WO2010095678A1 - 含フッ素ジカルボン酸誘導体およびそれを用いた高分子化合物 - Google Patents
含フッ素ジカルボン酸誘導体およびそれを用いた高分子化合物 Download PDFInfo
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- WO2010095678A1 WO2010095678A1 PCT/JP2010/052425 JP2010052425W WO2010095678A1 WO 2010095678 A1 WO2010095678 A1 WO 2010095678A1 JP 2010052425 W JP2010052425 W JP 2010052425W WO 2010095678 A1 WO2010095678 A1 WO 2010095678A1
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- 0 Cc1c(C)c([N+](*)[O-])cc([N+]([O-])=O)c1 Chemical compound Cc1c(C)c([N+](*)[O-])cc([N+]([O-])=O)c1 0.000 description 4
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- NNTKZPQZOSKWDE-UHFFFAOYSA-N Cc(c(C)c1)cc(C#N)c1C#N Chemical compound Cc(c(C)c1)cc(C#N)c1C#N NNTKZPQZOSKWDE-UHFFFAOYSA-N 0.000 description 1
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- OPVAJFQBSDUNQA-UHFFFAOYSA-N Cc(cc1)c(C)cc1C(O)=O Chemical compound Cc(cc1)c(C)cc1C(O)=O OPVAJFQBSDUNQA-UHFFFAOYSA-N 0.000 description 1
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- XEKUBCZESJYSHO-UHFFFAOYSA-N Cc(cc1)cc2c1Nc(ccc(C)c1)c1N2 Chemical compound Cc(cc1)cc2c1Nc(ccc(C)c1)c1N2 XEKUBCZESJYSHO-UHFFFAOYSA-N 0.000 description 1
- YYRGGPFBECTTQH-UHFFFAOYSA-N Cc(cc1)cc2c1Nc1cc(C)ccc1N2 Chemical compound Cc(cc1)cc2c1Nc1cc(C)ccc1N2 YYRGGPFBECTTQH-UHFFFAOYSA-N 0.000 description 1
- QYKONCJMGHXSRX-UHFFFAOYSA-N Cc(cc1)cc2c1Oc1cc(C)ccc1O2 Chemical compound Cc(cc1)cc2c1Oc1cc(C)ccc1O2 QYKONCJMGHXSRX-UHFFFAOYSA-N 0.000 description 1
- CJPKVRYHWJTPOL-UHFFFAOYSA-N Cc(cc1)cc2c1Oc1ccc(C)cc1O2 Chemical compound Cc(cc1)cc2c1Oc1ccc(C)cc1O2 CJPKVRYHWJTPOL-UHFFFAOYSA-N 0.000 description 1
- IBJDGNVJTZEYRU-UHFFFAOYSA-N Cc(cc1[N+]([O-])=O)c(C)cc1[N+]([O-])=O Chemical compound Cc(cc1[N+]([O-])=O)c(C)cc1[N+]([O-])=O IBJDGNVJTZEYRU-UHFFFAOYSA-N 0.000 description 1
- QMDZSCLOPWSXRB-UHFFFAOYSA-N Cc1c(C(O)=O)c(C(O)=O)c(C(O)=O)c(C(O)=O)c1C Chemical compound Cc1c(C(O)=O)c(C(O)=O)c(C(O)=O)c(C(O)=O)c1C QMDZSCLOPWSXRB-UHFFFAOYSA-N 0.000 description 1
- LAWILYMDMLNTLZ-UHFFFAOYSA-N Cc1c(C)c(C#N)cc(C#N)c1 Chemical compound Cc1c(C)c(C#N)cc(C#N)c1 LAWILYMDMLNTLZ-UHFFFAOYSA-N 0.000 description 1
- CPSSMIFTUQKPSF-UHFFFAOYSA-N Cc1c(C)c(C(O)=O)cc(C(O)=O)c1 Chemical compound Cc1c(C)c(C(O)=O)cc(C(O)=O)c1 CPSSMIFTUQKPSF-UHFFFAOYSA-N 0.000 description 1
- RIZUCYSQUWMQLX-UHFFFAOYSA-N Cc1c(C)c(C(O)=O)ccc1 Chemical compound Cc1c(C)c(C(O)=O)ccc1 RIZUCYSQUWMQLX-UHFFFAOYSA-N 0.000 description 1
- RYRZSXJVEILFRR-UHFFFAOYSA-N Cc1c(C)c(C(O)=O)ccc1C(O)=O Chemical compound Cc1c(C)c(C(O)=O)ccc1C(O)=O RYRZSXJVEILFRR-UHFFFAOYSA-N 0.000 description 1
- FVHAWXWFPBPFOS-UHFFFAOYSA-N Cc1c(C)c([N+]([O-])=O)ccc1 Chemical compound Cc1c(C)c([N+]([O-])=O)ccc1 FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 description 1
- AHXDSVSZEZHDLV-UHFFFAOYSA-N Cc1ccc2Sc(cc(C)cc3)c3Sc2c1 Chemical compound Cc1ccc2Sc(cc(C)cc3)c3Sc2c1 AHXDSVSZEZHDLV-UHFFFAOYSA-N 0.000 description 1
- XTLNLAUJNYMFIN-UHFFFAOYSA-N Cc1ccc2Sc(ccc(C)c3)c3Sc2c1 Chemical compound Cc1ccc2Sc(ccc(C)c3)c3Sc2c1 XTLNLAUJNYMFIN-UHFFFAOYSA-N 0.000 description 1
- VWORSRCREDPQQI-UHFFFAOYSA-N NC(C(C(O)=O)=[I]C(C(O)=O)=C1N)=C1I Chemical compound NC(C(C(O)=O)=[I]C(C(O)=O)=C1N)=C1I VWORSRCREDPQQI-UHFFFAOYSA-N 0.000 description 1
- VYRXSWRWQPGSME-UHFFFAOYSA-N NC(C(O)=C1I)=[I]C(N)=C1O Chemical compound NC(C(O)=C1I)=[I]C(N)=C1O VYRXSWRWQPGSME-UHFFFAOYSA-N 0.000 description 1
- AGWFZGBPVDGNTR-UHFFFAOYSA-N Nc(c(C(C(F)(F)F)(C(F)(F)F)O)c(c(N)c1C(C(F)(F)F)(C(F)(F)F)O)I)c1I Chemical compound Nc(c(C(C(F)(F)F)(C(F)(F)F)O)c(c(N)c1C(C(F)(F)F)(C(F)(F)F)O)I)c1I AGWFZGBPVDGNTR-UHFFFAOYSA-N 0.000 description 1
- UOYVQRUCYMBFLD-UHFFFAOYSA-N Nc(c(C(CO)(F)F)c(c(N)c1C(CO)(F)F)I)c1I Chemical compound Nc(c(C(CO)(F)F)c(c(N)c1C(CO)(F)F)I)c1I UOYVQRUCYMBFLD-UHFFFAOYSA-N 0.000 description 1
- HEFJWSHMEZPNCJ-UHFFFAOYSA-N OC(C(F)(F)F)(C(F)(F)F)c(c(C(O)=O)c(c(C(C(F)(F)F)(C(F)(F)F)O)c1C(O)=O)I)c1I Chemical compound OC(C(F)(F)F)(C(F)(F)F)c(c(C(O)=O)c(c(C(C(F)(F)F)(C(F)(F)F)O)c1C(O)=O)I)c1I HEFJWSHMEZPNCJ-UHFFFAOYSA-N 0.000 description 1
- VHIUIXQQEBLBNT-UHFFFAOYSA-N OC(C(F)(F)F)(C(F)(F)F)c(c(O)c(c(C(C(F)(F)F)(C(F)(F)F)O)c1O)I)c1I Chemical compound OC(C(F)(F)F)(C(F)(F)F)c(c(O)c(c(C(C(F)(F)F)(C(F)(F)F)O)c1O)I)c1I VHIUIXQQEBLBNT-UHFFFAOYSA-N 0.000 description 1
- MWFGQQZJZYUEBH-UHFFFAOYSA-N OC(c(c(I)c(C(O)=O)c(O)c1I)c1O)=O Chemical compound OC(c(c(I)c(C(O)=O)c(O)c1I)c1O)=O MWFGQQZJZYUEBH-UHFFFAOYSA-N 0.000 description 1
- OEFLKXSOCUUQLL-UHFFFAOYSA-N OCC(c(c(C(O)=O)c(c(C(CO)(F)F)c1C(O)=O)I)c1I)(F)F Chemical compound OCC(c(c(C(O)=O)c(c(C(CO)(F)F)c1C(O)=O)I)c1I)(F)F OEFLKXSOCUUQLL-UHFFFAOYSA-N 0.000 description 1
- XYEYWYXWZKBXJV-UHFFFAOYSA-N OCC(c(c(O)c(c(C(CO)(F)F)c1O)I)c1I)(F)F Chemical compound OCC(c(c(O)c(c(C(CO)(F)F)c1O)I)c1I)(F)F XYEYWYXWZKBXJV-UHFFFAOYSA-N 0.000 description 1
- SAJBMQRNTIIIMH-UHFFFAOYSA-N [O-][N+](c(c(C(C(F)(F)F)(C(F)(F)F)O)c(c([N+]([O-])=O)c1C(C(F)(F)F)(C(F)(F)F)O)I)c1I)=O Chemical compound [O-][N+](c(c(C(C(F)(F)F)(C(F)(F)F)O)c(c([N+]([O-])=O)c1C(C(F)(F)F)(C(F)(F)F)O)I)c1I)=O SAJBMQRNTIIIMH-UHFFFAOYSA-N 0.000 description 1
- OZBHTDNWMYIWAW-UHFFFAOYSA-N [O-][N+](c(c(C(CO)(F)F)c(c([N+]([O-])=O)c1C(CO)(F)F)I)c1I)=O Chemical compound [O-][N+](c(c(C(CO)(F)F)c(c([N+]([O-])=O)c1C(CO)(F)F)I)c1I)=O OZBHTDNWMYIWAW-UHFFFAOYSA-N 0.000 description 1
- OYWOEPBJMFOCPE-UHFFFAOYSA-N [O-][N+](c(c(O)c(c(O)c1[N+]([O-])=O)I)c1I)=O Chemical compound [O-][N+](c(c(O)c(c(O)c1[N+]([O-])=O)I)c1I)=O OYWOEPBJMFOCPE-UHFFFAOYSA-N 0.000 description 1
- YHPGYETXMDIFBY-UHFFFAOYSA-N [O-][N+](c1c(C(O)=O)c(I)c(C(O)=O)c([N+]([O-])=O)c1I)=O Chemical compound [O-][N+](c1c(C(O)=O)c(I)c(C(O)=O)c([N+]([O-])=O)c1I)=O YHPGYETXMDIFBY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/52—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen
- C07C57/58—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/62—Halogen-containing esters
- C07C69/65—Halogen-containing esters of unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
Definitions
- the present invention relates to a novel fluorine-containing dicarboxylic acid derivative and a novel polymer compound using the same.
- Polyester, polyamide, polyimide, and polybenzoxazole have been developed as highly reliable organic polymers.
- Their cores include polyamides such as nylon and Kevlar (registered trademark), polyarylates used for liquid crystalline polymers, polyimides such as Kapton (registered trademark), and polysylates represented by Zylon (registered trademark).
- Many different polymers such as benzoxazole have been put into practical use.
- polyester there are a method of polycondensation of dicarboxylic acid and diol in the presence of a condensing agent, or a method of derivatizing dicarboxylic acid into acid chloride or ester and polycondensing with diol. Be taken.
- polyamide a method of polycondensation of dicarboxylic acid and diamine in the presence of a condensing agent, or a method of derivatizing dicarboxylic acid into carboxylic acid chloride or ester and polycondensing with diamine is employed.
- polyimide a method of dehydrating and ring-closing after polymerization of diamine and tetracarboxylic dianhydride is used.
- polybenzoxazole a method of polycondensation of dicarboxylic acid and bisaminophenol in the presence of a condensing agent, or a method of derivatizing dicarboxylic acid into acid chloride or ester and polycondensation with bisaminophenol is employed.
- aromatic polyesters, aromatic polyamides and derivatives thereof are attracting attention in the printed circuit board, semiconductor field, and display field because of their high reliability and excellent dimensional stability.
- aromatic polyesters, aromatic polyamides and derivatives thereof are attracting attention in the printed circuit board, semiconductor field, and display field because of their high reliability and excellent dimensional stability.
- electrical characteristics such as lower dielectric constant There is a need for improvements.
- Fluorine-containing aromatic polymer compounds are highly reliable for the properties of fluororesins such as water repellency, oil repellency, low water absorption, corrosion resistance, transparency, photosensitivity, low refractive index, and low dielectric properties. It has been developed or put into practical use in a wide range of material fields, mainly in the field of advanced materials. Attempts have been made to introduce fluorine into diamine, which is a monomer of condensed polymer, and diamines, dihydroxy monomers, and hexafluoroisopropenyl groups in which hydrogen atoms of the benzene ring are substituted with fluorine atoms or trifluoromethyl groups.
- a fluorine-containing aromatic polymer compound derived from a bishydroxyamine monomer having a central atomic group and aromatic hydroxyamine on both sides thereof has been put into practical use.
- Patent Document 1 a fluorinated aromatic polyamide that achieves both visible light transparency and dimensional stability is obtained by directly introducing a trifluoromethyl group into an aromatic ring having a rigid base. This generally enables a polymerization process that requires a reaction in sulfuric acid to be polymerized in an organic solvent by the effect of introducing fluorine.
- the mother character is rigid, in order to obtain a flexible film, heating at a high temperature of 280 ° C. or higher is required, and the application is limited.
- Patent Document 2 realizes both light transparency and high heat resistance in the 850 nm band by substituting all the hydrogen atoms of rigid wholly aromatic polyester with fluorine atoms or trifluoromethyl groups. Since the mother character is rigid, a high polymerization temperature of 300 ° C. or higher is required to increase the degree of polymerization.
- Non-Patent Document 1 discloses a dicarboxylic acid monomer in which a fluorinated methylene group is bonded to the ortho position of a fully fluorinated benzene ring, but derivatization to a polymer compound is described. Absent.
- Non-Patent Document 2 discloses bis (2-ethoxycarbonyl-1,1,2,2-tetrafluoroethyl) benzene, but there is no description of a polymer using the same.
- an object of the present invention is to provide a polycondensation polymer compound having a sufficiently low dielectric constant as a semiconductor protective film and capable of forming a film at a relatively low temperature of 250 ° C. or lower.
- the present inventors have obtained a novel fluorinated dicarboxylic acid or fluorinated dicarboxylic acid derivative bonded to an aromatic ring via a fluorinated methylene group, and those The inventors have arrived at the invention of a novel polymer compound obtained using In polyesters and polyamides obtained by condensation polymerization from phthalic acid derivatives disclosed in Patent Documents 1 and 2, curing (polymerization) is performed at 250 ° C. because two carboxyl groups are directly substituted on the aromatic ring.
- the fluorine-containing dicarboxylic acid according to the present invention has a low dielectric constant and flexibility when heated at 250 ° C.
- a polymer compound having a heterocycle obtained by cyclizing a part of the structure of the polyester or polyamide of the present invention also exhibits characteristics of being excellent in low dielectric constant and flexibility.
- a fluorinated dicarboxylic acid derivative represented by the general formula (M-1) or an acid anhydride of the fluorinated dicarboxylic acid is reacted with 2 to 4 reactive groups which respond to the reactivity of these carbonyl group sites.
- a and A ′ are each independently a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, or a substituent having 6 to 10 carbon atoms. And may form an active ester group together with the CO group (carbonyl group) in the formula.
- each Ar 1 is an aromatic ring optionally having a substituent
- the hydrogen atom on the aromatic ring is a fluorine atom, chlorine atom, hydroxyl group, amino group, nitro group, cyano group, hydroxy group A carbonyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (wherein the hydrogen atom on the alkyl group may be substituted with a hydroxyl group or a fluorine atom), 1 to 6 carbon atoms A linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxycarbonyl group having 1 to 6 carbon atoms, or a monovalent group consisting of an optionally substituted aromatic ring May be substituted.
- Y 1 is a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , O, S, C (CH 3 ) 2 , C (CF 3 ) 2 , SO 2 , CO, NH, COO (ester) , A divalent group in which one or more kinds selected from a CONH group or two or more same or different groups selected from these groups are bonded, and p represents an integer of 0 to 3. Two dangling bonds are bonded to different carbon atoms of the same or different aromatic rings.
- each Ar 2 is an aromatic ring which may have a substituent, and the hydrogen atom on the aromatic ring is a fluorine atom, chlorine atom, hydroxyl group, amino group, nitro group, cyano group, hydroxy group A carbonyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (wherein the hydrogen atom on the alkyl group may be substituted with a hydroxyl group or a fluorine atom), 1 to 6 carbon atoms A linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxycarbonyl group having 1 to 6 carbon atoms, or a monovalent group consisting of an optionally substituted aromatic ring May be substituted.
- Y 2 is each independently a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , O, S, C (CH 3 ) 2 , C (CF 3 ) 2 , SO 2 , CO, NH, COO (Ester), one type selected from CONH groups, or a divalent group in which two or more types selected from these groups are bonded.
- Q has the same meaning as Q in formula (M-1).
- R 2 is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring and a heterocyclic ring, and may contain a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom or a nitrogen atom, A part of the hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group or a cyano group, and a part of the carbon atoms are an oxygen atom, a sulfur atom, a nitrogen atom, It may be substituted with a carbonyl group or a sulfonyl group.
- m is a positive integer.
- R 3 is a tetravalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and a heterocyclic ring, and may contain a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, or a nitrogen atom.
- a part of hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group or a cyano group, and a part of carbon atoms may be an oxygen atom, a sulfur atom or a nitrogen atom.
- a carbonyl group and a sulfonyl group may be substituted.
- m is a positive integer.
- Q has the same meaning as Q in formula (M-1).
- R 3 has the same meaning as R 3 in the general formula (4).
- R 4 is a tetravalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and a heterocyclic ring, and may contain a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom, or a nitrogen atom.
- a part of hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group or a cyano group, and a part of carbon atoms may be an oxygen atom, a sulfur atom or a nitrogen atom.
- a carbonyl group and a sulfonyl group may be substituted.
- m is a positive integer.
- Q has the same meaning as Q in formula (M-1).
- R 4 has the same meaning as R 4 in the general formula (5).
- Q has the same meaning as Q in formula (M-1).
- R 1 is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring and a heterocyclic ring, and may contain a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom or a nitrogen atom, A part of the hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group or a cyano group, and a part of the carbon atoms are an oxygen atom, a sulfur atom, a nitrogen atom, It may be substituted with a carbonyl group or a sulfonyl group.
- m is a positive integer.
- Q is a divalent organic group having an aromatic ring which may have a substituent
- the hydrogen atom on the aromatic ring is a fluorine atom, chlorine atom, hydroxyl group, amino group, nitro group, cyano group Group, a hydroxycarbonyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (wherein the hydrogen atom on the alkyl group may be substituted with a hydroxyl group or a fluorine atom), carbon number 1 to 6 linear, branched or cyclic alkoxy groups, 1 to 6 carbon linear, branched or cyclic alkoxycarbonyl groups, or an aromatic ring optionally having a substituent.
- D and D ′ are each independently a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, or a substituent having 6 to 10 carbon atoms. Or can form an active ester group with a CO group (carbonyl group) in the formula.
- the fluorine-containing polymer compound such as polyester and polyamide of the present invention is required to have a sufficient degree of polymerization by heating at a temperature of 250 ° C. or less, which is strongly demanded as the semiconductor chip itself has low heat resistance. And the resulting film has high flexibility and can be used as a protective film having excellent electrical properties (low dielectric constant).
- a polymer compound having a heterocycle obtained by ring-closing the polyester or polyamide of the present invention also exhibits the characteristics of excellent low dielectric constant and flexibility, and can be used as a protective film.
- fluorine-containing dicarboxylic acids and derivatives thereof are extremely useful for the production of such fluorine-containing polymer compounds.
- fluorinated dicarboxylic acid derivative includes a fluorinated dicarboxylic acid.
- the fluorine-containing dicarboxylic acid derivative of the present invention is represented by the following general formula (M-1) or general formula (M-2).
- -CF 2 COA, -CF 2 COA ' , - CF 2 COD and -CF 2 COD' is attached to the same or different aromatic ring carbons.
- —CF 2 COD and —CF 2 COD ′ in the formula are not bonded to adjacent carbon atoms of the same aromatic ring. When adjacent to each other in this way, it is difficult to obtain a polymer lacking in polymerizability.
- Q is a divalent organic group having an aromatic ring which may have a substituent.
- a divalent organic group is an organic group obtained by removing two hydrogen atoms from a compound having one or more aromatic rings.
- the aromatic ring is a monocyclic or condensed ring having 4 to 20 carbon atoms.
- the linking group Y between the aromatic rings is a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , O, S, C (CH 3 ) 2 , C (CF 3 ) 2 , SO 2 , CO, NH, COO (ester), a linking group composed of a divalent group in which two or more of the same or different groups selected from these groups or selected from these groups are bonded, You may couple
- aromatic ring examples include a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, phenanthrene ring, chrysene ring, triphenylene ring, tetraphen ring, pyrene ring, picene ring, pentaphen ring, perylene ring, pyrrole ring, Examples include a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, and a pyridazine ring. Of these, a benzene ring, naphthalene, and a pyridine ring are
- the hydrogen atom on the aromatic ring is a fluorine atom, a chlorine atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a hydroxycarbonyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (wherein A hydrogen atom on the alkyl group may be substituted with a hydroxyl group or a fluorine atom), a straight chain having 1 to 6 carbon atoms, a branched or cyclic alkoxyl group, a straight chain having 1 to 6 carbon atoms, It may be substituted with a branched or cyclic alkoxycarbonyl group.
- examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, Examples include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group and the like.
- Examples of the hydrogen atom on the alkyl group substituted with a hydroxyl group include, for example, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, 4-hydroxy-n- Examples thereof include a butyl group, a 5-hydroxy-n-pentyl group, a 6-hydroxy-n-hexyl group, a hydroxycyclopentyl group, and a hydroxycyclohexyl group.
- Examples of the hydrogen atom on the alkyl group substituted with a fluorine atom include, for example, a monofluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, penta Examples include a fluoroethyl group, a heptafluoro-n-propyl group, a heptafluoroisopropyl group, and a nonafluoro-n-butyl group.
- the hydrogen atom on the alkyl group is substituted with a hydroxyl group and a fluorine atom, such as difluorohydroxymethyl group, 2-hydroxy-1,1,2,2-tetrafluoroethyl group, 1,1-difluoro-2 -Hydroxyethyl group, 2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl group and the like.
- a fluorine atom such as difluorohydroxymethyl group, 2-hydroxy-1,1,2,2-tetrafluoroethyl group, 1,1-difluoro-2 -Hydroxyethyl group, 2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl group and the like.
- Examples of the linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, Examples thereof include a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a sec-pentoxy group, a tert-pentoxy group, an n-hexoxy group, an isohexoxy group, a cyclopentoxy group, and a cyclohexoxy group.
- Examples of the straight, branched or cyclic alkoxycarbonyl group having 1 to 6 carbon atoms include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, and isobutoxy.
- each Ar 1 is an aromatic ring optionally having a substituent
- the hydrogen atom on the aromatic ring is a fluorine atom, chlorine atom, hydroxyl group, amino group, nitro group, cyano group, hydroxy group A carbonyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (wherein the hydrogen atom on the alkyl group may be substituted with a hydroxyl group or a fluorine atom), 1 to 6 carbon atoms A linear, branched or cyclic alkoxy group, a linear, branched or cyclic alkoxycarbonyl group having 1 to 6 carbon atoms, or a monovalent group consisting of an optionally substituted aromatic ring May be substituted.
- Y 1 is a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , O, S, C (CH 3 ) 2 , C (CF 3 ) 2 , SO 2 , CO, NH, COO (ester) , A divalent group in which one or more kinds selected from a CONH group or two or more same or different groups selected from these groups are bonded, and p represents an integer of 0 to 3. Two dangling bonds are bonded to different carbon atoms of the same or different aromatic rings.
- the structure of the aromatic ring as a divalent organic group when p is 0 can be illustrated more specifically as follows.
- the dotted line indicates the substitution position of —CF 2 COA or —CF 2 COA ′ or —CF 2 COD or —CF 2 COD ′.
- the two difluoromethylene groups in the formula do not bind to the carbon atoms of the adjacent aromatic rings, in other words, the adjacent carbon atoms simultaneously serve as the starting point of the dotted line. Excluding structure.
- the amino group in the structure of the aromatic ring Q which may have the above substituent may be an amino group protected by a protecting group.
- protecting groups for protecting amino groups include tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, allyloxycarbonyl group, phthaloyl Group, p-toluenesulfonyl group, 2-nitrobenzenesulfonyl group and the like.
- each Ar 2 is an aromatic ring which may have a substituent
- the hydrogen atom on the aromatic ring is a fluorine atom, chlorine atom, hydroxyl group, amino group, nitro group, cyano group, hydroxy group A carbonyl group, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (wherein the hydrogen atom on the alkyl group may be substituted with a hydroxyl group or a fluorine atom), 1 to 6 carbon atoms
- Y 2 is each independently a single bond, CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , O, S, C (CH 3 ) 2 , C (CF 3 ) 2 , SO 2 , CO, NH, COO (Ester), one type selected from CONH groups, or a divalent group in which two or more types selected from these groups are bonded.
- the structure of the divalent organic group Q having an aromatic ring is not limited to the structure exemplified above. Of the structures exemplified above, those shown below are particularly preferred.
- a and A ⁇ are each independently, D and D ⁇ are each independently a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, A linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms, an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and an active ester group together with a CO group (carbonyl group) in the formula May be formed.
- linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec- Examples thereof include a butoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a sec-pentoxy group, a tert-pentoxy group, an n-hexoxy group, an isohexoxy group, a cyclopentoxy group, and a cyclohexoxy group. Of these, a methoxy group and an ethoxy group are preferable.
- aryloxy group which may have a substituent having 6 to 10 carbon atoms include, for example, phenoxy group, o-tolyloxy group, m-tolyloxy group, p-tolyloxy group, p-hydroxyphenoxy group, p-nitrophenoxy group, A polychlorophenoxy group, 1-naphthoxy group, benzyloxy group, pyridyloxy group and the like can be mentioned. Of these, p-nitrophenoxy group is preferred.
- examples of A and A ′ and D and D ′ include a succinimidoxy group and an o-phthalimidoxy group that form an active ester group together with a carbonyl group (CO).
- hydroxyl group, chlorine atom, succinimidoxy group and ethoxy group are particularly preferable as A and A 'and D and D'.
- examples of the acid anhydride of the fluorine-containing dicarboxylic acid represented by the general formula (M-1) include AOCF 2 C— and AOCF 2 C— in the adjacent ring carbons. In the case where they are bonded to each other, those derived from acid anhydrides can be mentioned.
- polycondensation polymer compounds obtained from Q having various substituents hydroxyl group, carboxyl group, alkoxy group, hexafluoroisopropanol group, amino group, etc. function as a crosslinking site and are complementary crosslinking agents in three dimensions. It can bridge
- the amino group protected with a nitro group and a protecting group can be modified or deprotected and similarly three-dimensionally crosslinked.
- fluorine-containing dicarboxylic acid The fluorine-containing dicarboxylic acid according to the present invention is represented by the following general formula (M-3).
- Q is synonymous with Q in the general formula (M-1), and the specific structure can again be the same as that in the general formula (M-1).
- a dihalogenoaryl compound preferably a diiodoaryl compound
- a halogenodifluoroacetate ester preferably ethyl bromodifluoroacetate
- reaction formula [1] A general reaction formula is shown below (reaction formula [1]).
- X 1 , X 2 , X 3 and X 4 are each independently a halogen atom
- R is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and a substitution having 6 to 10 carbon atoms
- the amount of the halogenodifluoroacetate used to act on the dihalogenoaryl compound is not particularly limited, but is usually 1.8 to 3 mol, preferably 1 mol per mol of the dihalogenoaryl compound. 1.9 to 2.2 mol, more preferably substantially 2 mol.
- the amount is less than 1.8 mol, the dihalogenoaryl compound is not consumed in the reaction, and when the amount is 3 mol or more, the side reaction takes precedence and the yield of the desired bis (alkoxycarbonyldifluoromethyl) aryl compound decreases. .
- the amount of copper used to act on the dihalogenoaryl compound is not particularly limited, but is usually 1 to 20 mol, preferably 2 to 15 mol, per 1 mol of the dihalogenoaryl compound. More preferably, it is 3 mol to 10 mol.
- As the shape of the copper used a powdery one is preferable and a coarse one is not preferable.
- the reaction is preferably performed in a solvent.
- a solvent it is preferable to use a polar solvent such as acetonitrile, N, N-dimethylformamide, N, N-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, more preferably N, N-dimethylformamide or dimethyl sulfoxide. It is. These solvents may be used alone or in combination of two or more.
- the reaction temperature is usually in the range of room temperature to 100 ° C., preferably 40 to 80 ° C., and more preferably 50 to 60 ° C.
- the reaction time depends on the reaction temperature, it is usually several minutes to 100 hours, preferably 30 minutes to 50 hours, and more preferably 1 to 20 hours. ), And using an analytical instrument such as gas chromatography, the end point of the reaction is preferably the time when the raw dihalogenoaryl compound is consumed.
- a bis (alkoxycarbonyldifluoromethyl) aryl compound can be obtained by ordinary means such as extraction and recrystallization. If necessary, it can be purified by column chromatography, distillation, recrystallization or the like.
- the hydrolysis reaction is carried out in the presence of a base catalyst, and the base includes one or more alkali metal hydroxides, bicarbonates, carbonates, ammonia, and amines.
- the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate and the like.
- alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate and potassium carbonate are preferred, and are alkali metal hydroxides.
- Sodium hydroxide and potassium hydroxide are particularly preferred.
- the molar ratio of the base to the bis (alkoxycarbonyldifluoromethyl) aryl compound is usually 0.01 to 10, preferably 1.0 to 5, and more preferably 1 to 3.
- This reaction is usually performed in the presence of water.
- the molar ratio of water with respect to the bis (alkoxycarbonyldifluoromethyl) aryl compound is usually 1 or more and there is no upper limit. However, if too much water is used, the efficiency is lowered, so 100 or less is preferable, and more preferably 50 It is as follows.
- organic solvent used in combination is not particularly limited, but an organic solvent obtained by the reaction and capable of extracting the bis (hydroxycarbonyldifluoromethyl) aryl compound from the aqueous layer, for example, esters such as ethyl acetate and n-butyl acetate; diethyl ether Preferred are organic solvents that are not miscible with water, such as ethers such as methylene chloride and alkyl halides such as chloroform.
- the use ratio of the organic solvent is usually 5 parts by mass or more, preferably 10 parts by mass or more, and more preferably 20 to 90 parts by mass with respect to 100 parts by mass in total of water and the organic solvent.
- the reaction temperature is usually from 0 to 100 ° C., preferably from 5 to 80 ° C.
- the reaction time is usually from 10 minutes to 16 hours, preferably from 30 minutes to 6 hours, but a nuclear magnetic resonance apparatus (NMR)
- NMR nuclear magnetic resonance apparatus
- a bis (hydroxycarbonyldifluoromethyl) aryl compound can be obtained by ordinary means such as extraction and recrystallization. If necessary, it can be purified by column chromatography, distillation, recrystallization or the like.
- Chlorination is achieved by bringing the resulting bis (hydroxycarbonyldifluoromethyl) aryl compound into contact with a chlorinating agent in the absence of a solvent or in the presence of a solvent and heating.
- chlorinating agent used examples include general-purpose chlorinating agents such as thionyl chloride, sulfuryl chloride, phosgene, oxalyl chloride, phosphoryl chloride, phosphorus trichloride, phosphorus pentachloride, dichlorotriphenylphosphorane, and dibromotriphenylphosphorane.
- general-purpose chlorinating agents such as thionyl chloride, sulfuryl chloride, phosgene, oxalyl chloride, phosphoryl chloride, phosphorus trichloride, phosphorus pentachloride, dichlorotriphenylphosphorane, and dibromotriphenylphosphorane.
- Thionyl chloride, phosphoryl chloride, and oxalyl chloride are particularly inexpensive and highly reactive. Therefore, chlorination using these reagents is particularly preferable.
- the amount of the chlorinating agent used is 1.6 to 20 mol per mol of the bis (hydroxycarbonyldifluoromethyl) aryl compound, and 2 to 10 mol is particularly preferred.
- the solvent can be used without particular limitation as long as it is inert under the conditions of chlorination.
- benzene, toluene, xylene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like can be used.
- the chlorinating agent also serves as a solvent, so that it is not necessary to use a solvent.
- the reaction temperature for chlorination is 25 to 200 ° C., more preferably 30 to 120 ° C., and the reaction time is usually 10 minutes to 16 hours, preferably 30 minutes to 6 hours. It is preferable to use an analytical instrument such as (NMR) or gas chromatography and use the point of time when the bis (hydroxycarbonyldifluoromethyl) aryl compound as a raw material is consumed as the end point of the reaction.
- an analytical instrument such as (NMR) or gas chromatography
- a bis (hydroxycarbonyldifluoromethyl) aryl compound can be obtained by ordinary means such as extraction and recrystallization. If necessary, it can be purified by column chromatography, distillation, recrystallization or the like.
- the fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1) or the acid anhydride of the fluorine-containing dicarboxylic acid responds to the reactivity of these carbonyl group sites. It is a polymer compound obtained by polycondensation with a polyfunctional compound having one reactive group. Q, A and A ′ in the formula are the same as described above.
- Examples of the reactive group that responds to the reactivity of the carbonyl group site of the polyfunctional compound include a hydroxyl group and its activated group, an amino group and its activated group, and the like.
- the polyfunctional compound requires at least two reactive groups, and may have a plurality of types of reactive groups, but preferably two of them are the same reactive group.
- This fluorine-containing dicarboxylic acid derivative is a compound having two —CF 2 CO— groups.
- three or more functional groups including this —CF 2 CO— group are added. Can have at the same time.
- these functional groups are effectively used, but it is preferable to preferentially use the reactivity of the —CF 2 CO— group.
- m means the number of repeating monomer units (degree of polymerization), preferably 5 to 10,000, preferably 10 to 1,000. Further preferred.
- the polymer of the present invention is a mixture of polymers having a certain degree of polymerization degree, but in terms of the weight average molecular weight of the polymer, it is generally preferably from 1,000 to 5,000,000, particularly preferably from 2,000 to 200,000. The degree of polymerization and molecular weight can be set to desired values by appropriately adjusting the conditions of the polymerization method described later.
- the fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1) or the acid anhydride of the fluorine-containing dicarboxylic acid according to the present invention is contacted with the diol represented by the following general formula (2) within a predetermined temperature range. By making it, it can superpose
- Q, A and A ′ are the same as described above.
- Diols can also be used as actives having groups activated for reaction with carboxyl groups to increase reactivity.
- the activator include alkali metal (lithium, sodium, potassium) salts (dialkoxide) of diol.
- R 1 is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring and a heterocyclic ring, and contains a fluorine atom, a chlorine atom, an oxygen atom, a sulfur atom or a nitrogen atom.
- a part of the hydrogen atom may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group or a cyano group, and a part of the carbon atom may be an oxygen atom, a sulfur atom, It may be substituted with a nitrogen atom, a carbonyl group, or a sulfonyl group.
- m is a positive integer.
- the method for producing the polyester of the present invention is not particularly limited, and a known method can be used. That is, the fluorine-containing dicarboxylic acid represented by the general formula (M-3) is directly dehydrated and condensed with the diol represented by the general formula (2) in the presence of a condensing agent, thereby being represented by the general formula (6). Can be produced.
- a and A ⁇ are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a straight chain having 1 to 6 carbon atoms.
- a linear, branched or cyclic alkoxy group, an aryloxy group which may have a substituent of 6 to 10 carbon atoms, and an acid anhydride of a fluorine-containing dicarboxylic acid derivative are represented by the general formula (2)
- a polymer represented by the general formula (6) can be produced by reacting with a diol.
- a polymer dissolution accelerator that is, a metal salt such as lithium bromide or lithium chloride, a dehydrating agent such as sulfuric acid, phosphoric acid or phosphorus pentoxide, or an acid acceptor such as amine can be used.
- the reaction may be carried out in an organic solvent at a temperature of -20 to 80 ° C.
- a fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1) (where A and A ′ are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) or an acid of the fluorine-containing dicarboxylic acid
- M-1 a fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1)
- a and A ′ are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
- the ratio of the total number of moles of the fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1) used in the polymerization or the acid anhydride of the fluorine-containing dicarboxylic acid to the total number of moles of the diol is 0.5 to 1 Is generally in the range of .5, and more preferably in the range of 0.8 to 1.2. Similar to a normal polycondensation reaction, the closer this ratio is to 1, the larger the molecular weight of the resulting polymer.
- the organic solvent that can be used is not particularly limited as long as both components of the raw material are dissolved, but N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide, N-methyl-2- Amido solvents such as pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Examples include lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, and ⁇ -methyl- ⁇ -butyrolactone.
- polyamide refers to “polyamide diol type polymer compound”, “highly fluorinated polyamide” described later, “polybenzoxazole” obtained by ring closure from these, “heterocyclic type polymer compound” May be included.
- the fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1) or the acid anhydride of the fluorine-containing dicarboxylic acid according to the present invention is brought into contact with the diamine represented by the general formula (3) within a predetermined temperature range. It can superpose
- Q, A and A ′ are the same as described above.
- Q has an amino group
- it can be used as it is when subjected to polycondensation, but it is preferable to use it after protecting the amino group with the above-mentioned protecting group.
- diamine represented by the general formula (3) will be described.
- Diamines can also be used as actives having groups activated for reaction with carboxyl groups to increase reactivity.
- both amino groups of the diamine are trialkylsilylamino groups (the alkyl group is selected from a methyl group, an ethyl group, a propyl group, and an i-propyl group, and the three may be the same or different. And the like.).
- R 2 in the general formula (3) and the general formula (7) is a divalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and a heterocyclic ring, and includes a fluorine atom, a chlorine atom, an oxygen atom, A sulfur atom or a nitrogen atom may be contained, and a part of the hydrogen atom may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group, or a cyano group. A part thereof may be substituted with an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group or a sulfonyl group.
- m is a positive integer.
- diamine represented by the general formula (3) 1,4-diaminocyclohexane, 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3 '-Bistrifluoromethyl-4,4'-diaminobiphenyl, 3,3'-bistrifluoromethyl-5,5'-diaminobiphenyl, bis (trifluoromethyl) -4,4'-diaminodiphenyl, bis (fluorinated Alkyl) -4,4′-diaminodiphenyl, dichloro-4,4′-diaminodiphenyl, dibromo-4,4′-diaminodiphenyl, bis (fluorinated alkoxy) -4,4′-diaminodiphenyl, diphenyl-4, 4'-diaminodiphenyl, 4,4'-bis (4-ami
- the production method of the polyamide of the present invention can be used without any particular limitation to known methods. That is, the fluorine-containing dicarboxylic acid represented by the general formula (M-3) is subjected to direct dehydration condensation with the diamine represented by the general formula (3) in the presence of a condensing agent, whereby the heavy compound represented by the general formula (7) is represented. Coalescence can be manufactured.
- a and A ′ are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a straight chain having 1 to 6 carbon atoms.
- a linear, branched or cyclic alkoxy group, an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and an acid anhydride of a fluorine-containing dicarboxylic acid derivative are represented by the general formula (3).
- a polymer represented by the general formula (7) can be produced by reacting with diamine.
- a polymer dissolution accelerator that is, a metal salt such as lithium bromide or lithium chloride, a dehydrating agent such as sulfuric acid, phosphoric acid or phosphorus pentoxide, or an acid acceptor such as amine can be used.
- the reaction may be carried out in an organic solvent at a temperature of -20 to 80 ° C.
- a polymer dissolution accelerator is used, polymerization can be performed even when A and A 'of the fluorine-containing dicarboxylic acid derivative are a hydroxyl group or an alkoxy group.
- a fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1) (where A and A ′ are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom) or an acid of the fluorine-containing dicarboxylic acid
- M-1 a fluorine-containing dicarboxylic acid derivative represented by the general formula (M-1)
- a and A ′ are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
- the ratio of the total number of moles of the fluorine-containing dicarboxylic acid derivative represented by formula (M-1) used in the polymerization or the acid anhydride of the fluorine-containing dicarboxylic acid to the total number of moles of the diamine is 0.5 to 1. Is generally in the range of .5, and more preferably in the range of 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer this ratio is to 1, the larger the molecular weight of the resulting polymer.
- the organic solvent that can be used is not particularly limited as long as both components of the raw material are dissolved, but N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide, N-methyl-2- Amido solvents such as pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, Examples include lactones such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, and ⁇ -methyl- ⁇ -butyrolactone.
- Q has an amino group
- it can be used as it is when subjected to polycondensation, but it is preferable to use it after protecting the amino group with the above-mentioned protecting group.
- R 3 in the general formula (4) and the general formula (8) is a tetravalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, and a heterocyclic ring, and includes a fluorine atom, a chlorine atom, an oxygen atom, A sulfur atom or a nitrogen atom may be contained, and a part of the hydrogen atom may be substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group, or a cyano group. A part thereof may be substituted with an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, or a sulfonyl group.
- m is a positive integer.
- diaminodiol represented by the general formula (4) examples include 2,4-diamino-1,5-cyclohexanediol, 2,4-diamino-1,5-benzenediol, 3 , 3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) ketone, bis (3-amino-4- Hydroxyphenyl) sulfide, bis (3-amino-4-hydroxyphenyl) ether, bis (3-hydroxy-4-aminophenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2, 2-bis (3-hydroxy-4-aminophenyl) propane, bis (3-hydroxy-4-aminophenyl) methane, 2,2-bis 3-amino-4-hydroxyphenyl) hexafluoropropan
- a known method can be used as the method for producing the polyamide diol type polymer compound of the present invention without any particular limitation. That is, the fluorine-containing dicarboxylic acid represented by the general formula (M-3) is subjected to direct dehydration condensation with the diaminodiol represented by the general formula (4) in the presence of the condensing agent, thereby obtaining the general formula (8). A polymer can be produced.
- a and A ′ are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a straight chain having 1 to 6 carbon atoms.
- a linear, branched or cyclic alkoxy group, an aryloxy group having a substituent of 6 to 10 carbon atoms, and an acid anhydride of a fluorine-containing dicarboxylic acid derivative are represented by the general formula (4)
- a polymer represented by the general formula (8) can be produced by reacting with diaminodiol.
- a polymer dissolution accelerator that is, a metal salt such as lithium bromide or lithium chloride, a dehydrating agent such as phosphoric acid or phosphorus pentoxide, or an acid acceptor such as amine can be used.
- the method and conditions for this polymerization reaction are not particularly limited. Since the elementary reaction of the polymerization is an amide formation reaction, the same method and solvent species as the polyamide production represented by the general formula (7) described above can be used.
- the polyamide phenol resin (polyamide diol type polymer compound) obtained by the above method can be derived into a polybenzoxazole resin represented by the general formula (9) by further dehydrating and ring-closing.
- R 3 in the general formula (9) are the same as R 3 in the general formula (4).
- a known method can be used for the dehydration ring-closing reaction without particular limitation.
- the cyclization reaction can be performed by various methods that promote dehydration conditions such as heat, acid catalyst, and base catalyst.
- the treatment can be carried out at a temperature of 80 to 400 ° C., but a temperature range of 150 to 350 ° C. is particularly preferred.
- the heating time is about 10 minutes to 10 hours, but is usually about 30 minutes to 2 hours.
- the ring closure temperature is 150 ° C. or lower, the ring closure rate is low, and thus the film strength of polybenzoxazole is impaired, and when it is 350 ° C. or higher, the film is colored or brittle.
- the acid catalyst p-toluenesulfonic acid, methanesulfonic acid and the like can be used, and as the base catalyst, triethylamine, pyridine and the like can be used.
- the polybenzoxazole after ring closure is soluble in an organic solvent, it can be chemically ring-closed in an organic solution using a dehydrating reagent such as acetic anhydride and an organic base such as pyridine and triethylamine.
- the ring After applying the highly fluorinated polyamide resin represented by the general formula (10) to various articles, the ring can be closed.
- resin modification accompanied by a large change in physical properties such as improvement in heat resistance, change in solubility, reduction in refractive index and dielectric constant, and expression of water and oil repellency can be performed.
- R 4 in the general formula (5) and the general formula (10) is a tetravalent organic group containing one or more selected from an alicyclic ring, an aromatic ring, a condensed polycyclic aromatic ring, and a heterocyclic ring, and is a fluorine atom May contain a chlorine atom, an oxygen atom, a sulfur atom or a nitrogen atom, and a part of the hydrogen atom is substituted with a fluorine atom, a chlorine atom, an alkyl group, a fluoroalkyl group, a carboxyl group, a hydroxyl group or a cyano group.
- some of the carbon atoms may be substituted with an oxygen atom, a sulfur atom, a nitrogen atom, a carbonyl group, or a sulfonyl group.
- m is a positive integer.
- diaminodiol substituted with the hexafluoroisopropanol moiety represented by the general formula (5) include the following compounds, but the present invention is not limited thereto. is not.
- the polymerization reaction method and conditions of the “highly fluorinated polyamide” of the present invention are not particularly limited. Since the elementary reaction of the polymerization is an amide formation reaction, the same method, conditions and solvent types as those for producing the polyamide resin represented by the general formula (7) can be used.
- the highly fluorinated polyamide resin represented by the general formula (10) obtained by the above method is further derived by dehydration and ring closure into a “heterocyclic polymer compound” represented by the general formula (11). can do.
- the R 4 in the general formula (11) is synonymous with R 4 in the general formula (5).
- the conditions for the dehydration ring closure reaction are not particularly limited, but cyclization can be performed by various methods that promote dehydration conditions such as heat, acid catalyst, and base catalyst.
- a known method can be used for the dehydration ring-closing reaction without particular limitation.
- the cyclization reaction can be performed by various methods that promote dehydration conditions such as heat, acid catalyst, and base catalyst.
- the treatment can be carried out at a temperature of 80 to 400 ° C., but a temperature range of 150 to 350 ° C. is particularly preferred, and the ring can be substantially closed at about 250 ° C.
- the ring closing temperature is 150 ° C. or lower, the resulting film strength is impaired because the ring closing rate is low, and when it is 350 ° C. or higher, the film is colored or brittle.
- the acid catalyst p-toluenesulfonic acid, methanesulfonic acid and the like can be used, and as the base catalyst, triethylamine, pyridine and the like can be used.
- the base catalyst triethylamine, pyridine and the like can be used.
- the "heterocyclic polymer” after ring closure is soluble in an organic solvent, it should be chemically closed in an organic solution using a dehydrating reagent such as acetic anhydride and an organic base such as pyridine or triethylamine. Is also possible.
- the heterocycle of the “heterocyclic polymer compound” represented by the general formula (11) can be formed by dehydration and ring closure under milder conditions than the oxazole ring represented by the general formula (9).
- heterocyclic polymer represented by the general formula (11) contains a heterocycle containing a trifluoromethyl group, it is more than the polybenzoxazole represented by the general formula (9). Furthermore, it exhibits low dielectric constant, low water absorption, and high transparency.
- polyester and polyamide of the present invention can be used in a varnish state dissolved in an organic solvent, or in a powder state, a film state, or a solid state.
- additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator, and a sensitizer may be mixed in the obtained fluoropolymer as necessary. Absent. When using in varnish, apply it on a substrate such as glass, silicon wafer, metal, metal oxide, ceramics, resin, etc.
- the film is usually heated to increase the degree of polymerization to obtain a film (coating film) having desired characteristics. In this case, it can be carried out at a temperature of about 150 to 350 ° C., but is preferably carried out at 300 ° C. or lower, more preferably 250 ° C. or lower.
- the polyamide represented by the general formula (8) or the general formula (10) is ring-closed by this heating to form a polybenzoxazole represented by the general formula (9) or a “heterocycle” represented by the general formula (11).
- Type polymer compound ”.
- organic solvent used here examples include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformamide, hexamethylphosphoric triamide, N-methyl-2-pyrrolidone, and ⁇ -butyrolactone.
- lactones such as ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -butyrolactone, concentrated sulfuric acid and the like.
- Example 2 Synthesis of ⁇ , ⁇ 4 , ⁇ , ⁇ 4 tetrafluoro-1,4-benzenediacetic acid
- a 250 mL glass flask was added 15 g of the diester obtained in Example 1 (purity 74%, 34 mmol), 40 mL of water, and 9.6 g of a 48% aqueous sodium hydroxide solution (115 mmol / 3.3 equivalents), and 18 hours at room temperature. After stirring, the completion of the reaction was confirmed by 19 F NMR. Then, it wash
- Example 4 Synthesis of ⁇ , ⁇ 3 , ⁇ , ⁇ 3 tetrafluoro-1,3-benzenediacetic acid
- 21 g of the diester obtained in Example 3 purity 52%, 34 mmol
- 40 mL of water and 9.6 g of a 48% aqueous sodium hydroxide solution (115 mmol / 3.3 equivalents)
- 18 hours at room temperature After stirring, the completion of the reaction was confirmed by 19 F NMR. Then, it wash
- Example 5 Synthesis of ⁇ , ⁇ 4 , ⁇ , ⁇ 4 tetrafluoro-1,4-benzenediacetyl chloride To a 250 mL glass flask equipped with a condenser, 49 g (purity 90%, 167 mmol / 1.0 equivalent) of dicarboxylic acid obtained in the same manner as in Examples 1 and 2 and 50 mL of acetonitrile were added, and 50 g (420 mmol) of thionyl chloride was added thereto. /2.5 equivalents) was added dropwise and stirred at room temperature for 18 hours.
- Example 8 Synthesis of 5-methoxy- ⁇ , ⁇ 4 , ⁇ , ⁇ 4 tetrafluoro-1,3-benzenediacetic acid To a 250 mL glass flask was added 15 g of the diester obtained in Example 7 (purity 75%, 32 mmol), 40 mL of water, and 10.0 g of a 48% aqueous sodium hydroxide solution (120 mmol / 3.8 equivalents), and 18 hours at room temperature. After stirring, the completion of the reaction was confirmed by 19 F NMR.
- Example 12 Synthesis of 2,2 '-(diphenyl-4,4'-diyl) bis (2,2-difluoroacetyl chloride) To a 250 mL glass flask equipped with a condenser, 43 g (purity 80%, 100 mmol / 1.0 equivalent) of dicarboxylic acid prepared in the same manner as in Examples 11 and 12 and 80 mL of acetonitrile were added, and 30 g of thionyl chloride (250 mmol / 2) was added thereto. 0.5 equivalent) was added dropwise and stirred at room temperature for 24 hours.
- reaction was carried out at 100 ° C. for 17 hours at a carbon monoxide pressure of 2 MPa.
- 50 mL of 2N hydrochloric acid was added to the reaction solution.
- the organic layer was separated by extraction with 50 mL of isopropyl ether.
- 60 mL of a 7% aqueous sodium hydroxide solution was added, and the aqueous layer was separated.
- the aqueous layer was washed with 30 mL of heptane, and 60 mL of 6N hydrochloric acid was added.
- the precipitated solid was isolated by filtration and washed with 50 mL of heptane.
- Carboxylic acid chloride 1 Preparation of [5- [2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl] -1,3-benzenedicarboxylic acid chloride 50 mL of glass To the flask, 3.5 g (10.5 mmol) of 5- [2,2,2-trifluoro-1-hydroxy-1- (trifluoromethyl) ethyl] -1,3-benzenedicarboxylic acid obtained in Reference Example 5 was added. ) And 20 ml thionyl chloride. Then, it was made to react at 70 degreeC for 5 hours, stirring.
- Polymer 1 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape.
- DMF N, N-dimethylformamide
- the film thickness was about 10 ⁇ m, the film thickness was measured using a HP-4284A Precision LCR meter manufactured by Hewlett-Packard at a frequency of 100 kHz in accordance with JIS-K6911, and the relative dielectric constant was calculated according to the following formula (hereinafter referred to as “the dielectric constant”). The same).
- the physical properties of the film are shown in Table 1.
- Relative permittivity (capacitance measurement value ⁇ film thickness) / (vacuum permittivity ⁇ measurement area)
- Example 14 Synthesis of Polymer 2 3.03 g (10.0 mmol) of the acid chloride ( ⁇ , ⁇ 3 , ⁇ , ⁇ 3 tetrafluoro-1,3-benzenediacetyl chloride) obtained in Example 6 and 2. By using 28 g (10.0 mmol) and 20.0 g of N-methyl-2-pyrrolidone (NMP), 3.99 g (yield 87%) of polymer 2 was obtained in the same manner as in Example 10. It was. The results of specific viscosity measurement of the obtained polymer 2 are shown in Table 1.
- Polymer 2 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 15 Synthesis of Polymer 3 3.33 g (10.0 mmol) of the acid chloride (5-methoxy- ⁇ , ⁇ 3 , ⁇ , ⁇ 3 tetrafluoro-1,3-benzenediacetyl chloride) obtained in Example 9 in terms of pure component, bisphenol 4.21 g (86% yield) of A was obtained in the same manner as in Example 10 using 2.28 g (10.0 mmol) of A and 20.0 g of N-methyl-2-pyrrolidone (NMP). Polymer 3 was obtained. The results of measuring the specific viscosity of the obtained polymer 3 are shown in Table 1.
- Polymer 3 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 16 Synthesis of Polymer 4 3.03 g (10.0 mmol) of the acid chloride obtained in Example 5 in terms of pure content, 3.36 g (10.0 mmol) of diol 1, and 20.30 g of N-methyl-2-pyrrolidone (NMP). Using 0 g, 4.64 g (yield 82%) of polymer 4 was obtained in the same manner as in Example 10. Table 1 shows the results of measurement of the specific viscosity of the obtained polymer 4.
- Polymer 3 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 17 Synthesis of Polymer 5 3.03 g (10.0 mmol) of the acid chloride obtained in Example 6 in terms of pure content, 3.36 g (10.0 mmol) of diol 1, and 20.30 g of N-methyl-2-pyrrolidone (NMP). Using 0 g, 4.81 g (yield 85%) of polymer 5 was obtained in the same manner as in Example 10. The results of measuring the specific viscosity of the obtained polymer 5 are shown in Table 1.
- Polymer 5 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 18 Synthesis of polymer 6 3.03 g (10.0 mmol) of the acid chloride obtained in Example 5 in terms of pure component, 2.26 g (10.0 mmol) of diamine 1, and 20.20 g of N-methyl-2-pyrrolidone (NMP). Using 0 g, 4.24 g (yield 93%) of polymer 6 was obtained in the same manner as in Example 10. The results of measuring the specific viscosity of the obtained polymer 6 are shown in Table 1.
- Polymer 6 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 19 Synthesis of Polymer 7 3.03 g (10.0 mmol) of the acid chloride obtained in Example 6 in terms of pure amount, 2.26 g (10.0 mmol) of diamine 1, and 20.20 g of N-methyl-2-pyrrolidone (NMP). In the same manner as in Example 10, 4.154 g (yield 91%) of polymer 7 was obtained using 0 g. The results of measuring the specific viscosity of the obtained polymer 7 are shown in Table 1.
- Polymer 7 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 20 Synthesis of polymer 8 3.03 g (10.0 mmol) of the acid chloride obtained in Example 5 in terms of pure content, 3.34 g (10.0 mmol) of diamine 2, and 20.35 N-methyl-2-pyrrolidone (NMP). In the same manner as in Example 10, 4.81 g (yield 85%) of polymer 8 was obtained using 0 g. Table 1 shows the results of measurement of the specific viscosity of the obtained polymer 8.
- Polymer 8 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 21 Synthesis of polymer 9 3.03 g (10.0 mmol) of the acid chloride obtained in Example 6 in terms of pure content, 3.34 g (10.0 mmol) of diamine 2 and 20.20 N-methyl-2-pyrrolidone (NMP). Using 0 g, 4.47 g (yield 79%) of polymer 9 was obtained in the same manner as in Example 10. The results of measuring the specific viscosity of the obtained polymer 9 are shown in Table 1.
- Polymer 9 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 22 Synthesis of polymer 10 3.03 g (10.0 mmol) of the acid chloride obtained in Example 5 in terms of pure content, 3.20 g (10.0 mmol) of diamine 3 and 20.20 g of N-methyl-2-pyrrolidone (NMP). Using 0 g, 4.52 g (yield 82%) of polymer 10 was obtained in the same manner as in Example 10. Table 1 shows the results of measurement of the specific viscosity of the obtained polymer 10.
- Polymer 10 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 23 Synthesis of polymer 11 3.03 g (10.0 mmol) of the acid chloride obtained in Example 6 in terms of pure content, 3.66 g (10.0 mmol) of diaminodiphenol 1, and N-methyl-2-pyrrolidone (NMP) Using 20.0 g, 5.07 g (yield 85%) of polymer 11 was obtained in the same manner as in Example 10. Table 1 shows the results of measurement of specific viscosity of the obtained polymer 11.
- Example 24 Synthesis of polymer 12 Polymer 11 (1.00 g) obtained in Example 20 and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. From the infrared absorption spectrum (IR) analysis, it was confirmed that the structure of the obtained film was polymer 12. Table 1 shows the physical properties (dielectric constant) of the obtained film. Similarly, when heat treatment was further performed at 300 ° C. for 1 hour, and the same observation and measurement were performed, a flexible transparent film having a retained shape was obtained, and the relative dielectric constant was not subjected to additional heat treatment. It did not change.
- DMF N-dimethylformamide
- Example 25 Synthesis of polymer 13 3.03 g (10.0 mmol) of the acid chloride obtained in Example 5 in terms of pure content, 5.30 g (10.0 mmol) of diaminodiol 1 synthesized according to the method described in JP-A-2007-119503, Then, 6.01 g (yield 79%) of polymer 13 was obtained in the same manner as in Example 10 using 20.0 g of N-methyl-2-pyrrolidone (NMP). The results of measuring the specific viscosity of the obtained polymer 13 are shown in Table 1.
- Example 26 Synthesis of Polymer 14 Polymer 13 (1.00 g) obtained in Example 22 and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. From the IR analysis, it was confirmed that the structure of the obtained film was polymer 14. Table 1 shows the physical properties (dielectric constant) of the obtained film. Similarly, when heat treatment was further performed at 300 ° C. for 1 hour, and the same observation and measurement were performed, a flexible transparent film having a retained shape was obtained, and the relative dielectric constant was not subjected to additional heat treatment. It did not change.
- DMF N-dimethylformamide
- Example 27 Synthesis of Polymer 15 Bisphenol A (2.28 g, 10.0 mmol) and N-methyl-2-pyrrolidone (NMP) (20.0 g) were placed in a 100 ml three-necked flask equipped with a stirrer, and the mixture was stirred under a nitrogen atmosphere under ice cooling. To this, 0.20 g (1.0 mmol) of terephthalic acid chloride and 2.73 g (9.0 mmol) of the acid chloride obtained in Example 5 were slowly added over a period of 10 minutes or more.
- NMP N-methyl-2-pyrrolidone
- Polymer 1 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 28 Synthesis of polymer 22 2.79 g (10.0 mmol) of 2,2 ′-(diphenyl-4,4′-diyl) bis (2,2-difluoroacetyl chloride) obtained in Example 12 in terms of pure content and 3 of diol 1
- Example 13 using 5.36 g (10.0 mmol) and 20.0 g of N-methyl-2-pyrrolidone (NMP), 5.78 g (yield 90%) of polymer 22 was obtained. Obtained.
- Table 1 shows the results of measurement of specific viscosity of the obtained polymer 22.
- Polymer 22 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 29 Synthesis of polymer 23 2.79 g (10.0 mmol) of 2,2 ′-(diphenyl-4,4′-diyl) bis (2,2-difluoroacetyl chloride) obtained in Example 12 in terms of pure content and 3 of diamine 2 .34 g (10.0 mmol) and 20.0 g N-methyl-2-pyrrolidone (NMP) were used in the same manner as in Example 10 to obtain 5.64 g (88% yield) of polymer 23. Obtained. Table 1 shows the results of measurement of specific viscosity of the obtained polymer 23.
- Polymer 23 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. Table 1 shows the physical properties of the obtained film.
- Example 30 Synthesis of Polymer 24 2.79 g (10.0 mmol) of 2,2 ′-(diphenyl-4,4′-diyl) bis (2,2-difluoroacetyl chloride) obtained in Example 12 was converted into pure diol diphenol 1 5.72 g (yield 85%) of polymer in the same manner as in Example 10 using 3.66 g (10.0 mmol) and 20.0 g N-methyl-2-pyrrolidone (NMP) 24 was obtained. The results of measuring the specific viscosity of the obtained polymer 24 are shown in Table 1.
- Example 31 Synthesis of polymer 25
- the obtained polymer 24 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution.
- the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere.
- the film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. From the infrared absorption spectrum (IR) analysis, it was confirmed that the structure of the obtained film was polymer 25.
- Table 1 shows the physical properties of the obtained film.
- Example 32 Synthesis of polymer 26 2.79 g (10.0 mmol) of 2,2 ′-(diphenyl-4,4′-diyl) bis (2,2-difluoroacetyl chloride) obtained in Example 12 in terms of pure component, In the same manner as Example 10 using 5.30 g (10.0 mmol) and 30.0 g N-methyl-2-pyrrolidone (NMP), 6.85 g (82% yield) of polymer 26 Got. The results of measuring the specific viscosity of the obtained polymer 26 are shown in Table 1.
- Example 33 Synthesis of polymer 27
- the obtained polymer 26 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution.
- the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere.
- the film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. From the infrared absorption spectrum (IR) analysis, it was confirmed that the structure of the obtained film was polymer 27.
- Table 1 shows the physical properties of the obtained film.
- Example 10 Synthesis of polymer 16
- Polymer 16 was obtained in the same manner as in Example 10 except that 2.0 g (10.0 mmol) of terephthalic acid chloride was used instead of the acid chloride obtained in Example 5.
- the results of specific viscosity measurement of the obtained polymer 16 are shown in Table 1.
- Polymer 16 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After filtering the obtained solution, the filtrate was spin-coated on a glass substrate, and was heat-treated in a nitrogen atmosphere at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour. The degree of polymerization was low and many cracks occurred.
- DMF N, N-dimethylformamide
- Example 15 Synthesis of polymer 17 In Example 15, Polymer 17 was obtained in the same manner as in Example 15 except that 2.0 g (10.0 mmol) of terephthalic acid chloride was used instead of the acid chloride obtained in Example 5. Table 1 shows the results of measurement of specific viscosity of the obtained polymer 17.
- Polymer 17 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After filtering the obtained solution, the filtrate was spin-coated on a glass substrate, and was heat-treated in a nitrogen atmosphere at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour. The degree of polymerization was low and many cracks occurred.
- DMF N, N-dimethylformamide
- Structure 18-1 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece created on the glass substrate was peeled off to obtain a flexible transparent film having a retained shape. From the IR analysis, it was confirmed that the obtained film was a mixed polymer of the structure 18-1 and the structure 18-2 (polymer 18). Moreover, many cracks generate
- DMF N, N-dimethylformamide
- Polymer 19 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. Although the film piece created on the glass substrate was peeled off, a transparent film with poor flexibility was obtained. From the IR analysis, the structure of the obtained film was confirmed to be polymer 20. Table 1 shows the physical properties of the obtained film.
- Polymer 21 (1.00 g) and N, N-dimethylformamide (DMF) (4.00 g) were mixed to prepare a uniform solution. After the obtained solution was filtered, the filtrate was spin-coated on a glass substrate, and heat-treated at 80 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 250 ° C. for 1 hour in a nitrogen atmosphere. The film piece prepared on the glass substrate had many cracks because of the low degree of polymerization.
- DMF N, N-dimethylformamide
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Abstract
Description
本明細書において、「含フッ素ジカルボン酸誘導体」には、含フッ素ジカルボン酸を含むものとする。
本発明にかかる含フッ素ジカルボン酸は、下記一般式(M-3)で表される。
本発明の高分子化合物は、一般式(M-1)で表される含フッ素ジカルボン酸誘導体または該含フッ素ジカルボン酸の酸無水物を、これらのカルボニル基部位の反応性に応答する2~4個の反応性基を有する多官能性化合物と重縮合させて得られる高分子化合物である。
本発明にかかる一般式(M-1)で表される含フッ素ジカルボン酸誘導体または該含フッ素ジカルボン酸の酸無水物を、下記一般式(2)で表されるジオールと所定の温度範囲で接触させることで、下記一般式(6)で表されるポリエステルへと、重合することができる。
本明細書において、「ポリアミド」は後述する「ポリアミドジオール型高分子化合物」、「高度にフッ素化されたポリアミド」、これらから閉環して得られる「ポリベンゾオキサゾール」、「ヘテロ環型高分子化合物」を包含することがある。
一般式(M-1)で表される含フッ素ジカルボン酸誘導体は、一般式(4)で表されるジアミノジオールと所定の温度範囲で接触させ、一般式(8)で表される「ポリアミドジオール型高分子化合物」へと重合することができる。
一般式(M-1)で表される、本発明の含フッ素ジカルボン酸は、一般式(5)で表されるヘキサフルオロイソプロパノール部位が置換したジアミノジオールと所定の温度範囲で接触させ、一般式(10)で表される「高度にフッ素化されたポリアミド」へと重合することができる。
[1,4-ベンゼンジ酢酸α,α4,β,β4テトラフルオロ-1,4-ジエチルエステルの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=7.69(s,4H),4.29(q,J=7.1Hz,4H;C-CH2CH3のCH2),1.29(t,J=7.1Hz,6H;C-CH2CH3のCH3).
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-104.68(s,4F)。
[α,α4,β,β4テトラフルオロ-1,4-ベンゼンジ酢酸の物性]
1H NMR(測定溶媒:重ジメチルスルホキシド,基準物質:テトラメチルシラン);δ=7.75(s,4H).
19F NMR(測定溶媒:重ジメチルスルホキシド,基準物質:トリクロロフルオロメタン);δ=-102.54(s,4F)。
[1,3-ベンゼンジ酢酸α,α3,β,β3テトラフルオロ-1,3-ジエチルエステルの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=7.85(s,1H),7.73(d,J=7.8Hz,2H),7.55(t,J=7.1Hz,1H),4.29(q,J=7.1Hz,4H;C-CH2CH3のCH2),1.30(t,J=7.1Hz,6H;C-CH2CH3のCH3).
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-104.35(s,4F)。
[α,α3,β,β3テトラフルオロ-1,3-ベンゼンジ酢酸の物性]
1H NMR(測定溶媒:重ジメチルスルホキシド,基準物質:テトラメチルシラン);δ=7.85‐7.65(m,4H).
19F NMR(測定溶媒:重ジメチルスルホキシド,基準物質:トリクロロフルオロメタン);δ=-102.30(s,4F)。
[α,α4,β,β4テトラフルオロ-1,4-ベンゼンジアセチルクロリドの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=7.76(s,4H).
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-101.32(s,4F)。
[α,α3,β,β3テトラフルオロ-1,3-ベンゼンジアセチルクロリドの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=7.86(s,1H),7.81(d,J=7.8Hz,2H),7.67(t,J=7.1Hz,1H).
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-101.10(s,4F)。
[5-メトキシ-1,3-ベンゼンジ酢酸α,α4,β,β4テトラフルオロ-1,4-ジエチルエステルの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=6.37(s,2H),6.44(s,1H),4.13(q,J=7.0Hz,4H;C-CH2CH3のCH2),3.73(s,3H;O-CH3のCH3),1.30(t,J=7.0Hz,6H;C-CH2CH3のCH3).
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-104.30(s,4F)。
[5-メトキシ-α,α4,β,β4テトラフルオロ-1,4-ベンゼンジ酢酸の物性]
1H NMR(測定溶媒:重ジメチルスルホキシド,基準物質:テトラメチルシラン);δ=12.30(s,1H;OH),6.42(s,2H),6.46(s,1H),3.77(s,3H;O-CH3のCH3).
19F NMR(測定溶媒:重ジメチルスルホキシド,基準物質:トリクロロフルオロメタン);δ=-103.50(s,4F)。
[5-メトキシ-α,α3,β,β3テトラフルオロ-1,3-ベンゼンジアセチルクロリドの物性]
1H NMR(測定溶媒:重ジメチルスルホキシド,基準物質:テトラメチルシラン);δ=6.41(s,2H),6.45(s,1H),3.76(s,3H;O-CH3のCH3).
19F NMR(測定溶媒:重ジメチルスルホキシド,基準物質:トリクロロフルオロメタン);δ=-102.30(s,4F)。
[2,2’-(ジフェニル-4,4’-ジイル)ビス(2,2-ジフルオロ酢酸)ジエチルエステルの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=7.60(d,J=8.5Hz,4H),7.56(d,J=8.5Hz,4H),4.22(q,J=7.1Hz,4H;C-CH2CH3のCH2),1.22(t,J=7.1Hz,6H;C-CH2CH3のCH3).
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-104.15(s,4F)。
[2,2’-(ジフェニル-4,4’-ジイル)ビス(2,2-ジフルオロ酢酸)の物性]
1H NMR(測定溶媒:重ジメチルスルホキシド,基準物質:テトラメチルシラン);δ=7.89(d,J=8.5Hz,4H),7.69(d,J=8.5Hz,4H).
19F NMR(測定溶媒:重ジメチルスルホキシド,基準物質:トリクロロフルオロメタン);δ=-102.12(s,4F)。
[2,2’-(ジフェニル-4,4’-ジイル)ビス(2,2-ジフルオロアセチルクロリド)の物性]
1H NMR(測定溶媒:重ジメチルスルホキシド,基準物質:テトラメチルシラン);δ=7.75(d,J=8.5Hz,4H),7.57(d,J=8.5Hz,4H).
19F NMR(測定溶媒:重ジメチルスルホキシド,基準物質:トリクロロフルオロメタン);δ=-100.92(s,4F)。
[1-[2,2,2-トリフルオロ-1-ヒドロキシ-1-(トリフルオロメチル)エチル]-3,5-ジブロモベンゼンの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=7.79(s,3H)。
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-76.0(s,6F,CF3)。
[5-[2,2,2-トリフルオロ-1-ヒドロキシ-1-(トリフルオロメチル)エチル]-1,3-ベンゼンジカルボン酸の物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=9.27(s,1H),8.58(m,1H),8.46(s,2H)。
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-73.5(s,6F,CF3)。
50mLのガラスフラスコに、参考例5で得られた5-[2,2,2-トリフルオロ-1-ヒドロキシ-1-(トリフルオロメチル)エチル]-1,3-ベンゼンジカルボン酸3.5g(10.5mmol)と塩化チオニル20mlを投入した。その後、攪拌しながら70℃で5時間反応させた。反応後、塩化チオニルを留去し、目的とするカルボン酸クロリド1である[5-[2,2,2-トリフルオロ-1-ヒドロキシ-1-(トリフルオロメチル)エチル]-1,3-ベンゼンジカルボン酸クロリドを3.8g、収率98%で得た。
[[5-[2,2,2-トリフルオロ-1-ヒドロキシ-1-(トリフルオロメチル)エチル]-1,3-ベンゼンジカルボン酸クロリドの物性]
1H NMR(測定溶媒:重クロロホルム,基準物質:テトラメチルシラン);δ=8.52(m,1H),8.41(s,2H)。
19F NMR(測定溶媒:重クロロホルム,基準物質:トリクロロフルオロメタン);δ=-72.7(s,6F,CF3)。
比誘電率=(容量測定値×フィルムの厚み)/(真空の誘電率×測定面積)
Claims (11)
- 一般式(M-1)で表される含フッ素ジカルボン酸誘導体または該含フッ素ジカルボン酸の酸無水物を、これらのカルボニル基部位の反応性に応答する2~4個の反応性基を有する多官能性化合物と重縮合させて得られる高分子化合物。
- 二価の有機基Qが、下記一般式(a)で表される二価の有機基であることを特徴とする、請求項1に記載の高分子化合物。
- 二価の有機基Qが、下記一般式(b)で表される二価の有機基であることを特徴とする、請求項1に記載の高分子化合物。
- 多官能性化合物を一般式(3)で表されるジアミンとして重縮合させて得られる一般式(7)で表される請求項1~4のいずれか1項に記載の高分子化合物。
- 多官能性化合物を一般式(4)で表されるジアミノジオールとして重縮合させて得られる一般式(8)で表される請求項1~4のいずれか1項に記載の高分子化合物。
- 多官能性化合物を一般式(5)で表されるヘキサフルオロイソプロパノール部位が置換したジアミノジオールとして重縮合させて得られる一般式(10)で表される請求項1~4のいずれか1項に記載の高分子化合物。
- 多官能性化合物を一般式(2)で表されるジオールとして重縮合させて得られる一般式(6)で表される請求項1~4のいずれか1項に記載の高分子化合物。
- 一般式(M-2)で表される含フッ素ジカルボン酸誘導体。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05112635A (ja) | 1991-10-23 | 1993-05-07 | Hitachi Ltd | 全フツ素化全芳香族ポリエステル及びそれを用いた光学部品 |
JP2003012596A (ja) * | 2001-06-28 | 2003-01-15 | Central Glass Co Ltd | 含フッ素脂環式ジカルボン酸化合物の製造方法 |
JP2003012601A (ja) * | 2001-06-28 | 2003-01-15 | Central Glass Co Ltd | 脂環式含フッ素ジカルボン酸およびそれを用いた重合体または感光性材料用組成物 |
JP2004143416A (ja) * | 2002-08-29 | 2004-05-20 | National Cardiovascular Center | フッ素含有単量体およびその製造方法、並びに、フッ素含有重合体およびその製造方法 |
JP2006056939A (ja) * | 2004-08-18 | 2006-03-02 | Sumitomo Electric Ind Ltd | 熱可塑性フッ素化ポリベンゾオキサゾール樹脂、その前駆体、成形体、これらの製造方法、及び樹脂組成物 |
JP2007119503A (ja) | 2004-10-13 | 2007-05-17 | Central Glass Co Ltd | 含フッ素重合性単量体及びそれを用いた高分子化合物 |
JP2009041002A (ja) * | 2007-07-17 | 2009-02-26 | Central Glass Co Ltd | 新規な含フッ素ジカルボン酸およびそれを用いた新規な高分子化合物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004143406A (ja) * | 2002-08-28 | 2004-05-20 | Sekisui Chem Co Ltd | ポリエステル系樹脂微粒子及びポリエステル系樹脂微粒子の製造方法 |
WO2004039863A1 (ja) | 2002-10-31 | 2004-05-13 | Toray Industries, Inc. | 脂環式または芳香族のポリアミド、ポリアミドフィルム、それらを用いた光学用部材およびポリアミドのコポリマ |
JP5114938B2 (ja) * | 2006-12-19 | 2013-01-09 | セントラル硝子株式会社 | 含フッ素ジアミンおよびそれを用いた高分子化合物 |
US7806275B2 (en) * | 2007-05-09 | 2010-10-05 | The United States Of America As Represented By The Secretary Of The Interior, The Bureau Of Reclamation | Chlorine resistant polyamides and membranes made from the same |
-
2010
- 2010-02-18 US US13/201,766 patent/US8809451B2/en not_active Expired - Fee Related
- 2010-02-18 CN CN2010800087363A patent/CN102325824B/zh not_active Expired - Fee Related
- 2010-02-18 WO PCT/JP2010/052425 patent/WO2010095678A1/ja active Application Filing
- 2010-02-18 KR KR1020117021657A patent/KR101290226B1/ko not_active IP Right Cessation
- 2010-02-18 EP EP10743804.6A patent/EP2395040A4/en not_active Withdrawn
- 2010-02-18 JP JP2010033260A patent/JP5768320B2/ja active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05112635A (ja) | 1991-10-23 | 1993-05-07 | Hitachi Ltd | 全フツ素化全芳香族ポリエステル及びそれを用いた光学部品 |
JP2003012596A (ja) * | 2001-06-28 | 2003-01-15 | Central Glass Co Ltd | 含フッ素脂環式ジカルボン酸化合物の製造方法 |
JP2003012601A (ja) * | 2001-06-28 | 2003-01-15 | Central Glass Co Ltd | 脂環式含フッ素ジカルボン酸およびそれを用いた重合体または感光性材料用組成物 |
JP2004143416A (ja) * | 2002-08-29 | 2004-05-20 | National Cardiovascular Center | フッ素含有単量体およびその製造方法、並びに、フッ素含有重合体およびその製造方法 |
JP2006056939A (ja) * | 2004-08-18 | 2006-03-02 | Sumitomo Electric Ind Ltd | 熱可塑性フッ素化ポリベンゾオキサゾール樹脂、その前駆体、成形体、これらの製造方法、及び樹脂組成物 |
JP2007119503A (ja) | 2004-10-13 | 2007-05-17 | Central Glass Co Ltd | 含フッ素重合性単量体及びそれを用いた高分子化合物 |
JP2009041002A (ja) * | 2007-07-17 | 2009-02-26 | Central Glass Co Ltd | 新規な含フッ素ジカルボン酸およびそれを用いた新規な高分子化合物 |
Non-Patent Citations (4)
Title |
---|
JOURNAL OF FLUORINE CHEMISTRY, vol. 125, 2004, pages 509 - 515 |
JOURNAL OF FLUORINE CHEMISTRY, vol. 125, 2004, pages 763 - 765 |
JOURNAL OF FLUORINE CHEMISTRY, vol. 8, 1976, pages 11 - 22 |
See also references of EP2395040A4 |
Cited By (4)
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KR101606158B1 (ko) | 2011-05-30 | 2016-03-24 | 샌트랄 글래스 컴퍼니 리미티드 | 함불소 중합성 단량체 및 그것을 사용한 고분자 화합물 |
WO2014084188A1 (ja) * | 2012-11-28 | 2014-06-05 | セントラル硝子株式会社 | 含フッ素重合性単量体およびそれを用いた高分子化合物 |
JP2016059919A (ja) * | 2014-09-12 | 2016-04-25 | セントラル硝子株式会社 | 気体分離膜 |
WO2022030447A1 (ja) * | 2020-08-05 | 2022-02-10 | セントラル硝子株式会社 | 含フッ素ジアミンまたはその塩、含フッ素ジアミンまたはその塩の製造方法、ポリアミド、ポリアミドの製造方法、ポリアミド溶液、ポリアミド環化体、ポリアミド環化体の製造方法、高周波電子部品用絶縁材、高周波電子部品用絶縁材の製造方法、高周波電子部品、高周波機器および高周波電子部品製造用絶縁材料 |
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JP2010215904A (ja) | 2010-09-30 |
KR101290226B1 (ko) | 2013-07-30 |
US8809451B2 (en) | 2014-08-19 |
KR20110127226A (ko) | 2011-11-24 |
EP2395040A1 (en) | 2011-12-14 |
CN102325824B (zh) | 2013-05-01 |
US20110301305A1 (en) | 2011-12-08 |
EP2395040A4 (en) | 2013-08-28 |
JP5768320B2 (ja) | 2015-08-26 |
CN102325824A (zh) | 2012-01-18 |
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