounding quantity of each component in a polymerization solution was as showing in Table 3 at the time of a polymerization start, and the quantity of the polymerization solution was 250 mL.
  • the polymerization solution was prepared and polymerized in a nitrogen atmosphere, and the system was stirred with a magnetic stirrer during the polymerization in order to make the system uniform.
  • the polymerization was stopped by adding a small amount of methanol to the polymerization solution.
  • the polymer was precipitated by adding the polymerization solution to 1500 ml of a methanol solution containing about 1.5 vol% hydrochloric acid.
  • the precipitated polymer was collected by filtration.
  • the recovered polymer was washed twice or more with methanol and acetone, respectively, and dried under reduced pressure at 40 ° C. for 10 hours or more to obtain a dried product of the polymer.
  • terminal methyl carbon in polymer and methylene carbon adjacent thereto means terminal methyl carbon and adjacent methylene carbon contained in 1-Oct ′ in polymer.
  • carbon refers to the sum of the carbon contained in Nb ′ in the polymer and the carbon other than the terminal methyl carbon and the adjacent methylene carbon contained in 1-Oct ′ in the polymer.

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PCT/JP2014/055517 2013-03-11 2014-03-04 ノルボルネン系重合体溶液 WO2014141957A1 (ja)

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CN201480013451.7A CN105008433B (zh) 2013-03-11 2014-03-04 降冰片烯系聚合物溶液
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JP2016037045A (ja) * 2014-08-08 2016-03-22 ポリプラスチックス株式会社 金属樹脂積層体及び高周波用配線基板
JP2016037577A (ja) * 2014-08-08 2016-03-22 ポリプラスチックス株式会社 ノルボルネン系重合体溶液及び絶縁被膜の製造方法
KR20170012223A (ko) * 2014-05-23 2017-02-02 포리프라스틱 가부시키가이샤 환상 올레핀 공중합체의 제조방법

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CN114685715B (zh) * 2020-12-31 2024-05-03 江苏博睿光电股份有限公司 一种可交联热塑性环烯烃共聚物及其制备方法和应用

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