WO2001025313A1 - Fabrication de resine polyimide - Google Patents
Fabrication de resine polyimide Download PDFInfo
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- WO2001025313A1 WO2001025313A1 PCT/JP2000/007013 JP0007013W WO0125313A1 WO 2001025313 A1 WO2001025313 A1 WO 2001025313A1 JP 0007013 W JP0007013 W JP 0007013W WO 0125313 A1 WO0125313 A1 WO 0125313A1
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- polyimide resin
- polyimide
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- 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
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
Definitions
- the present invention relates to a method for producing a polyimide resin. More specifically, the present invention relates to a method for producing a polyimide resin which forms a polyimide by mixing a raw material polymer of the polyimide and heating and drying the mixture under reduced pressure.
- Polyimide is excellent in heat resistance among various organic polymers, and is therefore widely used in the fields of space and aviation, the field of electronic communication, and the field of device A.
- polyimide is formed by generating polyamic acid from diamine and an acid dianhydride in an organic solvent, and then subjecting the polyamic acid to cyclopolymerization to imidize the polyamic acid.
- a suitable dehydration-condensation reagent that is, a basic catalyst represented by a tertiary amine such as triethylamine, pyridine, picoline (for example, picoline), isoquinoline, or a basic catalyst and an anhydride such as acetic anhydride.
- a basic catalyst represented by a tertiary amine such as triethylamine, pyridine, picoline (for example, picoline), isoquinoline, or a basic catalyst and an anhydride such as acetic anhydride.
- a step of purifying the reaction mixture is required to remove tertiary amine or acetic anhydride in the system, and further, a dibasic diamine such as an aromatic is used as a diamine monomer.
- a salt is formed by a neutralization reaction before the polyamic acid is formed when mixed with the acid dianhydride, and the salt is precipitated. I will. Since this salt is in a stable state, the polymerization reaction cannot proceed to form a polyamic acid, and it is impossible to react with a dehydrating reagent to imidize the salt. For this reason, it was difficult to obtain a polyimide using an alicyclic diamine.
- the methods for obtaining polyimide without passing through an intermediate there is a method of reacting an acid dianhydride with diisocyanate.
- the reactivity between the acid dianhydride and the diisocyanate is lower than in the case where diamine and the acid dianhydride are used. Heating at a high temperature of about 250 ° C or more is required. Therefore, the types of organic solvents that can be used during the reaction are limited.
- diisocyanate and Z or acid dianhydride there was a problem that the solubility in a high-boiling organic solvent was poor, and the desired polyimide could not be synthesized.
- An object of the present invention is to solve the above problems, and an object of the present invention is to provide a method capable of easily producing a high molecular weight polyimide resin in a high yield. Disclosure of the invention
- the method for producing a polyimide resin of the present invention comprises: (a) a mixing step of mixing a raw material monomer of polyimide; and
- the starting monomer is An anhydride and a diamine
- the polyamic acid in the (d) drying step, may be produced in the absence of an azeotropic solvent and Z or a dehydration condensation reagent until the imidization reaction is completed. It may be a drying step of heating and drying under reduced pressure.
- a salt is generated in the (a) mixing step.
- the raw material monomers in the (a) mixing step, may be an acid dianhydride and a diisocyanate.
- the mixture may include an organic solvent.
- the atmosphere temperature is in the range of 80 ° C or more and 400 ° C or less
- the Z or pressure is in the range of 0.001 X 10 5 or more and 9X 10 5 Pa or less, and the pressure is 0.00 LX 10 or less. 5 or 6 X 10 5 P a that could be adjusted to the range.
- the drying step may be a step of heating the polyamic acid under reduced pressure in the absence of an azeotropic solvent and Z or a dehydration condensation reagent to complete the imidization reaction of the polyamic acid.
- the polyimide resin may have a Tg of 350 ° C. or less, and a Z or weight average molecular weight of 5,000 to 1,000,000.
- the molecular weight of the polyimide formed in the drying step is substantially the same as or increased from the theoretical molecular weight of the polyimide calculated from the weight average molecular weight of the polyamic acid before being subjected to the drying step. That you are doing.
- the polyimide resin may be a soluble polyimide soluble in an organic solvent.
- the acid dianhydride may be represented by a chemical formula (1)
- X represents a divalent organic group
- ⁇ and ⁇ represent a single bond or a divalent organic group.
- One or more kinds selected from acid dianhydrides represented by The combination may contain 10 mol% or more.
- X represents _C (CH 3 ) 2 —, -C (CF 3 ) 2 _, -CH 2 C (CH 3 ) 2 CH 2 _, — (CH 2 ) q — ( However, Q is an integer of 1 or more and 10 or less.), And
- T is, C l, F, B r , CH 3 -, either is a CH 3 0_
- T may be a divalent organic group selected from Tona Ru group.
- the diamine may be an aliphatic diamine, and Z or an alicyclic diamine.
- R is independently selected from the group consisting of C 1, F, Br hydroxy, carboxy, C 1-4 alkyl, and C 1-4 alkoxy
- A is independently a single bond, — C (CH 3 ) 2 -,-(CH 2 ) p— (where p is an integer of 1 or more), -C (CF J ? -, OS so.
- C ( ⁇
- R2 is hydrogen, an alkyl group having 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, A is a single bond, — C (CHJ 2 —, — S—, — ⁇ SO-S
- the ester dianhydride may be contained in an amount of 50 mol% or more based on the total amount of the acid dianhydride.
- diisocyanate has the following chemical formula (7)
- ⁇ represents a divalent organic group, and ⁇ is an integer of 1 to 10.
- a divalent organic group selected from the group consisting of —, —C ( 0) O—, and one NHCO— sell.
- the method for producing a polyimide resin of the present invention is a raw material monomer of polyimide, for example, After mixing the acid dianhydride and diamine, or the acid dianhydride and diisocyanate, and heating the mixture under reduced pressure, it is possible to form a desired polyimide without requiring an additional step.
- Basic features After mixing the acid dianhydride and diamine, or the acid dianhydride and diisocyanate, and heating the mixture under reduced pressure, it is possible to form a desired polyimide without requiring an additional step.
- a polyimide resin is formed by a mixing step of mixing these using an acid dianhydride and diamine, and a drying step of heating and drying this mixture under reduced pressure.
- the polyamic acid is formed by reacting the acid dianhydride with diamine. This reaction is typically performed in an organic solvent.
- the acid dianhydride as a raw material monomer used in the present invention is not particularly limited, but may be any one such as aromatic tetracarboxylic dianhydride or aliphatic or alicyclic tetracarboxylic dianhydride.
- An acid dianhydride can be used.
- aromatic tetracarboxylic dianhydride refers to those having at least one aromatic group in the molecule
- aliphatic tetracarboxylic dianhydride refers to Alicyclic and those having no aromatic group
- alicyclic tetracarboxylic dianhydride
- a compound containing at least one alicyclic group in the molecule and having no aromatic group is a compound containing at least one alicyclic group in the molecule and having no aromatic group.
- aromatic tetcarboxylic dianhydride examples include, but are not limited to, pyromellitic dianhydride, 3, 3 ', 4, 4'-benzophenonetetracarboxylic dianhydride, 3, 3', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthylenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-Biphenylethertetracarboxylic dianhydride, 3,3', 4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4 4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-monofurantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy
- R 1 represents a divalent organic group having an aromatic ring
- R 2 and R 3 each represent a hydrogen atom or an alkyl group.
- R 4 represents a divalent organic group having an aromatic ring
- R 5 and R 6 each represent a hydrogen atom or an alkyl group.
- Examples of the aliphatic or alicyclic tetracarboxylic dianhydride include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride,
- tetracarboxylic dianhydrides as described above can be used alone or in combination of two or more.
- the divalent organic group represented by X typically has 1 to 24 carbon atoms, and is an aliphatic group, an alicyclic group, an aromatic group, and an aromatic group.
- Each of the divalent organic groups represented by Z in the chemical formula (1) or Y in the chemical formula (2) is typically an organic group having at least one hetero atom in its main chain. Examples include, but are not limited to, oxygen, zeolite, nitrogen, silicon, phosphorus, and the like.
- X represents one C (CH 3 ) 2 —, — C (CF 3 ) 2 —, — CH 2 C (CH 3 ) 2 CH 2 —, — (CH 2 ) q— (Q is an integer from 1 to 10) and
- T is any one of Cl, F, Br, CH 3 — and CH 3
- T is any one of Cl, F, Br, CH 3 — and CH 3
- X and Z can both be selected from the ranges of the above specific examples.
- thermoplastic polyimide resin having both excellent heat resistance (thermal decomposability) and workability can be formed.
- diamines can be used as the diamine used as a raw material monomer in the method of the present invention.
- any diamine can be used, such as aromatic diamines and aliphatic or cycloaliphatic diamines.
- aromatic diamine examples include, but are not limited to, p-phenylenediamine, m-phenylenediamine, 4,4 ′ diaminodiphenylmethane, 4,4 ′ diaminodiphenylethane, 4,4 'Diaminodiphenyl ether, 4, 4' diaminodiphenyl sulphide, 4, 4'-diaminodiphenyl sulphone, 1,5-diaminonaphthalene, 3, 3'- dimethyl-1,4 '-Diaminobiphenyl, 5-amino-1_ (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'aminophenyl) 1-1,3,3-trimethylindane, 4,4' —Diaminobenzanilide, 3,5—Diamino-3′—Trifluoromethylbenzanilide, 3,5-Diamino-14′1-Trifluorometylbenzanilide, 3,4′—
- aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene, and a hetero atom other than the nitrogen atom of the amino group is also exemplified.
- aliphatic or alicyclic diamine examples include, but are not limited to, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4 , 4-diaminoheptamethylene Diamine, 1,4-diaminocyclohexane, isophoronediamine, tetrahydrocyclocyclopentagenenediamine, hexahydro-1,4,7-methodinoindylenediethylenediamine, tricyclo [6,2,1,0] 2 ⁇ 7 ]-didecylenedimethyldiamine, 4,4 '-diamines such as methylenebis (cyclohexylamine).
- 1,3-propanediamine tetramethylenediamine
- pentamethylenediamine octamethylenediamine
- nonamethylenediamine 4
- 4-diaminoheptamethylene Diamine 1,4-d
- R 9 represents a hydrocarbon group having 1 to 12 carbon atoms, y is independently an integer of 1 to 3, and z is an integer of 1 to 20.
- the above diamine compounds can be used alone or in combination of two or more.
- the preferred diamine used in the method of the present invention is represented by the following formula (4) or (5):
- R is independently C, F, Br, a hydroxy group, a carboxy group, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom.
- the diamine represented by the chemical formula (4) and the chemical formula (5) is
- R 1 is hydrogen, C and F, Br, CH 3 —, or CH 30 —
- R 2 is hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
- A is a alkoxy group
- A is a single bond
- m is 0, 1 or 2
- n is 1, or
- k is an integer of 0 or more, preferably 1 or more and 4 or less.
- thermoplastic polyimide having excellent heat resistance (thermal decomposition resistance) and processability is formed.
- At least one diamine selected from the group consisting of the compounds represented by the chemical formulas (4) and (5) is used in an amount of at least 10 mol%, preferably at least 30 mol%, based on the total amount of diamine used. More preferably, it is desirable to use 50% or more.
- the organic solvent that can be used in the mixing step is typically an organic polar solvent.
- the organic polar solvent that can be used is not particularly limited.
- Examples thereof include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-getylformamide; —Acetamide solvents such as dimethylacetamide and N, N-getylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; phenol, o_cresol, m-cresol, Or phenolic solvents such as p-cresol, xylenol, halogenated phenols and catechol; ethereal solvents such as tetrahydrofuran and dioxane; alcoholic solvents such as methanol, ethanol and butanol; and cellosolve solvents such as butylcellosesolve Or hexame Tylphosphoramide, aptyrolactone and the like. It is desirable to use these solvents alone or as
- the mixture of the acid dianhydride and diamine is then heated under reduced pressure to synthesize polyimide, so that it is advantageous in the process to select an organic solvent having as low a boiling point as possible.
- the polyamic acid is obtained by reacting any of the above diamines with an acid dianhydride in an organic solvent.
- an acid dianhydride is added to the dissolved or dispersed slurry in an organic solvent.
- an acid dianhydride is added to the dissolved or dispersed slurry in an organic solvent.
- the order of addition may be reversed so that the diamine component is added to the acid dianhydride component.
- the molar ratio between the diamine component and the acid dianhydride component can be adjusted to obtain an arbitrary polyamic acid polymer.
- each of the diamine component and the Z or acid dianhydride component may be a single type, or a mixture of two or more types. These Can be added to the organic solvent in any order.
- the first diamine component and the second diamine component may be added to an organic polar solvent first, and then an acid dianhydride component may be added to form a polyamic acid polymer solution.
- the first diamine component may be added first to the organic polar solvent, the acid dianhydride component may be added, and then the second diamine component may be added to form a polyamic acid polymer solution.
- the first diamine component may be added to the organic polar solvent first, then the first acid dianhydride component may be added, and then the second acid dianhydride may be added to form a polyamic acid polymer solution. .
- first diamine component and the second diamine component are first added to the organic polar solvent, the first acid dianhydride component is added, then the second acid dianhydride is added, and the polyamic acid is added. It may be a polymer solution.
- the reaction temperature of the polyamic acid formation reaction in the mixing step of the acid dianhydride and diamine is preferably from ⁇ 20 ° C. to 90 ° C.
- the reaction time is not particularly limited, but is about 30 minutes to 24 hours.
- the average molecular weight (weight average molecular weight) of the polyamic acid to be formed is desirably 5,000 to 1,000,000.
- the average molecular weight is less than 50,000, the molecular weight of the obtained polyimide composition is also low, and the resin becomes brittle even when the polyimide composition is used as it is, which is not preferable.
- Exceeding the viscosity is undesirable because the viscosity of the polyamic acid varnish (that is, the polyamic acid dissolved in the organic solvent used in the reaction) becomes too high and handling becomes difficult.
- the acid dianhydride used as a raw material contains a tetracarboxylic acid that has been opened by hydrolysis or a substance obtained by hydrolyzing one of the acid dianhydrides, the polymerization reaction of polyamic acid will occur.
- these ring-opened anhydride moieties are closed again by overheating under reduced pressure during imidization to give an acid anhydride structure. During this time, it may react with residual amine in the system. Therefore, an improvement in the molecular weight of the obtained polyimide can be expected.
- the polyimide obtained by the method of the present invention is typically substantially the same in the theoretical molecular weight of the polyimide calculated from the weight average molecular weight of the polyamic acid before being subjected to the drying step. Or increasing.
- the molecular weight of the polyimide is typically at least 90% or more, based on the average weight molecular weight of the polyamic acid. Preferably, it means 95% or more, more preferably 97% or more.
- the molecular weight of the polyamic acid can be increased up to about 10 times, up to 20 times, or up to 40 times by selecting the heating conditions under reduced pressure.
- the imidization reaction step is performed in the absence of an azeotropic solvent and Z or a dehydration condensation reagent.
- the imidization step is performed in the presence of a dehydration / condensation reagent for the purpose of chemically removing generated water, the reaction product of the dehydration / condensation reagent and water is present in the system. Since it remains, there is a problem that a step of further removing these is required.
- the imidation reaction step is azeotropic. Since the reaction can be carried out in the absence of a neutral solvent and Z or a dehydration condensation reagent, the above problem can be avoided.
- dehydration-condensation reagent refers to any reagent that can be added to promote the removal of generated water in the dehydration polycondensation in the imidization reaction, and typically can promote the imidization reaction Any catalyst and any compound that itself can chemically react with water are collectively referred to.
- dehydration condensation reagents include basic catalysts such as tertiary amines such as triethylamine, pyridine, picoline (eg, 3-picoline) and isoquinoline, and aliphatic acid anhydrides such as acetic anhydride. Combinations with objects are also examples.
- the imidization reaction step is performed by heating the polyamic acid under reduced pressure until the imidization reaction is completed.
- “Imidation reaction is completed” means that the imidization reaction is performed until the imidization ratio becomes 95% or more, preferably 98% or more, more preferably 99% or more.
- the ratio specified by It is determined by the absorbance ratio of the characteristic absorption of the imide group measured by IR.
- the imidation ratio in this specification refers to any of the following.
- the heating conditions for imidization are preferably 8O: ⁇ 400 ° C.
- the heating temperature is preferably 100 or more, and more preferably 120 ° C or more, in order to efficiently perform imidation and efficiently remove water and remaining organic solvents. It is desirable to set the maximum temperature of the heating below the thermal decomposition temperature of the polyimide to be formed. Usually, the imidization is almost completed at about 200-350 ° C, so the maximum temperature can be about 250-350.
- the temperature may be maintained at a constant value within the above temperature range, or may be gradually increased within the temperature range.
- the pressure reduction condition during the imidization reaction in the drying step is preferably a low pressure, but may be any pressure under which the solvent can be efficiently removed under the above heating conditions.
- the pressure in the imidization reaction is preferably 0. 9X 10 5 ⁇ 0. 0 0 1 X 1 0 5 P a, preferably, 0. 8X 10 5 ⁇ 0. 0 0 1 X 1 0 5 P a, more desirably from 0. 7 X 1 0 5 ⁇ 0. 0 1 X 1 0 5 Pa.
- any apparatus and conditions known to those skilled in the art that can be heated and dried under reduced pressure can be used.
- a vacuum oven can be used as a batch method.
- a batch-type apparatus such as a vacuum oven, a mixture of an acid dianhydride and diamine is usually heated under reduced pressure.
- a twin-screw or triple-screw extruder with a decompression device can be used as a continuous method.
- a twin-screw or three-screw extruder with a decompression device refers to a general melt extruder that performs hot melt extrusion of a thermoplastic resin, and can remove the solvent by reducing the pressure. It is accompanied by a device. The mixture of the acid dianhydride and diamine is heated under reduced pressure while being kneaded by a twin-screw or three-screw extruder to remove a solvent that may be present, thereby obtaining a polyimide resin.
- a solvent having a high boiling point not a solvent having a high solubility and a low boiling point can be used. It is possible to efficiently perform high-temperature treatment while removing it out of the system, and perform imidation through the generation of polyamic acid. The imidization reaction is completed in one step, and no high-molecular weight is required without a purification step. A tough resin can be obtained.
- the mixture of the product and diamine may be performed in an organic solvent or in the absence of an organic solvent (that is, without a solvent).
- the selection of the acid dianhydride and diamine, the mixing ratio, the solvent to be selected, and the step of drying by heating under reduced pressure are basically the same as in the above embodiment.
- both the acid dianhydride and diamine are dissolved in the organic solvent.However, even when one or both compounds are not completely dissolved, the polyimide formation reaction does not proceed. Can proceed. Similarly, when mixing is carried out in the absence of an organic solvent, it is preferred that the acid dianhydride and diamine are compatible with each other, but even if they are completely incompatible, they may be acceptable.
- the diamine and the acid dianhydride may be reacted to form a polyamic acid, or one part or not reacted at all.
- the reaction to the polyamic acid and the imidation reaction from the polyamic acid to the polyimide can also be performed.
- the reaction of diamine and acid dianhydride hardly proceeds in the mixing step, but in the subsequent step of drying by heating under reduced pressure, one or both components are melted.
- the reaction with the polyamic acid and the imidization proceed by also serving as the solvent. Therefore, when a non-solvent is used, the diamine component and / or acid dianhydride component must have a lower melting point than the heating temperature.
- Efficient high-temperature treatment enabled the imidation reaction between the acid dianhydride and diamine through the formation of the polyamic acid, making it possible to produce polyimide.
- the reduced pressure condition, the heating condition, and the apparatus used for the reduced pressure heating are the same as those described above.
- the imidation reaction is completed in one step by heating under reduced pressure, and Polyimide resins can be obtained directly.
- the raw material monomers are an acid dianhydride and a diisocyanate, and a mixing step of mixing them, and a drying step of heating and drying the reaction mixture under reduced pressure. And a method for producing a polyimide resin.
- the mixing of diisocyanate and the acid dianhydride as the raw material monomers is carried out in an organic solvent or in the absence of an organic solvent (that is, without solvent). You may.
- the acid dianhydride and the diisocyanate are both preferably dissolved in the organic solvent, but one or both of the acid dianhydride and the diisocyanate are completely dissolved. Even without dissolution, the polyimide formation reaction can proceed.
- the acid dianhydride and the diisocyanate are preferably compatible with each other, but may not be completely compatible with each other. The formation reaction can proceed.
- the acid dianhydride that can be used as a raw material monomer in the method of the present invention is not particularly limited as long as it is an acid dianhydride, and the above-described aromatic tetracarboxylic dianhydride or aliphatic or alicyclic tetracarboxylic acid Any acid dianhydride such as dianhydride can be used. These acid dianhydrides can be used alone or in combination of two or more. Examples thereof include the acid dianhydride used in the embodiment in which the raw material monomers are a diamine and an acid dianhydride.
- the divalent organic group represented by X typically has 1 to 24 carbon atoms, and is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof. It is an organic group having a dent.
- X is preferably an organic group having an aliphatic group having 1 to 20 carbon atoms, an alicyclic group, an aromatic group, and a combination thereof, and more preferably ,
- polyimide resin By using an acid dianhydride represented by the above formula (6), in addition to excellent solubility in an organic solvent, it has excellent heat resistance (thermal decomposability), low water absorption, and processability.
- Polyimide resin may be formed.
- At least one ester bond-containing acid dianhydride represented by the above formula (6) is used in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, based on the total amount of the acid dianhydrides. It is preferable to use at least mol%. By including such a large amount of ester dianhydride, there is an advantage that a polyimide having particularly low water absorption can be synthesized.
- the diisocyanate that can be used as a raw material monomer in the method of the present invention is not particularly limited.
- Aromatic diisocyanates such as sodium and tetramethylxylene diisocyanate. If necessary, in addition to these aromatic diisocyanates, fats such as hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, etc.
- a group or an alicyclic diisocyanate may be used in combination.
- the definitions of "aromatic”, “aliphatic” and “alicyclic” are the same as in the case of the acid dianhydride. These diisocyanates can be used alone or in combination of two or more.
- Y represents a divalent organic group, and n is an integer of 0 to 10.
- Y is particularly preferably a hydrocarbon group.
- a polyimide resin having excellent heat resistance (thermal decomposition resistance), low water absorption, and processability in addition to solubility in an organic solvent can be formed.
- the amount of at least one diisocyanate represented by the above chemical formula (7) is at least 50 mol%, preferably at least 70 mol%, more preferably at least 90 mol%, based on the total amount of diisocyanate. It is preferable to use the above.
- the ratio of diisocyanate to acid dianhydride is substantially equimolar.
- the diisocyanate and the acid dianhydride may be mixed while being dissolved using an organic solvent.On the other hand, the mixing is performed in the absence of a solvent such as an organic solvent. You may. When mixing is performed in an organic solvent, it is preferable that both the acid dianhydride and the diisocyanate are dissolved in the organic solvent, but one or both of the acid dianhydride and the diisocyanate are completely dissolved.
- the polyimide may not be dissolved in an organic solvent, and the polyimide formation reaction can proceed.
- the acid dianhydride and the diisocyanate are preferably compatible with each other, but may not be completely compatible with each other, and the polyimide forming reaction may be performed. Can progress.
- the acid dianhydride and the diisocyanate may be solid or liquid, and if solid, may be melted by heating.
- the organic solvent that can be used is typically an organic polar solvent.
- the organic polar solvent that can be used is not particularly limited, and examples thereof include the same organic solvents as those described above.
- the solvent is not particularly limited, but it is advantageous in the process to select a solvent having as low a boiling point as possible.
- a drying step in which a reaction mixture obtained by mixing an acid dianhydride and a diisocyanate is heated under reduced pressure, in a drying step, when the imidation is mixed in a solvent, the solvent is removed and the imidization is performed. At the same time.
- the mixture of the acid dianhydride and the diisocyanate is dried by heating under reduced pressure.
- the procedure is the same as that exemplified in the above-mentioned method for obtaining a polyimide resin from an acid dianhydride and diamine, using any apparatus and conditions known to those skilled in the art that can be dried by heating under reduced pressure.
- the heating conditions and the reduced pressure conditions in the drying step are the same as those described in the method for obtaining a polyimide resin from acid dianhydride and diamine.
- the imidization reaction does not proceed sufficiently.
- the desired polyimide resin was obtained for the first time through a step of precipitating and refining the same in a poor solvent such as methanol. In the present invention, such a purification step is not required.
- the solvent can be removed from the system positively, and the high-temperature treatment can be carried out efficiently to perform imidization.
- the imidation reaction between the acid dianhydride and the diisocyanate is heated under reduced pressure, whereby the imidization is completed in one step, and the desired polyimide resin undergoes a purification step.
- imidization proceeds to a high degree and a completed polyimide resin can be obtained in good yield. As a result, a tough resin having a high molecular weight can be obtained.
- a high molecular weight polyimide resin can be produced in high yield.
- resin means a polymer substance having sufficient strength and processability as a molding material.
- the polyimide resin formed by the method of the present invention preferably has an average molecular weight (weight-average molecular weight) of 5,000 to 1,000, 0000, as a resin from the above viewpoint. And more preferably 5,000 to 200,000. If the average molecular weight is less than 50,000, the polyimide resin tends to be brittle, which is not preferable. On the other hand, if the average molecular weight exceeds 1, 000, 0000, the workability of the resin becomes poor, and there is an unfavorable tendency.
- the polyimide resin formed by the method of the present invention is preferably soluble in an organic solvent.
- “soluble in an organic solvent” means that It means that the solvent has a solubility of at least 5% by weight, preferably 10% by weight or more in N, N-dimethylformamide.
- Polyimides soluble in such organic solvents can be used in an imidization reaction in which heating is performed under reduced pressure in the presence of an organic solvent, without the risk of phase separation of components during the reaction, and the imidization proceeds smoothly until the reaction is completed. This is preferable in that it can proceed.
- the mixing ratio of diamine and the acid dianhydride which are the raw material monomers of the polyimide resin of the present invention, is basically preferably substantially equimolar, but in another embodiment, in order to control the terminal,
- the diamine may be added in more than the acid dianhydride. If diamine is frequently used, the final product, polyimide resin, can have amino groups, rather than carboxyl groups, at most of the ends of the molecule. In this way, by controlling the end of the polyimide resin by the amount of diamine, the terminal amino-type polyimide molecule can be used in combination with, for example, an epoxy resin which is a resin having a reactivity with an amino group.
- the molar ratio of the diamine (or amine) component to the acid dianhydride component is preferably 100: 100 to 100: 50, more preferably 100: 100 to: 100: 70, and more preferably 100: 100. It can range from ⁇ 100: 90.
- the mixing ratio may be the same as that of diisocyanate in a larger amount than acid dianhydride.
- the polyimide resin as a final product can have an isocyanate group instead of a carboxy group at most of the terminal of the molecule.
- the terminal isocyanate type polyimide molecule can be used in combination with, for example, an epoxy resin which is a resin having reactivity with an isocyanate group.
- the molar ratio of the diisocyanate component to the acid dianhydride component is preferably 100: 100 to 100: 50, and more preferably.
- ESDA 2,2-bis (4-hydroxyphenyl) propanedibenzoate 3,3 ', 4,4'-tetracarboxylic dianhydride
- 6 FDA 2,2'-hexaflu Oropropylidene difluoric dianhydride
- BAPS—M bis [4- (3-aminophenoxy) phenyl] sulfone
- DMAc is N, N-dimethylacetamide
- DMF is N, N— Represents dimethylformamide.
- T g was measured by a Shimadzu DSC CELL SCC-41 (differential scanning calorimeter) under a nitrogen stream at a heating rate of 1 O: min., Over a temperature range from room temperature to 400 ° C.
- the weight average molecular weight (Mw) was measured using a Waters GPC under the following conditions: (Column: two KD-806M products from Shode X, at a temperature of 60, detector: RI, flow rate: lmlZ min, Developing solution: DMF (lithium bromide 0.03M, phosphoric acid 03M), sample concentration: 0.2 wt%, injection volume: 201, reference substance: polyethylene oxide).
- the imidation ratio of the obtained resin was determined by preparing a standard sample in the following manner and comparing it.
- DMF solution is cast on a PET film, dried by heating at 100 ° C for 10 minutes and 130 ° C for 10 minutes under atmospheric pressure, peeled off from the PET film, fixed on a pin frame, and furthermore, under atmospheric pressure, 150 ⁇ X 60 minutes, 200 ⁇ 60 minutes, 250 ° C. for 60 minutes, sequentially heating to complete the imidization, obtaining a 5 im thick polyimide film.
- This is referred to as a standard polyimide.
- the IR of each film was measured to determine the ratio of the absorption (1780 cm one 1 near) the absorption of the Z benzene ring (near 1500 cm one 1) imide.
- the ratio of the absorption Z of the imide obtained in 1 and the ratio of the benzene ring are 100%
- the ratio of the absorption of the imide Z and the ratio of the benzene ring in 2 is calculated as the imidation ratio.
- FT-IRS YSTEM2000 manufactured by PerkinElmer
- N, N-dimethylformamide as an organic solvent, add 5 g of polyimide to 95 g of the solvent, stir well at 20 ° C, and visually check whether the polyimide is completely dissolved. I checked in.
- thermoplastic polyimide It was taken out of the vacuum oven to obtain 85.4 g of thermoplastic polyimide.
- the Mw of this polyimide was 100,000, that of Mori 8 was 190, and the imidation ratio was 100%.
- the reaction mixture was poured into methanol for purification, separated by filtration, and the obtained solid was purified by a Soxhlet extractor (methanol solvent) for 6 hours and dried to obtain 70 g of a white polyimide powder. .
- the Mw of this polyimide was 70,000, Tgl 90, and the imidization ratio was 98%.
- the polyamic acid was directly imidized by heating and decompression by the following evaporative separation apparatus. 42 kg of imide composition recovered for 150 kg of amic acid solution used
- Evaporation separator twin screw extruder with the same diameter of 40 mm (BT-40—S2—48
- Heating temperature can be set individually.
- Decompression part Four holes are provided in the heating part.
- the pressure can be reduced while kneading.
- Heating temperature 4 blocks, set to 180 :, 230 ° C, 280, 28 Ot :, respectively.
- Rotary speed of twin screw extruder 100 rpm
- Polyamide acid is directly imidized by heating and decompression by the following evaporative separation device
- Evaporation separation unit SC processor manufactured by Kurimoto Tetsusho (paddle with two axes rotating in different directions)
- An evaporation chamber is provided in the section to have a large evaporation ability.
- This device is cylindrical and one of the tubes
- Heating temperature 280
- Example 4 500 g of the polyamic acid solution used in Example 2 was placed in a reaction vessel equipped with a stirrer, water lg was added, and the mixture was stirred at 40 ° C. for 2 hours. After the completion of the stirring, the Mw of the polyamic acid was 4,500.
- thermoplastic polyimide 400 g was placed in a Teflon-coated vat and imidized in a vacuum oven under the same conditions as in Example 1. It was taken out from the vacuum oven to obtain 112 g of a thermoplastic polyimide.
- the Mw of this polyimide was 1490,000, the Tg was 145, and the imidation ratio was 100%.
- the Mw of the polyimide was 33,000, and that of M8 was 135, and the imidation ratio was 95%.
- imidization does not normally proceed because acetic anhydride reacts with the hydroxyl group and carboxy group in the side chain. Therefore, chemical imidization using acetic anhydride as a dehydrating agent cannot be performed. (Example 6)
- the Mw of this polyimide was 28,000, and that of the polyimide was 155, and the imidation ratio was 94%.
- chemical imidization cannot be performed because acetic anhydride reacts with the carboxylic acid.
- thermoplastic polyimide It was taken out of the vacuum oven to obtain 85.4 g of thermoplastic polyimide.
- This polyimide had an Mw of 47,000, a cinch of 190, and an imidation ratio of 100%, and showed solubility in DMF.
- heating was performed under reduced pressure in the summer without waiting for the generation of polyamic acid, and polymerization and imidization proceeded simultaneously in the drying step.
- the mixed solution obtained in the same manner as in Example 7 was continuously stirred for 30 minutes to obtain a polyamic acid solution.
- a polyamic acid solution To 250 g of this polyamic acid solution, 9.3 g (0.2 mol) of / 3 picoline, 50 g (0.49 mol) of acetic anhydride, and 100 g of DMF were added to the above reaction solution, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the mixture was heated to about 100 ° C., and further stirred for 1 hour to imidize. These reactions were performed under a nitrogen stream.
- this solution was dripped little by little into methanol stirred at high speed for purification.
- the filamentous polyimide precipitated in methanol was pulverized with a mixer, subjected to Soxhlet washing with methanol, and dried at 110 ° C. for 2 hours to obtain 70 g of a polyimide powder.
- the Mw of this polyimide was 40,000, Tgl 90, and the imidation ratio was 98%.
- the mixed solution obtained in the same manner as in Example 7 was continuously stirred for 30 minutes to obtain a polyamic acid solution.
- 250 g of this polyamic acid solution, 50 g of toluene and 9.3 g of 3-picoline were put into a 2000 ml separable flask equipped with a stirrer and a Dean-Stark reflux condenser, and heated and stirred at 170 ° C. Heating and stirring were performed until water generation ceased (about 4 hours). These reactions were performed under a nitrogen stream.
- the imide had a Mw of 50,000, a chow of 160, and an imidation ratio of 100%, indicating solubility in DMF.
- thermoplastic polyimide 300 g was placed in a Teflon-coated vat and heated in a vacuum oven at 210 mm for 30 minutes at a pressure of 5 mmHg (approximately 0.007 atm). It was taken out from the vacuum oven to obtain 91.0 g of a thermoplastic polyimide.
- the polyimide had an Mw of 90,000, a chode of 180, and an imidation ratio of 100%, and showed solubility in DMF.
- Heating was performed under reduced pressure of 5 mmHg (about 0.007 atm) for 30 minutes at 210 ⁇ X.
- thermoplastic polyimide It was taken out from the vacuum oven to obtain 91.0 g of thermoplastic polyimide. This port
- Mw of Liimide is 50,000, Tgl 65t :, imidation rate is 100%, DMF
- Example 11 250 g of the mixed solution obtained in 1 was imidized by stirring at 130 for 3 hours.
- the solvent was purified for 6 hours, and dried to obtain 70 g of a white polyimide powder.
- the Mw of this polyimide was 4000 and the Tg was 170.
- Example 11 The mixed solution obtained in Example 11 was subjected to the following operation by the evaporative separation device used in Example 2.
- the compound had a Mw of 60,000 and a Tg of 200, and was soluble in DMF.
- Heating temperature 28 0 (each block)
- Example 11 An experiment was performed using the mixed solution of diisocyanate and acid dianhydride used in Example 1.
- Example 13 The same evaporator and separator as in Example 13 were used, and the heating was reduced under the same operating conditions.
- BTDA Tetracarboxylic dianhydride
- a method for easily producing a high molecular weight polyimide resin in a high yield is provided by heating and drying a mixture obtained by mixing the raw material monomers of polyimide under reduced pressure.
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- Chemical Kinetics & Catalysis (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00964744A EP1260538B1 (en) | 1999-10-06 | 2000-10-06 | Process for producing polyimide resin |
US10/110,122 US6790930B1 (en) | 1999-10-06 | 2000-10-06 | Process for producing polyimide resin |
DE60045314T DE60045314D1 (de) | 1999-10-06 | 2000-10-06 | Verfahren zur herstellung eines polyimidharzes |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28613199 | 1999-10-06 | ||
JP11/286131 | 1999-10-06 | ||
JP11/323326 | 1999-11-12 | ||
JP32332699 | 1999-11-12 | ||
JP2000/222815 | 2000-07-24 | ||
JP2000222815 | 2000-07-24 |
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WO2001025313A1 true WO2001025313A1 (fr) | 2001-04-12 |
Family
ID=27337230
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/007013 WO2001025313A1 (fr) | 1999-10-06 | 2000-10-06 | Fabrication de resine polyimide |
Country Status (4)
Country | Link |
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US (1) | US6790930B1 (ja) |
EP (1) | EP1260538B1 (ja) |
DE (1) | DE60045314D1 (ja) |
WO (1) | WO2001025313A1 (ja) |
Cited By (9)
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JP2003011308A (ja) * | 2001-07-03 | 2003-01-15 | Kanegafuchi Chem Ind Co Ltd | フィルム状積層部材 |
JP2004027137A (ja) * | 2002-06-28 | 2004-01-29 | Mitsui Chemicals Inc | 熱可塑性ポリイミドの製造方法 |
KR100683086B1 (ko) * | 2001-07-09 | 2007-02-16 | 가부시키가이샤 가네카 | 수지 조성물 |
KR101548877B1 (ko) * | 2014-08-29 | 2015-09-01 | 연세대학교 원주산학협력단 | 단량체의 염을 거쳐 제조되는 폴리이미드 및 그 제조방법 |
JPWO2015020019A1 (ja) * | 2013-08-06 | 2017-03-02 | 三菱瓦斯化学株式会社 | ポリイミド樹脂粉末の製造方法及び熱可塑性ポリイミド樹脂粉末 |
KR101728833B1 (ko) | 2015-09-02 | 2017-04-20 | 연세대학교 원주산학협력단 | 단량체 염을 이용한 폴리이미드 공중합체 제조방법 |
JP2021024893A (ja) * | 2019-07-31 | 2021-02-22 | 株式会社カネカ | 重合体製造システム及び製造方法 |
WO2022244576A1 (ja) * | 2021-05-21 | 2022-11-24 | 本州化学工業株式会社 | 溶融加工用材料及び溶融加工品 |
WO2022244581A1 (ja) * | 2021-05-21 | 2022-11-24 | 本州化学工業株式会社 | 無色透明加工品用ポリイミド樹脂材料、新規なポリイミド |
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US7019104B1 (en) * | 1999-11-01 | 2006-03-28 | Kaneka Corporation | Diamine novel acid dianhydride and novel polyimide composition formed therefrom |
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WO2016032299A1 (ko) * | 2014-08-29 | 2016-03-03 | 연세대학교 원주산학협력단 | 단량체 염을 이용한 폴리이미드 제조방법 |
CN115536816B (zh) * | 2022-10-28 | 2024-02-20 | 中国科学院兰州化学物理研究所 | 一种热固性环氧树脂形状记忆聚合物及其制备方法 |
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JP2003011308A (ja) * | 2001-07-03 | 2003-01-15 | Kanegafuchi Chem Ind Co Ltd | フィルム状積層部材 |
KR100683086B1 (ko) * | 2001-07-09 | 2007-02-16 | 가부시키가이샤 가네카 | 수지 조성물 |
JP2004027137A (ja) * | 2002-06-28 | 2004-01-29 | Mitsui Chemicals Inc | 熱可塑性ポリイミドの製造方法 |
JPWO2015020019A1 (ja) * | 2013-08-06 | 2017-03-02 | 三菱瓦斯化学株式会社 | ポリイミド樹脂粉末の製造方法及び熱可塑性ポリイミド樹脂粉末 |
KR101548877B1 (ko) * | 2014-08-29 | 2015-09-01 | 연세대학교 원주산학협력단 | 단량체의 염을 거쳐 제조되는 폴리이미드 및 그 제조방법 |
KR101728833B1 (ko) | 2015-09-02 | 2017-04-20 | 연세대학교 원주산학협력단 | 단량체 염을 이용한 폴리이미드 공중합체 제조방법 |
JP2021024893A (ja) * | 2019-07-31 | 2021-02-22 | 株式会社カネカ | 重合体製造システム及び製造方法 |
JP7336302B2 (ja) | 2019-07-31 | 2023-08-31 | 株式会社カネカ | 重合体製造システム及び製造方法 |
WO2022244576A1 (ja) * | 2021-05-21 | 2022-11-24 | 本州化学工業株式会社 | 溶融加工用材料及び溶融加工品 |
WO2022244581A1 (ja) * | 2021-05-21 | 2022-11-24 | 本州化学工業株式会社 | 無色透明加工品用ポリイミド樹脂材料、新規なポリイミド |
Also Published As
Publication number | Publication date |
---|---|
EP1260538A4 (en) | 2003-01-02 |
US6790930B1 (en) | 2004-09-14 |
EP1260538A1 (en) | 2002-11-27 |
DE60045314D1 (de) | 2011-01-13 |
EP1260538B1 (en) | 2010-12-01 |
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