WO2009098791A1 - イミドオリゴマー及びこれを加熱硬化させてなるポリイミド樹脂 - Google Patents
イミドオリゴマー及びこれを加熱硬化させてなるポリイミド樹脂 Download PDFInfo
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- WO2009098791A1 WO2009098791A1 PCT/JP2008/063512 JP2008063512W WO2009098791A1 WO 2009098791 A1 WO2009098791 A1 WO 2009098791A1 JP 2008063512 W JP2008063512 W JP 2008063512W WO 2009098791 A1 WO2009098791 A1 WO 2009098791A1
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- oligomer
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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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
- C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
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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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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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
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
Definitions
- the present invention relates to a thermosetting imide oligomer, particularly to an imide oligomer which is excellent in moldability and can be obtained by heat curing to obtain a polyimide resin excellent in heat resistance.
- Polyimide resins are excellent in heat resistance and exhibit very high thermal decomposition temperatures, and thus are used as a carbon fiber reinforced structural material matrix in the field of rockets and satellites (see, for example, Non-Patent Document 1).
- Non-Patent Document 1 In recent years, in the field of LSI using Si wafers, electronic components using Si-C have been actively studied along with the increase in information density and speed, and in LSIs using Si-C, etc., 400 ° C. Although operation at a temperature above is assumed, the conventional polyimide resin which is said to be excellent in heat resistance can not be used. Then, use of various heat resistant polymer films is also examined not only in polyimide resin (for example, refer to nonpatent literature 2).
- thermosetting imide oligomers have been advanced in recent years. That is, after forming an imide oligomer by adding a crosslinking reactive functional group such as 4-phenylethynyl phthalic acid anhydride to the end of the imide oligomer, the crosslinking reaction between the oligomer chains proceeds by heating to cure the resin It is intended to obtain a polyimide resin molded product having high heat resistance.
- a crosslinking reactive functional group such as 4-phenylethynyl phthalic acid anhydride
- non-axial such as 2,3,3 ′, 4′-biphenyltetracarboxylic acid dianhydride
- transduced symmetrical biphenyl acid dianhydride is proposed (for example, refer patent document 1). It should be noted that while the usual polyimide structure is highly linear and the intermolecular interaction is very large, the introduction of such non-axisymmetric molecules causes the polyimide chain to exhibit helicity, thus the intermolecular interaction It becomes clear that the heat melting property and the coloring property are improved (see, for example, Non-Patent Document 3).
- oligomers are suitable for molding polyimide resins by resin transfer molding (RTM) and resin injection (RI) techniques (see, for example, Patent Document 2).
- the object of the present invention is to provide an imide oligomer which has excellent thermoforming property and heat resistance which is excellent as a polyimide resin after heat curing, and which can be easily and inexpensively obtained.
- non-axisymmetric aromatic diamines in which two amino groups are not introduced on the same axis for example, 3,4'-diamino
- 3,4'-diamino 3,4'-diamino
- the obtained imide oligomer has a helical property, so that the thermoforming property is excellent.
- the inventors have found that the polyimide resin obtained by heat curing the imide oligomer exhibits excellent heat resistance, and completes the present invention.
- the imide oligomer according to the present invention is characterized by having a non-axisymmetric site derived from one non-axisymmetric aromatic diamine molecule represented by the following general formula (1) only in the central part of the oligomer chain. It is a thing.
- the said imide oligomer is represented by following General formula (2).
- X is an acid dianhydride residue, Y is a diamine residue, Z is a crosslinkable reactive group, n is (X-Y) Average degree of polymerization of polyimide moiety is 1 to 10)
- W in the general formula (1) or (2) is —O— or —CH 2 —.
- the average degree of polymerization n of each polyimide portion is 1 to 6, and the average molecular weight of the entire imide oligomer is 8,000 or less.
- acid dianhydride residue X is pyromellitic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 4,4'-biphthalic acid dianhydride , 3,3 ', 4,4'-diphenylsulfonic acid, 4,4'-oxydiphthalic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, naphthalene-1,4,5 , 8-Tetracarboxylic acid dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic acid dianhydride, at least one selected from 2,2-bis (4-carboxylic acid phenyl) propanoic acid dianhydride It is preferable that it originates in the above acid dianhydride.
- the diamine residue Y is 4,4′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4 -Bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] Derived from at least one or more diamines selected from hexafluoropropane, ⁇ , ⁇ '-bis (4-aminophenyl) -1,4-diisopropylbenzene, 3,3'-bis (4-aminophenyl) fluorene Is preferred.
- the terminal crosslinkable reactive group Z is 4-phenylethynylphthalic anhydride, phthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 2,5-norbornadiene-2, It is preferable to derive from at least one or more compounds selected from 3-dicarboxylic acid anhydride, maleic acid anhydride, propargylamine, phenylethynylaniline, ethynylaniline, aminostyrene and vinylaniline.
- amic acid oligomer according to the present invention is characterized by having a non-axisymmetric site derived from one non-axisymmetric aromatic diamine molecule represented by the above general formula (1) only in the central part of the oligomer chain. It is
- the polyimide resin according to the present invention is characterized in that the imide oligomer is cured by heating.
- the method for producing an imide oligomer according to the present invention is an imide oligomer having a non-axisymmetric site derived from one non-axisymmetric aromatic diamine molecule represented by the general formula (1) only in the central part of the oligomer chain.
- a non-axisymmetric aromatic diamine represented by the above general formula (1) is reacted with a large excess of acid dianhydride, thereby producing an oligomer precursor
- the method for producing an imide oligomer it is preferable to further include a step of adding a compound having a crosslinkable reactive group to the end of the imide oligomer or amic acid oligomer obtained in the step (C).
- one molecule of non-axisymmetric aromatic diamine for example, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane
- non-axisymmetric aromatic diamine for example, 3,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane
- the obtained imide oligomer has a helical property, and as a result, an imide oligomer having excellent thermoforming properties and excellent heat resistance as a polyimide resin after heat curing. Can be obtained easily and inexpensively.
- stereochemistry (A) of imide oligomer 1A It is a stereochemistry (A) of imide oligomer 1A, and a stereochemistry (B) of an imide oligomer which does not contain a non-axial symmetry site.
- the steric structure (A) of imide oligomer 1A having a non-axisymmetric site only at the center of the oligomer chain and the degree of polymerization of the polyimide portion is 2 (A), and the structure of the imide oligomer having a degree of polymerization of 6 (B).
- the imide oligomer according to the present invention is characterized by having a non-axisymmetric site derived from one non-axisymmetric aromatic diamine molecule represented by the following general formula (1) only in the central part of the oligomer chain is there.
- the compound represented by the above general formula (1) is one in which an amino group is bonded to the 3-position and 4-position respectively on two benzene rings bonded directly or via a specific functional group, It is an aromatic diamine in which the bonding position of the amino group does not have an axially symmetrical position about W, that is, non-axisymmetric.
- non-axisymmetric aromatic diamines represented by the above general formula (1) are 3,4′-benzidine (W is directly bonded), 3,4′-diaminodiphenyl ether (W is —O -), 3,4'-diaminodiphenylmethane (W is -CH 2 -), 3,4'-diaminodiphenyl ethane (W is -C 2 H 4 -), 3,4'-diaminodiphenyl isopropane (W is -C (CH 3) 2 -) , 3,4'- diaminodiphenyl difluoromethane (W is -CF 2 -), 3,4'- diaminodiphenyl tetrafluoroethane (W is -C 2 F 4 -), 3 , 4'-diaminodiphenyl hexafluoroisopropane (W is -C (CF 3) 2 -) , 3,4'- diamino
- 3,4'-diaminodiphenyl ether or 3,4'-diaminodiphenylmethane can be particularly preferably used.
- the imide oligomer according to the present invention can be obtained by polycondensation of any acid dianhydride and diamine at each terminal amino group of one non-axisymmetric aromatic diamine molecule represented by the above general formula (1) It is a compound to which each of the formed imide oligomer chains is added in an equal amount (equimolar), thereby having a non-axisymmetric site derived from one non-axisymmetric aromatic diamine molecule only in the central part of the oligomer chain. Become.
- the imide oligomer according to the present invention is represented, for example, by the following general formula (2).
- X is an acid dianhydride residue.
- the acid dianhydride used in the imide oligomer of the present invention is not particularly limited as long as it is axially symmetric and can form a polyimide structure by condensation reaction with a diamine.
- Examples of the acid dianhydride used in the present invention include pyromellitic acid dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid dianhydride, 4,4′-biphthalic acid dianhydride, 3 , 3 ', 4,4'-diphenylsulfonic acid, 4,4'-oxydiphthalic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, naphthalene-1,4,5,8- Examples thereof include tetracarboxylic acid dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic acid dianhydride, 2,2-bis (4-carboxylic acid phenyl) propanoic acid dianhydride and the like.
- 4,4′-oxydiphthalic acid dianhydride 4,4′-biphthalic acid dianhydride, 3,3 ′, 4,4′-diphenylsulfonic acid, 4,4 ′-(hexafluoroisopropyl) Phenyl) diphthalic acid dianhydride can be preferably used.
- Y is a diamine residue.
- the diamine used for the imide oligomer of the present invention is not particularly limited as long as it is axially symmetric and can form a polyimide structure by condensation reaction with an acid dianhydride.
- Examples of the diamine used in the present invention include 4,4′-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, and 1,4-bis ( 4-Aminophenoxy) benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane , ⁇ , ⁇ '-bis (4-aminophenyl) -1,4-diisopropylbenzene, 3,3'-bis (4-aminophenyl) fluorene and the like.
- Z is a crosslinkable reactive group.
- thermosetting is imparted by modifying the terminal with a compound having a crosslinkable reactive group.
- the compound having a crosslinkable reactive group used in the present invention include 4-phenylethynylphthalic anhydride, phthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 2,5-norbornadiene-2, Examples thereof include 3-dicarboxylic acid anhydride, maleic acid anhydride, propargylamine, phenylethynylaniline, ethynylaniline, aminostyrene, vinylaniline and the like.
- 4-phenylethynylphthalic acid anhydride and 5-norbornene-2,3-dicarboxylic acid anhydride can be particularly preferably used.
- n is 1 to 10 as the average degree of polymerization of the polyimide moiety represented by (X-Y).
- the average degree of polymerization can be appropriately adjusted by changing the ratio of non-axisymmetric aromatic diamine, acid dianhydride and diamine used for the production of imide oligomer.
- the average degree of polymerization of each polyimide portion exceeds 10, the heat melting property may be poor and the molding may be difficult.
- the average degree of polymerization of each polyimide portion is preferably 1 to 6, and more preferably 2 to 5.
- part is in the said range is obtained.
- the non-axisymmetric site derived from one non-axisymmetric aromatic diamine molecule is present only in the central part of the oligomer chain. Nevertheless, for example, as shown in FIG. 1, the oligomer chain as a whole exhibits a helical structure. And, as a result, the imide oligomer according to the present invention is thermally melted at a relatively low temperature, so thermoforming is easy, and the thermal decomposition temperature of the polyimide resin after heat curing reaches 500 ° C. or higher, and heat resistance Also very good.
- the conventional helical imide oligomer as described in Patent Document 1 is excellent in thermoformability and heat resistance of a polyimide resin after heat curing, it is relatively expensive non-axially symmetric. Since the compound is contained throughout the entire oligomer chain, there is a problem that the production cost is high.
- the helical imide oligomer according to the present invention only needs to have one non-axisymmetric compound in the oligomer chain, and the use of expensive non-axisymmetric compounds can be greatly reduced, so that excellent thermoforming can be achieved.
- the imide oligomer having heat resistance and heat resistance of the polyimide resin after heat curing can be easily and inexpensively obtained.
- the imide oligomer according to the present invention can be prepared, for example, by the following steps (A) to (C).
- acid dianhydride may be a large excess with respect to 1 mol of the non-axisymmetric aromatic diamine, but more specifically, for example, with respect to the non-axisymmetric aromatic diamine It may be about 2 to 20 times mole.
- the residue of the acid dianhydride used here corresponds to X in the general formula (2).
- aprotic solvents such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, NN-dimethylacetamide (DMAc), ⁇ -butyrolactam and the like can be mentioned.
- the reaction of the step (B) can be carried out continuously with the step (A), but when the polymerization reaction is carried out in an aprotic solvent as exemplified above, an amide moiety is usually formed in the molecule It is obtained as an amic acid oligomer having a and a carboxylic acid moiety.
- the amic acid oligomer dehydrates / cyclizes (imidizes) the amide moiety and the carboxylic acid moiety, for example, by adding an imidizing agent at a low temperature, or heating under reflux at a high temperature to form an imide oligomer. be able to.
- a compound having a crosslinkable reactive group is added to the end of the imide oligomer or amic acid oligomer obtained above.
- the reactive groups form a crosslinked structure upon heating, whereby the imide oligomer can be provided with a thermosetting property.
- the residue of the crosslinkable reactive group-containing compound used here corresponds to Z in the above general formula (2).
- the crosslinkable reactive group-containing compound may be any compound that can react with either the unreacted carboxylic acid group in the acid dianhydride or the unreacted amino group in the diamine.
- the addition amount of the crosslinkable reactive group-containing compound may be appropriately adjusted according to the equivalent of the reactive carboxylic acid group or amino acid group, but in the normal case, it is about 2 per 1 mol of non-axially symmetric aromatic diamine. It may be about molar.
- step (C) can be carried out continuously with the steps (A) to (B), and generally, all the steps (A) to (C) are carried out in the form of an amic acid oligomer, and finally an imide oligomer Convert to That is, addition of the crosslinkable reactive group-containing compound in step (C) is carried out in the state of the amic acid oligomer obtained in step (B), followed by, for example, addition of an imidation agent at low temperature or By heating and refluxing, the amide moiety and the carboxylic acid moiety are dehydrated / cyclized (imidized) to obtain an imide oligomer having a crosslinkable reactive group at the molecular terminal.
- amic acid oligomers not subjected to imidization in the above steps (A) to (C) are also within the scope of the present invention.
- Such amic acid oligomers can be easily converted to imide oligomers by dehydration / cyclization reaction by heating.
- the imide oligomer of the present invention can be obtained by heating and refluxing the amic acid oligomer solution of the present invention at a high temperature of about 150 to 245 ° C.
- the amic acid oligomer solution can be coated on a support having good removability such as a glass plate and heated to about 250 to 350 ° C. to be imidized to obtain the imide oligomer of the present invention. .
- reaction steps (A) to (C) it is preferable to carry out in the presence of an inert gas such as argon or nitrogen or in vacuum.
- an inert gas such as argon or nitrogen or in vacuum.
- the imide oligomer obtained as described above may, for example, be added while stirring the solution after completion of the reaction into a large amount of water and isolated by filtration. By drying at about 100 ° C., it can be used as a powdery imide oligomer. Also.
- the imide oligomer powder thus obtained can also be used as a solution dissolved in a suitable solvent, if necessary.
- the imide oligomer obtained as described above may be made into a polyimide resin having excellent heat resistance by heat curing with the oligomer alone or in the state of being impregnated with a fibrous reinforcing material such as carbon fiber. it can.
- the imide oligomer according to the present invention exhibits a helical structure and is excellent in moldability, it can be easily molded, for example, by a mold or the like, or to a fibrous reinforcing material or the like. Impregnation can also be carried out relatively easily.
- the heating temperature and the heating time can be appropriately adjusted according to the physical properties of the desired polyimide resin.
- the imide oligomer according to the present invention varies depending on the kind of the crosslinkable reactive group-containing compound, the thermosetting usually occurs at about 300 to 370 ° C. More specifically, for example, the imide oligomer is thermally melted by preliminarily heating at a temperature of about 210 to 320 ° C. for a predetermined time, and then the crosslinking reaction is performed by heating for a predetermined time at a temperature of 350 to 400 ° C. , To obtain a cured polyimide resin. By raising the heating temperature in each heating step or prolonging the heating time, the heat resistance of the cured polyimide resin is usually improved.
- the powder of the imide oligomer of the present invention can be filled in a mold and heat compression molded at 250 to 370 ° C. and about 0.5 to 5 MPa for about 1 to 5 hours to obtain a polyimide resin molded body .
- a fibrous reinforcing material such as carbon fiber
- pressure is further applied to 1 to 5 at 250 to 370 ° C.
- a fiber-containing composite of polyimide resin By heating for about time, a fiber-containing composite of polyimide resin can be obtained.
- the imide oligomer solution of the present invention is coated on a support having good removability such as a glass plate and heated at 250 to 350 ° C. for about 1 to 5 hours to obtain a polyimide resin film. it can.
- Imide oligomer 1A Under argon flow, 3.08 g of 3,4'-diaminodiphenyl ether and 19.08 g of 4,4'-oxydiphthalic acid anhydride were dissolved in 200 ml of dry N, N-dimethylacetamide and stirred at room temperature for about 30 minutes. . Thereafter, 17.98 g of 1,3-bis (3-aminophenoxy) benzene was added and stirred for about 1 hour. Finally, 7.68 g of 4-phenylethynylphthalic anhydride was added, and after stirring for about 1 hour at room temperature, the solvent was refluxed for about 12 hours to obtain an off-white suspension.
- the suspension was charged into 800 ml of ion-exchanged water, filtered, repeatedly washed with water several times, washed with methanol and filtered, and dried overnight at 120 ° C. to obtain a pale yellow powdery imide oligomer (imide oligomer 1A) .
- the obtained imide oligomer was measured by GPC (Aliance 2695: manufactured by Waters), and as a result, the number average molecular weight (Mn) was 5.2 ⁇ 10 3 g / mol (NMP solvent).
- the cured polyimide resin product obtained above was analyzed by TG-DTA (EASTAR 6000: manufactured by SII) under a nitrogen stream, and as a result, the 5% thermal decomposition temperature ( ⁇ 5 ) was 537.0 ° C. (a rise under a nitrogen stream) The temperature was 10 degrees / minute). Further, DSC: In the measurement by (Q200 TA Co.), the glass transition temperature of the cured polyimide resin (T g) is 185.2 ° C. (under nitrogen stream, heating rate: 10 ° C. / min) was. Moreover, the thermal expansion coefficient (CTE) of the polyimide resin hardened
- EZGraph made by shimad
- FIG. 1 (A) The steric structure of the imide oligomer 1A based on molecular orbital calculation is shown in FIG. 1 (A), and the steric structure of the imide oligomer containing no non-axisymmetric site is shown in FIG. 1 (B).
- the oligomer chain as a whole is helical by having only one molecule of 3,4'-diaminodiphenyl ether as a non-axisymmetric site at the center of the oligomer chain. It can be seen that Further, FIG.
- FIG. 2 (A) shows a steric structure of the imide oligomer 1A having a non-axisymmetric site only at the central portion of the oligomer chain and the degree of polymerization of the polyimide portion is 2, an imide having a degree of polymerization of the polyimide portion
- the steric structure of the oligomer is shown in FIG. 2 (B). As shown in the figure, even when the molecular chain length of the oligomer is increased to some extent, both side chains centered on the non-axisymmetric site do not become linear, and the oligomer chain as a whole is helical. It is understood that it shows.
- the imide oligomer according to the present invention can be easily thermoformed at a lower temperature, for example, as compared with the highly linear (crystalline) imide oligomer. It becomes possible.
- the polyimide resin formed by crosslinking the reactive group at the end of the imide oligomer forms a higher-order structure in which the above-mentioned helical structure is complicatedly entangled and crosslinked, and as a result, it is excellent It is considered that heat resistance can be obtained.
- Imide oligomer 2A In an argon stream, 3.37 g of 3,4'-diaminodiphenylmethane and 49.72 g of 4,4 '-(hexafluoroisopropylidene) diphthalic acid dianhydride are dissolved in 200 ml of dry N, N-dimethylacetamide for about 30 minutes. Stir at room temperature. Thereafter, 27.70 g of bis (4-aminophenyl) sulfone was added and stirred for about 1 hour. Finally, 9.25 g of 4-phenylethynylphthalic anhydride was added, and after stirring for about 1 hour at room temperature, the solvent was refluxed for about 12 hours to obtain an off-white suspension.
- the suspension was charged into 800 ml of ion-exchanged water, filtered, repeatedly washed with water several times, washed with methanol and filtered, and dried overnight at 120 ° C. to obtain a white powdery imide oligomer (imide oligomer 2A).
- the obtained imide oligomer was measured by GPC (Aliance 2695: manufactured by Waters), and as a result, the number average molecular weight (Mn) was 4.5 ⁇ 10 3 g / mol (NMP solvent).
- the polyimide resin cured product obtained above was analyzed by TG-DTA (EASTAR 6000: manufactured by SII) under a nitrogen stream, and as a result, the 5% thermal decomposition temperature ( ⁇ 5 ) was 527.7 ° C. (a rise in a nitrogen stream) The temperature was 10 degrees / minute). Further, DSC: In the measurement by (Q200 TA Co.), the glass transition temperature of the cured polyimide resin (T g) is 252.7 ° C. (under nitrogen stream, heating rate: 10 ° C. / min) was. Moreover, the thermal expansion coefficient (CTE) of the polyimide resin hardened
- EZGraph made by
- 3,4'-diaminodiphenyl ether or 3,4'-diaminodiphenylmethane to be a non-axisymmetric site is placed at the center of the oligomer chain, and the degree of polymerization of the side chain polyimide, or
- the 5% thermal decomposition temperature ( ⁇ 5 ) exceeds 500 ° C. as in the case of the above imide oligomers 1A and 2A. It was confirmed that all had excellent heat resistance.
- each non-axisymmetric aromatic diamine is used for each polyimide site.
- Imide oligomers 1J and 2D were prepared in exactly the same manner as the above imide oligomers 1A and 2A, except that they were introduced at the end (between each polyimide site and terminal reactive functional group), and after heat curing in the same manner as the above test. It was measured 5% thermal decomposition temperature (tau 5) and glass transition temperature (T g) for the polyimide resin. The results are shown in Tables 3 and 4 below.
- the imide oligomer has a helical property by arranging one non-axisymmetric aromatic diamine molecule only at the central part of the imide oligomer chain, and as a result, the thermoforming It can be seen that an imide oligomer having excellent heat resistance and excellent heat resistance as a polyimide resin after heat curing can be obtained easily and inexpensively.
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Abstract
Description
すなわち、本発明は、優れた熱成形性、及び加熱硬化後のポリイミド樹脂として優れた耐熱性を有するとともに、容易且つ安価に得ることのできるイミドオリゴマーを提供することを目的とするものである。
本発明にかかるイミドオリゴマーは、例えば、下記一般式(2)により表される。
(A)まず最初に、非軸対称性芳香族ジアミンと、これに対して大過剰量の酸二無水化物とを反応させることによって、非軸対称性芳香族ジアミン1分子を中心とした両側鎖に酸二無水化物を縮合したオリゴマー前駆体を調製する。
ここで、酸二無水化物の添加量は、非軸対称性芳香族ジアミン1モルに対して大過剰量であればよいが、より具体的には、例えば、非軸対称性芳香族ジアミンに対して2~20倍モル程度であればよい。なお、ここで用いる酸二無水化物の残基が、上記一般式(2)中、Xに相当する。また、反応に用いる溶媒としては、例えば、N-メチル-2-ピロリドン(NMP)、N,N-ジメチルホルムアミド、N-N-ジメチルアセトアミド(DMAc)、γ-ブチロラクタム等の非プロトン性溶媒が挙げられる。
なお、ここで用いるジアミンの残基が、上記一般式(2)中、Yに相当する。また、ジアミンとともに適当量の酸二無水化物をさらに添加してもよい。オリゴマー前駆体に対する酸二無水化物及びジアミンの添加割合を変化させることで、一分子当りのポリイミド構造の付加モル数を適宜調整することができる。本発明においては、上記一般式(2)中、nで表される各ポリイミド部位の平均重合度が1~10となるように、上記各成分の添加割合を調整する必要がある。
この架橋性反応基は加熱によって反応基同士が架橋構造を形成するため、これにより、イミドオリゴマーに熱硬化性を付与することができる。
なお、ここで用いる架橋性反応基含有化合物の残基が、上記一般式(2)中、Zに相当する。ここで、架橋性反応基含有化合物は、酸二無水化物における未反応カルボン酸基、ジアミンにおける未反応アミノ基のいずれかと反応し得るものであればよい。架橋性反応基含有化合物の添加量は、反応可能なカルボン酸基あるいはアミノ酸基の当量に合わせて適宜調整すればよいが、通常の場合、非軸対称性芳香族ジアミン1モルに対して約2モル程度であればよい。
最初に、非軸対称性芳香族ジアミンとして3,4’-ジアミノジフェニルエーテルを用いた場合のイミドオリゴマーの製造方法について説明する。
また、TMA(EASTAR6000:SII社製)により測定したポリイミド樹脂硬化物の熱膨張係数(CTE)は31ppmであった。また、ポリイミド樹脂硬化物を厚さ約75μmのフィルムとして、初期弾性率を測定(EZGraph:shimadzu社製)した結果、3.2GPaであった。
さらに、非軸対称部位をオリゴマー鎖中心部のみに有し、ポリイミド部位の重合度が2であるイミドオリゴマー1Aの立体構造図を図2(A)に、ポリイミド部位の重合度が6であるイミドオリゴマーの立体構造図を図2(B)に示す。同図に示すように、オリゴマーの分子鎖長がある程度長くなった場合であっても、非軸対称部位を中心とした両側鎖は直線状とはならずに、オリゴマー鎖が全体として螺旋性を示していることがわかる。
また、TMA(EASTAR6000:SII社製)により測定したポリイミド樹脂硬化物の熱膨張係数(CTE)は38ppmであった。また、ポリイミド樹脂硬化物を厚さ約75μmのフィルムとして、初期弾性率を測定(EZGraph:shimadzu社製)した結果、2.8GPaであった。
3,4’-ODA;3,4'-ジアミノジフェニルエーテル
3,4’-MDA;3,4’-ジアミノジフェニルメタン
1,3,3-APB;1、3-ビス(3-アミノフェノキシ)ベンゼン
4,4’-ODA;4,4’-ジアミノジフェニルエーテル
6FTPDA;2,2-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン
FDA;2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパン
SDA:ビス(4-アミノフェニル)スルフォン
DPSDA;ビス(4-アミノフェニル)スルフォン(ジアミン)
4,4’-ODPA;4,4'-オキシジフタル酸無水物
6FDPA:4,4'-(ヘキサフルオロイソプロピリデン)ジフタル酸二無水化物
PEPA;4-フェニルエチニルフタル酸無水化物
このことから、本発明のイミドオリゴマーを用い、加熱硬化時における温度や時間を適宜調整することで、要求される物性に応じた各種のポリイミド樹脂を製造することが可能であると考えられる。
Claims (11)
- 請求項1又は2に記載のイミドオリゴマーにおいて、一般式(1)又は(2)におけるWが-O-、又は-CH2-であることを特徴とするイミドオリゴマー。
- 請求項2又は3のいずれかに記載のイミドオリゴマーにおいて、各ポリイミド部位の平均重合度nがそれぞれ1~6であり、且つイミドオリゴマー全体の平均分子量が8000以下であることを特徴とするイミドオリゴマー。
- 請求項2から4のいずれかに記載のイミドオリゴマーにおいて、酸二無水化物残基Xが、ピロメリット酸二無水化物、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水化物、4,4'-ビフタリック酸二無水化物、3,3',4,4'-ジフェニルスルフォン酸、4,4'-オキシジフタル酸二無水化物、3,4,9,10-ペリレンテトラカルボン酸二無水化物、ナフタレン-1,4,5,8-テトラカルボン酸二無水化物、4,4'-(ヘキサフルオロイソプロピリデン)ジフタル酸二無水化物、2,2-ビス(4-カルボン酸フェニル)プロパン酸二無水化物から選ばれる少なくとも1種以上の酸二無水化物に由来することを特徴とするイミドオリゴマー。
- 請求項2から5のいずれかに記載のイミドオリゴマーにおいて、ジアミン残基Yが、4,4'-ジアミノジフェニルエーテル,1、3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパン、ビス(4-アミノフェニル)スルフォン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]ヘキサフルオロプロパン、α,α'-ビス(4-アミノフェニル)-1,4-ジイソプロピルベンゼン,3,3'-ビス(4-アミノフェニル)フルオレンから選ばれる少なくとも1種以上のジアミンに由来することを特徴とするイミドオリゴマー。
- 請求項2から6のいずれかに記載のイミドオリゴマーにおいて、末端の架橋性反応基Zが、4-フェニルエチニルフタル酸無水化物、無水フタル酸、5-ノルボルネン-2,3-ジカルボン酸無水化物、2,5-ノルボルナジエン-2,3-ジカルボン酸無水化物、マレイン酸無水物、プロパギルアミン、フェニルエチニルアニリン、エチニルアニリン、アミノスチレン、ビニルアニリンから選ばれる少なくとも一種以上の化合物に由来することを特徴とするイミドオリゴマー。
- 請求項1から7のいずれかに記載のイミドオリゴマーを加熱硬化させてなることを特徴とするポリイミド樹脂。
- 下記一般式(1)により表される非軸対称性芳香族ジアミン1分子に由来する非軸対称部位をオリゴマー鎖の中心部のみに有するイミドオリゴマーの製造方法であって、
(A)下記一般式(1)により表される非軸対称性芳香族ジアミンと、これに対して大過剰量の酸二無水化物とを反応させて、オリゴマー前駆体を調製する工程と、
(B)前記工程で得られたオリゴマー前駆体及び未反応酸二無水化物と、ジアミンとを重縮合反応させて、イミドオリゴマー又はアミック酸オリゴマーを調製する工程
を備えることを特徴とするイミドオリゴマーの製造方法。
- 請求項10に記載のイミドオリゴマーの製造方法において、さらに
(C)前記工程で得られたイミドオリゴマー又はアミック酸オリゴマーの末端に、架橋性反応基を有する化合物を付加する工程
を備えることを特徴とするイミドオリゴマーの製造方法。
Priority Applications (5)
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EP08791747A EP2246383A4 (en) | 2008-02-07 | 2008-07-28 | IMIDOLIGOMER AND THROUGH THERMAL HARDENING POLYIMID RESIN THEREOF |
US12/865,738 US20110003955A1 (en) | 2008-02-07 | 2008-07-28 | Imide Oligomer And Polyimide Resin Obtained By Thermal Curing Thereof |
CN200880126350.5A CN102015834B (zh) | 2008-02-07 | 2008-07-28 | 酰亚胺低聚物和使其加热固化而成的聚酰亚胺树脂 |
JP2008535822A JP4282750B1 (ja) | 2008-02-07 | 2008-07-28 | イミドオリゴマー及びこれを加熱硬化させてなるポリイミド樹脂 |
HK11109644.8A HK1155469A1 (en) | 2008-02-07 | 2011-09-13 | Imide oligomer and polyimide resin obtained by thermal curing thereof |
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TW200934808A (en) | 2009-08-16 |
HK1155469A1 (en) | 2012-05-18 |
CN102015834A (zh) | 2011-04-13 |
CN102015834B (zh) | 2013-10-16 |
US20110003955A1 (en) | 2011-01-06 |
EP2246383A1 (en) | 2010-11-03 |
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