CN104478932A - Phosphorus-containing polyimide and method for producing same - Google Patents

Phosphorus-containing polyimide and method for producing same Download PDF

Info

Publication number
CN104478932A
CN104478932A CN201410643564.7A CN201410643564A CN104478932A CN 104478932 A CN104478932 A CN 104478932A CN 201410643564 A CN201410643564 A CN 201410643564A CN 104478932 A CN104478932 A CN 104478932A
Authority
CN
China
Prior art keywords
phosphorous
polyimide
tetracarboxylic dianhydride
polyamic acid
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410643564.7A
Other languages
Chinese (zh)
Other versions
CN104478932B (en
Inventor
井上进介
坂本胜洋
难波悟
谷内暲
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Manac Inc
Original Assignee
Manac Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009276067A external-priority patent/JP5489682B2/en
Priority claimed from JP2009276066A external-priority patent/JP5570793B2/en
Application filed by Manac Inc filed Critical Manac Inc
Publication of CN104478932A publication Critical patent/CN104478932A/en
Application granted granted Critical
Publication of CN104478932B publication Critical patent/CN104478932B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • C07F9/65517—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring condensed with carbocyclic rings or carbocyclic ring systems
    • 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
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Disclosed are: a phosphorus-containing polyimide having a repeating unit represented by the belowmentioned general formula (II) (wherein R1, R2, and R3 are as described in the specification and the patent claims); a phosphorus-containing tetracarboxylic dianhydride that is the starting material thereof; and a method for producing the phosphorus-containing polyimide. The phosphorus-containing polyimide has excellent flame retardant properties.

Description

Phosphorous polyimide and manufacture method thereof
The application is the divisional application that the name submitted on December 3rd, 2010 is called the application for a patent for invention 201080054983.7 of " phosphorous polyimide and manufacture method thereof ".
Technical field
The present invention relates to a kind of phosphorous tetracarboxylic dianhydride, with its manufacture phosphorous polyimide and manufacture method.And then, the invention still further relates to and use these phosphorous polyimide or as circuit such as the various duplexer of the polyamic acid manufacture of its precursor and the flexible printing patch panels that uses these duplexers to manufacture.
Background technology
Usual polyimide is excellent in flame retardant resistance, thermotolerance, mechanical characteristics, electrical characteristic etc.; therefore, as the baseplate material of flexible printing patch panel, distribution and semiconductor element protective membrane, heat resistant adhesive, interlayer dielectic etc. and be widely used.
In recent years, for meeting the demand of compactization of electric power, e-machine etc., the Kapton of electric power, e-machine etc. is expected to be useful in.But along with the filming of polyimide, the flame retardant resistance of polyimide has the tendency of reduction.In addition, along with the high performance of the parts used in e-machine in recent years and element, CPU, have that its thermal discharge significantly increases, medial temperature also rises in machine a tendency, therefore expect stronger flame-retarded technology.On the other hand, from the viewpoint of environmental problem, when giving electric power, flame retardant resistance required by electronic product, just require to consider to the security of physical environment and human body, method that security is higher.
As the technology of giving polyimide flame retardant resistance, propose the method (such as, referenced patent document 1) mixed with the metal hydrate of magnesium hydroxide etc. by silicone-modified polyimide.But in the method, must carry out surface treatment additionally by phosphoric acid based surfactant to magnesium hydroxide, operation becomes complicated.Further, in the method, as the diamine component for base polymer, recommend the diamines in molecule with two or more hydroxyl, but such diamines may be not easy to obtain.
In addition, the method (such as, referenced patent document 2) being manifested flame retardant resistance by the specific polyimide resin of use containing silicon unit and the specific epoxy resin containing phosphoric is proposed.In the method, making phosphorus compound and epoxy resin reaction, target compound phosphorous epoxy resin can be obtained, but in order to make it have the function as epoxy resin, preferably must react to residue two epoxy group(ing), the higher limit of phosphorous rate only having 5 % by weight.Because the polyimide resin having imported silicon unit has inflammableness, thus for giving the polyimide resin composition that obtains in the method enough flame retardant resistances, must the low epoxy resin of polyhybrid thermotolerance.
In addition, as the method for giving resin combination flame retardant resistance, known has the method (such as, non-patent literature 1) of adding phosphorus compound in resin combination.But, in order to manifest flame retardant resistance with existing known technology, need to add phosphorus compound in a large number.
Prior art document
Patent documentation:
Patent documentation 1: JP 2008-63459 publication
Patent documentation 2: JP 2009-29982 publication
Non-patent literature:
Non-patent literature 1: ノ Application Ha ロ ゲ ン Xi Difficult combustible material To よ る Difficult burning Ji Intraoperative (エ ヌ テ イ mono-エ ス), p.28 (calendar year 2001 distribution)
Summary of the invention
The problem that invention will solve
The invention provides a kind of phosphorous tetracarboxylic dianhydride, with the phosphorous polyimide of its performance excellent flame characteristic manufactured for raw material and manufacture method thereof.
Technique means
The present inventor etc. find to have the phosphorus compound of ad hoc structure and have the reaction of dianhydride of ad hoc structure and the phosphorous polyimide that uses the phosphorous tetracarboxylic dianhydride with ad hoc structure be obtained by reacting by this to manufacture can't harm the character of existing polyimide and has excellent flame retardancy further, complete the present invention.First embodiment of the invention relates to the phosphorous tetracarboxylic dianhydride that following general formula (I) represents,
[changing 1]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound).
Second embodiment of the invention relates to the phosphorous polyimide with the repeating unit that following general formula (II) represents manufactured with these phosphorous tetracarboxylic dianhydrides,
[changing 2]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound, R 3for divalent organic group).
Third embodiment of the invention relates to the manufacture method of the phosphorous polyimide with the repeating unit that following general formula (II) represents, it is characterized in that, the phosphorous polyamic acid with the repeating unit that following general formula (III) represents is carried out heat and/or chemical closed loop
[changing 3]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound, R 3for divalent organic group),
[changing 4]
(in formula, R 1, R 2and R 3with above-mentioned synonym).
And then the present inventor finds by under the existence of phosphorus compound with ad hoc structure, carries out imidization, can obtain phosphorous polyimide, thus complete the present invention the polyamic acid with benzophenone skeletal.Therefore, fourth embodiment of the invention relates to the manufacture method of phosphorous polyimide, it is characterized in that, by the polyamic acid that following general formula (I ') represents,
[changing 5]
(in formula, R 3for divalent organic group), under the existence of the phosphorus compound represented at following general formula (1), carry out imidization,
[changing 6]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound).
Invention effect
The phosphorous tetracarboxylic dianhydride of first embodiment of the invention can be used as the raw material of the phosphorous polyimide with flame retardant resistance or stiffening agent, the properties-correcting agent as epoxy resin.In addition, the phosphorous polyimide of the flame retardant resistance using this phosphorous tetracarboxylic dianhydride to manufacture demonstrates excellent flame-retarding characteristic, can be used as having the heat resistant adhesive of flame retardant resistance, having the insulating material of the circuit substrate of flame retardant resistance.
In addition, the manufacture method of the phosphorous polyimide of fourth embodiment of the invention, that the polyamic acid with benzophenone skeletal being carried out to the short-cut method of imidization, is the method that can import the excellence of phosphorus compound in polyimide backbone under phosphorus compound exists.In addition, the phosphorous polyimide obtained by this manufacture method also demonstrates excellent flame-retarding characteristic, can be used as having the heat resistant adhesive of flame retardant resistance, having the insulating material etc. of the circuit substrate of flame retardant resistance.
Accompanying drawing explanation
Fig. 1 represent obtain in embodiment 1 compound (in general formula (I), R 1and R 2be phenyl) 1h-NMR schemes.
Fig. 2 represent obtain in embodiment 1 compound (in general formula (I), R 1and R 2be phenyl) 13c-NMR schemes.
Fig. 3 represent obtain in embodiment 1 compound (in general formula (I), R 1and R 2be phenyl) FT-IR figure.
Embodiment
Below embodiment of the present invention are described in detail.
I. phosphorous tetracarboxylic dianhydride
First, the phosphorous tetracarboxylic dianhydride of the raw material as the phosphorous polyimide of the present invention (sour composition) of first embodiment of the invention and manufacture method thereof are described.
(phosphorous tetracarboxylic dianhydride and manufacture method thereof)
The phosphorus compound that phosphorous tetracarboxylic dianhydride represented by general formula of the present invention (I) can be represented by benzophenone tetracarboxylic dianhydride and following general formula (1) reacts and obtains,
[changing 7]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein, and R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound).
As the concrete example of benzophenone tetracarboxylic dianhydride used herein, can 3 be enumerated, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride.
As the phosphorus compound that general formula (1) represents, preferred R 1and R 2be phenyl (wherein, at least one hydrogen atom on phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group) phosphorus compound, as object lesson, the diphenyl phosphine oxide (DPO) that following formula (1a) represents can be enumerated.
[changing 8]
Similarly, as the phosphorus compound that general formula (1) represents, preferred R 1and R 2in one be phenyl, another is phenoxy group, on respective phenyl ring, a carbon atom mutually with singly bound (wherein, at least one hydrogen atom on phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group) phosphorus compound, as concrete example, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA (registered trademark)) that following formula (1b) represents can be enumerated.
[changing 9]
The reaction of the phosphorus compound represented by benzophenone tetracarboxylic dianhydride and general formula (1), can obtain the phosphorous tetracarboxylic dianhydride that general formula of the present invention (I) represents:
[changing 10]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein, and R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring also can mutually with singly bound).As concrete example, following general formula (Ia) can be enumerated:
[changing 11]
Or the phosphorous tetracarboxylic dianhydride represented by following general formula (Ib),
[changing 12]
(in formula, R 1' and R 2' can be the same or different, alkyl or alkoxyl group for hydrogen, carbon number 1-6).
This reaction can at 40-250 DEG C, heat at the temperature of preferred 50-200 DEG C, more preferably 70-180 DEG C 1 point-12 hours, preferably 5 points-6 hours, more preferably 10 points-3 hours and carry out.
In the reaction, also solvent can be used.The solvent used, as long as be just not particularly limited the solvent of reaction in inertia, suitably can select according to the temperature of reaction expected.Can be used alone or two or more solvents used in combination with arbitrary proportion.Such as, ether solvent, N that the aromatic hydrocarbon that toluene, dimethylbenzene, ethylbenzene, methyl-phenoxide, chlorobenzene, dichlorobenzene, trichlorobenzene can be used such, tetrahydrofuran (THF), diglyme, triglyme are such, the aprotic polar solvent etc. that dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE (NMP), methyl-sulphoxide (DMSO) are such.The usage quantity of solvent is 50-1000 % by weight relative to benzophenone tetracarboxylic dianhydride, preferred 100-500 % by weight.
After reaction terminates, thick product can be obtained by concentration of reaction solution.With polar solvent, the such thick product of solvent cleaning of such as acetonitrile, ethyl acetate, methyl iso-butyl ketone (MIBK) can carry out purifying.Cleaned crystallization is filtered, under decompression or normal pressure, at the temperature of 40-250 DEG C, preferably 80-200 DEG C, makes it dry and obtain target compound.
II. phosphorous polyimide and manufacture method thereof
Then, to of the present invention second and the 3rd embodiment phosphorous polyimide and manufacture method be described.
(phosphorous polyamic acid and manufacture method thereof)
For the manufacture of phosphorous polyimide of the present invention, first, the phosphorous polyamic acid with the repeating unit that following general formula (III) represents as its precursor is manufactured:
[changing 13]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein, and R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound, R 3for the organic group of divalence.)
The manufacture of phosphorous polyamic acid can by the phosphorous tetracarboxylic dianhydride that will obtain in aforesaid method and Shi H 2n-R 3-NH 2the known method polymerization of the diamine component represented is carried out.Usually, polyreaction is carried out in a solvent under the solute concentration of 5-80 % by weight, preferably 10-50 % by weight.After reaction terminates, reaction soln can, directly as phosphorous polyamic acid solution (varnish), continue to use in imidization reaction.In addition, also from reaction soln, phosphorous polyamic acid can be separated, and then be dissolved in suitable solvent, modulate phosphorous polyamic acid solution.
Formula H 2n-R 3-NH 2the diamine component represented can be aromatic diamine, aliphatie diamine or ester ring type diamines, therefore, as R 3example, the divalent group of the monocyclic of carbon number 6-14 or condensation polycyclic formula aromatics can be enumerated (such as, phenylene, sub indenyl, naphthylidene, fluorenylidene), the divalent group of the fatty compounds of carbon number 2-12 (such as, the alkylidene group of carbon number 2-12, alkenylene or alkynylene) or carbon number 3-10 ester ring type compound divalent group (such as, the cycloalkylidene of carbon number 3-10 or sub-cycloalkenyl group), or can be the same or different two above-mentioned divalent groups directly or by bridge joint group (wherein, bridge joint group is selected from-O-,-CO-,-COO-,-OCO-,-SO 2-,-S-,-CH 2-,-C (CH 3) 2-and-C (CF 3) 2-) interconnected group (such as, biphenyl-4,4 '-two base, phenyl ether-4,4 '-two base, phenyl ether-3,4 '-two base, UVINUL MS 40,4 '-two base).These aromatic diamines, aliphatie diamine or ester ring type diamines can have the substituting group of more than one alkyl being selected from carbon number 1-6, thiazolinyl, alkynyl or alkoxyl group or halogen atom.
As the example of aromatic diamine composition used herein, the diamines with an aromatic series base can be enumerated: Ursol D, mphenylenediamine, p-benzylamine, an amino-benzylamine, diaminotoluene class, diamino xylene, diaminonaphthalene class, diaminoanthraquinone-class etc., there is the diamines of two aromatic series bases: 4, 4 '-benzidine, 3, 4 '-benzidine, 3, 3 '-benzidine, o-tolidine, between tolidine, dianisidine, 4, 4 '-diaminodiphenylmethane, 3, 4 '-diaminodiphenylmethane, 3, 3 '-diaminodiphenylmethane, 4, 4 '-diaminodiphenyl oxide, 3, 4 '-diaminodiphenyl oxide, 3, 3 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenylsulfone(DDS), 3, 4 '-diaminodiphenylsulfone(DDS), 3, 3 '-diaminodiphenylsulfone(DDS), 4, 4 '-diamino benzophenone, 3, 4 '-diamino benzophenone, 3, 3 '-diamino benzophenone, 3, 4-diaminobenzophenone, 2, 2-bis-(4-amino-benzene oxygen) propane, 2, 2-bis-(3-amino-benzene oxygen) propane, 2-(3-aminophenyl)-2-(4-aminophenyl) propane etc., there is the diamines of three aromatic series bases: 1,4-bis-(4-amino-benzene oxygen) benzene, 1,4-bis-(3-amino-benzene oxygen) benzene, 1,3-bis-(4-amino-benzene oxygen) benzene, 1,3-bis-(3-amino-benzene oxygen) benzene, 1,4-bis-(4-amino benzoyl) benzene, 1,4-bis-(3-amino benzoyl) benzene, 1,3-bis-(4-amino benzoyl) benzene, 1,3-bis-(3-amino benzoyl) benzene, 9,9-bis-(4-aminophenyl) fluorenes etc., there is the diamines of more than four aromatic series bases: 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] ether, two [4-(3-amino-benzene oxygen) phenyl] ether, 4,4 '-two (4-amino-benzene oxygen) benzophenone, 4,4 '-two (3-amino-benzene oxygen) benzophenone, Isosorbide-5-Nitrae-two [4-(2-, 3-or 4-amino-benzene oxygen) benzoyl) benzene, 1,3-bis-[4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] benzene, Isosorbide-5-Nitrae-two [3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] benzene, 1,3-bis-[3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] benzene, 4,4 '-two [4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] phenyl ether, 4,4 '-two [3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] phenyl ether, 4,4 '-two [4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] biphenyl, 4,4 '-two [3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] biphenyl, 4,4 '-two [4-(2-, 3-or 4-amino-benzene oxygen) benzoyl] sulfobenzide, 4,4 '-two [3-(2-, 3-or 4-amino-benzene oxygen) benzoyl] sulfobenzide etc.In addition, the substituting group of the alkyl that the hydrogen atom on the aromatic ring of these materials also can be selected from carbon number 1-6 by more than one, thiazolinyl, alkynyl or alkoxyl group or halogen atom substitutes.If consider the easiness of acquisition, preferably use 4 particularly, 4 '-diaminodiphenyl oxide, 3, 4 '-diaminodiphenyl oxide, 1, 4-bis-(4-amino-benzene oxygen) benzene, 1, 4-bis-(3-amino-benzene oxygen) benzene, 1, 3-bis-(4-amino-benzene oxygen) benzene, 1, 3-bis-(3-amino-benzene oxygen) benzene, 2, 2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 4, 4 '-two (4-amino-benzene oxygen) biphenyl, 4, 4 '-two (3-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] sulfone, 9, 9-bis-(4-aminophenyl) fluorenes.
As the example of aliphatics used herein or ester ring type diamine component, can 1 be enumerated, 2-quadrol, 1, 2-propylene diamine, 1, 3-propylene diamine, 1, 4-butanediamine, 1, 3-pentamethylene diamine, 1, 5-pentamethylene diamine, 1, 6-hexanediamine, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-undecane diamines, 1, 12-dodecamethylene diamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, 1, 3-bis-(aminomethyl) hexanaphthene, 1, 4-bis-(aminomethyl) hexanaphthene, 1, 3-diamino-cyclohexane, 1, 4-diamino-cyclohexane, 4, 4 '-diamino-dicyclohexyl methane, isophorone diamine etc.Consider the easiness of acquisition, particularly, preferably use 1,6-hexanediamine, 1,3-bis-(aminomethyl) hexanaphthene, Isosorbide-5-Nitrae-two (aminomethyl) hexanaphthene, 1,4-diamino-cyclohexane, 4,4 '-diamino-dicyclohexyl methane, isophorone diamine.
Can by independent for above-mentioned diamine component or two or more used in combination.And then the siloxane diamine that also can following general formula (IV) be used to represent in the scope of diamine component 1-50 % by mole carries out copolymerization:
[changing 14]
(in formula, m is the mixed number of the integer of 0-20, R 4represent methyl, sec.-propyl, phenyl, vinyl, R 5represent the bivalent hydrocarbon radical of carbon number 1-7, such as trimethylene, tetramethylene, phenylene etc.).
And then, be adjustment molecular weight, mono-amine compound or dicarboxylic anhydride can be added.The mono-amine compound used is aniline, PAP, 3-amino-phenol, 4-phenylaniline, 4-phenoxybenzamine, 3-amino-benzene acetylene, 4-amino-benzene acetylene etc., and dicarboxylic anhydride is maleic anhydride, Tetra hydro Phthalic anhydride, 4-phenylene-ethynylene Tetra hydro Phthalic anhydride, 4-ethynyl Tetra hydro Phthalic anhydride, trimellitic acid etc.The addition of mono-amine compound or dicarboxylic anhydride is different according to the difference of the molecular weight of the phosphorous polyimide of target compound, but is generally the mole number of the 1.0-several times of the difference of whole dianhydride of use and the mole number of diamine compound, and preferred 1.5-4.0 doubly.Add mono-amine compound when dianhydride is many, when diamine compound is many, add dicarboxylic anhydride.
Manufacture the solvent that the phosphorous polyamic acid of the present invention uses, as long as be just not particularly limited the solvent of reaction in inertia, such as, N can be used separately or with mixed style, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), tetramethyl-urea, tetrahydrofuran (THF) etc.Particularly preferably N,N-dimethylacetamide, N-Methyl pyrrolidone.In addition, also can be used in combination with arbitrary proportion by these solvents and toluene, dimethylbenzene, ethylbenzene, methyl-phenoxide, chlorobenzene, dichlorobenzene, trichlorobenzene, diglyme, triglyme equal solvent.In addition, these solvents also can use when separated phosphorous polyamic acid is dissolved to modulate phosphorous polyamic acid solution again.
Of the present invention have the phosphorous polyamic acid of repeating unit represented by general formula (III) and have the phosphorous polyimide of the repeating unit represented by general formula (II), not only refer to the phosphorous polyamic acid that the repeating unit only represented by general formula (III) is formed and the phosphorous polyimide that the repeating unit only represented by general formula (II) is formed, also comprise containing the material being main composition unit with repeating unit described separately.Therefore, in the object of harmless phosphorous polyimide of the present invention or the reactive scope as the phosphorous polyamic acid of its precursor, when manufacturing phosphorous polyamic acid, the tetracarboxylic dianhydride beyond the phosphorous tetracarboxylic dianhydride represented by above-mentioned general formula (I) partly can be used.
As such tetracarboxylic dianhydride, pyromellitic dianhydride can be enumerated, 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride, 2, 3 ', 3, 4 '-biphenyl tetracarboxylic dianhydride, 2, 2 ', 3, 3 '-biphenyl tetracarboxylic dianhydride, 4, the two O-phthalic acid dianhydride of 4 '-oxygen, 3, the two O-phthalic acid dianhydride of 4 '-oxygen, 3, the two O-phthalic acid dianhydride of 3 '-oxygen, 4, 4 '-benzophenone tetracarboxylic dianhydride, 4, 4 '-sulfobenzide tetracarboxylic dianhydride, 2, 2-bis-(3, 4-dicarboxyphenyi) propane dianhydride, 2, 2-bis-(3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 1, 2, 7, 8-naphthalene tetracarboxylic acid dianhydride etc.In order to be provided as the phosphorous polyimide with excellent flame characteristic of the object of the invention, in the tetracarboxylic dianhydride's composition used, phosphorous tetracarboxylic dianhydride represented by general formula (I) preferably uses more than 30 % by mole, more preferably uses more than 50 % by mole.
And then the manufacture of phosphorous polyamic acid also can save separation, the purge process of above-mentioned corresponding acid dianhydride.Namely, can will comprise the phosphorus compound that represented by benzophenone tetracarboxylic dianhydride and general formula (1) in a solvent in 40-250 DEG C, preferred 50-200 DEG C, more preferably heating 1 point-12 hours at 70-180 DEG C, preferably 5 points-6 hours, more preferably after the solution of 10 points of phosphorous tetracarboxylic dianhydrides obtained to 3 hours cools, add the diamine compound (diamine compound as previously mentioned) of expectation and add N if desired, N-N,N-DIMETHYLACETAMIDE, the solvent that METHYLPYRROLIDONE is such, solute concentration is made to be 5-80 % by weight, more preferably 10-50 % by weight carries out.
(manufacture method of phosphorous polyimide)
By making the phosphorous polyamic acid with the repeating unit that following general formula (III) represents obtained as described above carry out heat and/or chemical closed loop,
[changing 15]
(in formula, R 1and R 2can be identical, also can be different, be phenyl or phenoxy group, wherein, R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound, R 3for divalent organic group), the phosphorous polyimide with the repeating unit that following general formula (II) represents of the present invention can be obtained,
[changing 16]
(in formula, R 1, R 2and R 3with above-mentioned synonym.)
Phosphorous polyimide of the present invention can utilize known method that phosphorous polymeric amide acid heat and/or chemical closed loop (that is, dewatering) are manufactured.Such as, can be coated with on the base materials such as resin film such as the tinsels such as sheet glass, copper, aluminium or stainless steel or polyethylene terephthalate (PET), PEN (PEN), polyphenylene sulfide (PPS), polyimide, silicone resin or fluoro-resin that phosphorous polyamic acid solution makes its dried thickness be 0.1-250 μm, more preferably 1.0-100 μm, at 40-500 DEG C, more preferably 70-350 DEG C dry 1 point-5 hours, more preferably 3 points-3 hours, obtain phosphorous polyimide thus.The polyimide obtained can be peeled off from base material and as film morphology or directly use as duplexer.
In addition, can add in phosphorous polyamic acid solution toluene, dimethylbenzene, ethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene such with the solvent of water azeotropic, heat at 100-300 DEG C, more preferably 150-250 DEG C, system of being discharged by the water produced along with imidization is outer and carry out hot-imide, obtains phosphorous polyimide thus.Now, the nitrogen-containing heterocycle compound that pyridine, picoline, imidazoles can be used such or such three low-grade alkylamines etc. of triethylamine.Or, add diacetyl oxide, trifluoroacetic anhydride, N, the nitrogen-containing heterocycle compound that the dewatering agent that N-dicyclohexylcarbodiimide is such and pyridine, picoline, imidazoles are such or such three low-grade alkylamines etc. of triethylamine, dewater at 0-200 DEG C and carry out chemical imidization in 1-24 hour, obtain phosphorous polyimide thus also passable.The above-mentioned solution completing heat or chemical imidization like this can be injected the so independent solvent of water, methyl alcohol, ethanol, Virahol, acetone, toluene, dimethylbenzene or their mixing solutions, crystallization also filters, dry, pulverize and obtain the form of powdery.The polyimide obtained, can be directly used in injection molding or compressed moulding.In addition, as other purposes, it can be made to be dissolved in solvent, use as varnish, also can be coated in aforementioned substrates, make its drying obtain film morphology.
III. the manufacture method of phosphorous polyimide
The manufacture method of the phosphorous polyimide of fourth embodiment of the invention is described.
(manufacture method of polyamic acid)
For the manufacture of phosphorous polyimide of the present invention, first manufacture the polyamic acid that the general formula (I ') as its raw material represents,
[changing 17]
(in formula, R 3represent the organic group of divalence).
The polyamic acid that formula (I ') represents, can by benzophenone tetracarboxylic dianhydride and formula H 2n-R 3-NH 2the diamine component represented reacts and obtains.This manufacture method is not particularly limited, and available known method is carried out usually in a solvent under the solute concentration of 5-80 % by weight, preferably 10-50 % by weight.After reaction terminates, reaction soln can directly then use as polyamic acid solution (varnish) in imidization reaction.In addition, polyamic acid also can be made to be separated from reaction soln, and then to be dissolved in suitable solvent, modulate phosphorous polyamic acid solution thus.
The solvent used in the manufacture of polyamic acid, as long as be just not particularly limited the solvent of reaction in inertia, such as, can by N, dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE, methyl-sulphoxide, tetramethyl-urea, tetrahydrofuran (THF) etc. use under independent or mixed style.Particularly preferably N,N-dimethylacetamide, METHYLPYRROLIDONE.In addition, also can with arbitrary proportion toluene used in combination, dimethylbenzene, ethylbenzene, methyl-phenoxide, chlorobenzene, dichlorobenzene, trichlorobenzene, diglyme, triglyme equal solvent in these solvents.In addition, these solvents also can use when dissolving separated polyamic acid again thus modulate polyamic acid solution.
As the object lesson of the benzophenone tetracarboxylic dianhydride wherein used, can 3 be enumerated, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride.
The formula H wherein used 2n-R 3-NH 2the diamine component represented, it can be aromatic diamine, aliphatie diamine or ester ring type diamines, therefore, as the example of R3, the divalent group of the monocyclic of carbon number 6-14 or condensation polycyclic formula aromatics can be enumerated (such as, phenylene, sub indenyl, naphthylidene, fluorenylidene), the divalent group of the fatty compounds of carbon number 2-12 (such as, the alkylidene group of carbon number 2-12, alkenylene or alkynylene) or carbon number 3-10 ester ring type compound divalent group (such as, the cycloalkylidene of carbon number 3-10 or sub-cycloalkenyl group), or can be the same or different two above-mentioned divalent group is direct or (wherein bridge joint group is selected from-O-by bridge joint group,-CO-,-COO-,-OCO-,-SO 2-,-S-,-CH 2-,-C (CH 3) 2-and-C (CF 3) 2-) interconnected group (such as, biphenyl-4,4 '-two base, phenyl ether-4,4 '-two base, phenyl ether-3,4 '-two base, UVINUL MS 40,4 '-two base).These aromatic diamines, aliphatie diamine or ester ring type diamines can have the substituting group of more than one alkyl being selected from carbon number 1-6, thiazolinyl, alkynyl or alkoxyl group or halogen atom.
The example of aromatic diamine composition, aliphatics or ester ring type diamine component, with in the entry of above-mentioned (the phosphorous polyimide of II. and manufacture method thereof), each diamine compound that the example as aromatic diamine composition, aliphatics or ester ring type diamine component is specifically enumerated is identical.
Also can be independent or two or more used in combination by above-mentioned diamine component.And then the siloxane diamine that also can following general formula (IV) be used to represent in the scope of diamine component 1-50 % by mole carries out copolymerization,
[changing 18]
(in formula, m is the mixed number of the integer of 0-20, R 4represent methyl, sec.-propyl, phenyl, vinyl, R 5represent the divalent group of the hydrocarbon of carbon number 1-7, such as trimethylene, tetramethylene, phenylene etc.).
The polyamic acid utilizing benzophenone tetracarboxylic dianhydride and diamine component to be obtained by reacting of the present invention, not only refer to the polyamic acid that the repeating unit only represented by general formula (I ') is formed, also comprise containing with the polyamic acid of this repeating unit for main composition unit.Therefore, in the object of harmless phosphorous polyimide of the present invention or the reactive scope as the polyamic acid of its precursor, when manufacturing polyamic acid, the tetracarboxylic dianhydride beyond benzophenone tetracarboxylic dianhydride can partly be used.
As such tetracarboxylic dianhydride, PMA can be enumerated, 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride, 2, 3 ', 3, 4 '-biphenyl tetracarboxylic dianhydride, 2, 2 ', 3, 3 '-biphenyl tetracarboxylic dianhydride, 4, the two O-phthalic acid dianhydride of 4 '-oxygen, 3, the two O-phthalic acid dianhydride of 4 '-oxygen, 3, the two O-phthalic acid dianhydride of 3 '-oxygen, 4, 4 '-sulfobenzide tetracarboxylic dianhydride, 2, 2-bis-(3, 4-dicarboxyphenyi) propane dianhydride, 2, 2-bis-(3, 4-dicarboxyphenyi) hexafluoropropane dianhydride, 1, 2, 7, 8-naphthalene tetracarboxylic acid dianhydride etc.In order to be provided as the object of the invention, the phosphorous polyimide with excellent flame characteristic, in tetracarboxylic dianhydride's composition of use, the benzophenone tetracarboxylic dianhydride preferably used more than 30 % by mole, more preferably more than 50 % by mole.
And then, be adjustment molecular weight, mono-amine compound or dicarboxylic anhydride can be added.The mono-amine compound used is aniline, PAP, 3-amino-phenol, 4-phenylaniline, 4-phenoxybenzamine, 3-amino-benzene acetylene, 4-amino-benzene acetylene etc., and dicarboxylic anhydride is maleic anhydride, Tetra hydro Phthalic anhydride, 4-phenylene-ethynylene Tetra hydro Phthalic anhydride, 4-ethynyl Tetra hydro Phthalic anhydride, trimellitic acid etc.The addition of mono-amine compound or dicarboxylic anhydride is different according to the difference of the molecular weight of target compound polyimide, but is generally the mole number of the 1.0-several times of the difference of whole dianhydride of use and the mole number of diamine compound, and preferred 1.5-4.0 doubly.Add mono-amine compound when dianhydride is many, when diamine compound is many, add dicarboxylic anhydride.
(manufacture method of phosphorous polyimide)
The polyamic acid represented with following general formula (I ') obtained as described above,
[changing 19]
(in formula, R 3represent divalent organic group), manufacture by carrying out imidization under the existence of phosphorus compound that represents at following general formula (1),
[changing 20]
(in formula, R 1and R 2can be identical, also can be different, be phenyl or phenoxy group, wherein, R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound).While imidization, in polyimide backbone, import the phosphorus compound that general formula (1) represents, manufacture phosphorous polyimide.
As the phosphorus compound that general formula (1) represents, preferred R 1and R 2be phenyl (wherein, at least one hydrogen atom on phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group), as its concrete example, the diphenyl phosphine oxide (DPO) that following formula (1a) represents can be enumerated.
[changing 21]
Equally, preferably, as the phosphorus compound that general formula (1) represents, R 1and R 2one of them is phenyl, another is phenoxy group, a carbon atom on respective phenyl ring mutually with singly bound (wherein, at least one hydrogen atom on phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group), as concrete example, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA (registered trademark)) that following formula (1b) represents can be enumerated.
[changing 22]
The usage quantity of the phosphorus compound that general formula (1) represents is the mole number of the 0.5-several times of the mole number of the benzophenone tetracarboxylic dianhydride of use, preferred 0.8-4.0 times mole.
Under the existence of the phosphorus compound represented at general formula (1), imidization is carried out to the above-mentioned polyamic acid obtained like that, phosphorous polyimide can be manufactured thus.Such as, the phosphorus compound that general formula (1) represents can be added in the above-mentioned polyamic acid solution obtained like that after, implement imidization.Or, also in the solvent that with the addition of the phosphorus compound that general formula (1) represents in advance, polyamic acid can be manufactured as described above by benzophenone tetracarboxylic dianhydride and diamine component, then implements imidization.
Can the phosphorus compound that general formula (1) represents directly be made an addition in polyamic acid solution or reaction solvent, but also can in the solvent to reaction being inertia, such as N, dinethylformamide, N, in N-N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE, methyl-sulphoxide, tetramethyl-urea, tetrahydrofuran (THF), toluene, dimethylbenzene, ethylbenzene, methyl-phenoxide, chlorobenzene, dichlorobenzene, trichlorobenzene, diglyme, triglyme equal solvent, add after dissolving with the solute concentration of 5-90 % by weight, preferably 10-80 % by weight.
Then, the mixing solutions that can be coated with this polyamic acid and phosphorus compound on the base materials such as resin film such as the tinsels such as sheet glass, copper, aluminium or stainless steel or polyethylene terephthalate (PET), PEN (PEN), polyphenylene sulfide (PPS), polyimide, silicone resin or fluoro-resin makes dried thickness be 0.1-250 μm, more preferably 1.0-100 μm, at 40-500 DEG C, more preferably 70-350 DEG C dry 1 point-5 hours, more preferably 3 points-3 hours, obtain phosphorous polyimide thus.The phosphorous polyimide obtained can be peeled off from base material and as film morphology or directly use as duplexer.
In addition, can in the mixing solutions of this polyamic acid and phosphorus compound, add toluene, dimethylbenzene, ethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene like that and the solvent of water azeotropic, heat at 100-300 DEG C, more preferably 150-250 DEG C, system of being discharged by the water produced along with imidization is outer and carry out hot-imide, obtains phosphorous polyimide thus.Now, the nitrogen-containing heterocycle compound that pyridine, picoline, imidazoles also can be used such or such three low-grade alkylamines etc. of triethylamine.Or, add diacetyl oxide, trifluoroacetic anhydride, N, the nitrogen-containing heterocycle compound that the dewatering agent that N-dicyclohexylcarbodiimide is such and pyridine, picoline, imidazoles are such or such three low-grade alkylamines etc. of triethylamine, dewater 1-24 hour at 0-200 DEG C, and carry out chemical imidization, also can obtain phosphorous polyimide thus.The solution completing above-mentioned such heat or chemical imidization can be injected the so independent solution of water, methyl alcohol, ethanol, Virahol, acetone, toluene, dimethylbenzene or their mixing solutions, crystallization also filters, dry, pulverize and obtain powder form.The phosphorous polyimide obtained, can be directly used in injection molding or compressed moulding.In addition, as other purposes, it also can be made to be dissolved in solvent, use as varnish, also can be coated in aforementioned substrates, make its drying obtain film morphology.
IV. various duplexer, circuit
Metal laminate of the present invention, the phosphorous polyamic acid solution that such as record according to above-mentioned (the phosphorous polyimide of II. and manufacture method thereof) entry can be manufactured coat thickness 0.5-400 μm, more preferably 1.0-200 μm copper, the tinsel such as aluminium or stainless steel at least side on, make its dried thickness be 0.1-250 μm, more preferably 1.0-100 μm, at 40-500 DEG C, more preferably 70-350 DEG C dry 1 point-5 hours, more preferably 3 points-3 hours, manufacture thus.
Or, on at least side of the phosphorous Kapton that can obtain in the record according to above-mentioned (the phosphorous polyimide of II. and manufacture method thereof) or (manufacture method of the phosphorous polyimide of III.) entry, via tackiness agents such as epoxy resin, crylic acid resin, polyimide resin classes, metal foil laminated with the copper of thickness 0.5-400 μm, more preferably 1.0-200 μm, aluminium or stainless steel etc., under normal pressure or pressurized conditions, process at 100-500 DEG C, preferably 150-350 DEG C and manufacture.
Aromatic polymer duplexer of the present invention, such as, the phosphorous polyamic acid solution that the record according to above-mentioned (the phosphorous polyimide of II. and manufacture method thereof) entry can be manufactured, being coated on thickness is 0.5-400 μm, more preferably the aromatic polyester of 1.0-200 μm, polyphenylene sulfide, aromatic polyimide, PAEK, aromatic copolycarbonate, aromatic liquid crystal polymer, or the aromatic polymer such as polybenzoxazole makes its dried thickness be 0.1-250 μm, more preferably 1.0-100 μm, at 40-500 DEG C, more preferably at 70-350 DEG C dry 1 point-5 hours, more preferably 3 points-3 hours, manufacture therefrom.
In addition, be 0.5-400 μm at thickness, more preferably the aromatic polyester of 1.0-200 μm, polyphenylene sulfide, aromatic polyimide, PAEK, aromatic copolycarbonate, aromatic liquid crystal polymer, or the aromatic polymer such as polybenzoxazole, or thickness is 0.5-400 μm, more preferably the copper of 1.0-200 μm, aluminium, or on any one side of the tinsel such as stainless steel, such as be coated with the record according to above-mentioned (the phosphorous polyimide of II. and manufacture method thereof) entry and the phosphorous polyamic acid solution manufactured, after making another one overlapping with coated face, by lamination or heat pressurization, be situated between can manufacturing and have the aromatic polymer metallic composite laminated body of phosphorous polyimide of the present invention.
On above-mentioned such metal laminate of manufacturing and aromatic polymer metallic composite laminated body, circuit pattern can be made by known method, and use as circuit.The circuit using phosphorous polyimide of the present invention to make has excellent flame retardant resistance, can provide safe electric power, e-machine thus.
Embodiment
Below in order to make embodiment of the present invention distinct, show embodiment and comparative example, but the present invention only should not be only limitted to the embodiment that illustrates herein.
Measuring method and the flame retardant resistance evaluation method of the soltion viscosity of the compound obtained in embodiment, purity, fusing point or second-order transition temperature, NMR and infrared absorption spectrum are as follows.
Soltion viscosity: use Brookfield viscometer (Tokyo gauge system), measure at the temperature of 25 DEG C.
Purity: use HPLC (Shimadzu Seisakusho Ltd.'s system) and post (eastern ソ mono-society TSKgelODS-80TM) to measure.Solution, by dissolved samples in the mixed solution of acetonitrile/water or after making it disperse, heats 15 minutes and modulates by sample solution at 60 DEG C.Elutriant uses acetonitrile/water/Phosphoric Acid, and purity utilizes area percentage to calculate.
Fusing point or second-order transition temperature: utilize differential scanning calorimeter (Shimadzu Seisakusho Ltd. DSC-60), be warming up to 40-400 DEG C with per minute 10 DEG C, and measure.Utilize and resolve software, calculate fusing point or second-order transition temperature from the extrapolation point of DSCDSC curve.
NMR: modulation is mixed with compound and heavy DMSO (Cambrige IsotopeLaboratories, Inc. system, the DMSO-d containing 0.05%TMS 6) solution, utilize NMR (NEC society system, JNM-AL400) to carry out 1h-NMR measure and 13c-NMR measures.
Infrared absorption spectrum: use IR determinator (パ mono-キ Application エ Le マ mono-society Spectrum 100 FT-IR Spectrometer), utilize KBr method, or use IR determinator (Shimadzu Seisakusho Ltd. Prestage 21), utilize ATR method to measure infrared absorption spectrum.
The evaluation of flame retardant resistance: test film film being cut into 200mm × 50mm size.Test film is rolled into cylindrical shape, is vertically fixed in clip, and sample bottom burner carry out twice 3 seconds burning, combustion time within 10 seconds be more than zero, 10 seconds be ×.
embodiment 1
general formula (I) (R 1 and R 2 be phenyl) synthesis of phosphorous tetracarboxylic dianhydride that represents
Diphenyl phosphine oxide (Aldrich) 2.8g (0.014mol), 3 is loaded in the four-hole boiling flask possessing stirrer, thermometer, nitrogen ingress pipe and cooling tube, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (ダ イ セ Le chemistry society system) 3.5g (0.011mol) and toluene 25g, under nitrogen flowing, stirring 4 hours at 110 DEG C.After reaction terminates, toluene is all distilled removing, after being cooled to 80 DEG C, add acetonitrile 10g.After being cooled to room temperature, leach the solid of precipitation, with toluene and acetonitrile cleaning.By the solid dry evening at 60 DEG C obtained, obtain the thick purified 2.8g of purity 94.2%.With acetonitrile, heated wash is carried out to this thick purified, obtain purity 97.5%, fusing point is the purifying product of 151 DEG C.By purifying product 1h-NMR represents in FIG, 13c-NMR represents in fig. 2, and FT-IR figure (the KBr method based on パ mono-キ Application エ Le マ mono-society Spectrum 100 FT-IRSpectrometer) represents in figure 3.
1H-NMR(400MHz，DMSO-d 6)：δ(ppm)＝7.08(d，J＝10Hz，1H)，7.48(ddd，J＝7.6，7.6，3.6Hz，4H)，7.59(ddd，J＝7.6，7.6，1.2Hz，2H)，7.76(ddd，J＝12.4，7.5，1.2Hz，4H)，8.06(d，J＝8.0Hz，2H)，8.23(dd，J＝8.0，1.2Hz，2H)，8.29(s，2H).
13C-NMR(400MHz，DMSO-d 6)：δ(ppm)＝75.0(d，J＝16.4Hz)，123.1，125.8，128.7(d，J＝52.8Hz)，130.7(d，J＝537.6Hz)，131.0，131.2(d，J＝39.6Hz)，131.9，132.5(d，J＝13.2Hz)，133.9，148.3(d，J＝16.8Hz)，162.5，162.6.
embodiment 2
general formula (II) (R 1 and R 2 be phenyl, R 3 for diphenyl ether-4,4 '-two base) represent phosphorous the synthesis of polyimide
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, load 4, the phosphorous tetracarboxylic dianhydride 26.2207g (0.05mol) of synthesis in 4 '-diamino-diphenyl ether (Wakayama refine society's system) 10.0118g (0.05mol), embodiment 1, NMP205g, under nitrogen flowing, stirred at ambient temperature 12 hours, synthesize phosphorous polyamic acid.Reaction soln (solute concentration 15%, viscosity (Brookfield viscometer: Tokyo gauge system) 5,500mPas) is directly used as phosphorous polyamic acid solution.The phosphorous polyamic acid solution obtained is coated with on a glass, dried thickness is made to be 25 μm, after 90 DEG C, 130 DEG C, 180 DEG C at each temperature dry 30 minutes, peel off from sheet glass and be fixed in metal frame, carrying out the thermal treatment of 1 hour at 200 DEG C, 250 DEG C at each temperature.Obtain the phosphorous polyimide that thickness is the film morphology of 25 μm.
embodiment 3
general formula (II) (R 1 and R 2 be phenyl, R 3 for Isosorbide-5-Nitrae-phenylene oxygen base biphenyl-4,4 '-two base oxy-1,4-phenylene) synthesis of phosphorous polyimide that represents
3 are loaded in the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 8.5602g (0.027mol), diphenyl phosphine oxide (DPO) 5.3713g (0.027mol), diglyme 47.4g, heat 3 hours at 160 DEG C, synthesize phosphorous tetracarboxylic dianhydride.The solution comprising this dianhydride is cooled to room temperature, load 4,4 '-two (4-amino-benzene oxygen) biphenyl (BAPB) 9.7876g (0.027mol), NMP47.4g, at room temperature stir 12 hours under nitrogen flowing, synthesize phosphorous polyamic acid.Reaction soln (solute concentration 20%, viscosity (Brookfield viscometer: Tokyo gauge system) 8,000mPas) is directly used as phosphorous polyamic acid solution.Be applied to sheet glass similarly to Example 2 and carry out drying and thermal treatment, obtaining the phosphorous polyimide that thickness is the film morphology of 20 μm.
comparative example 1
3 are loaded in the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 16.1113g (0.05mol), 4,4 '-diaminodiphenyl oxide 10.0118g (0.05mol), NMP148g, at room temperature stir 12 hours under nitrogen flowing, synthesize phosphorous polyamic acid.Reaction soln (solute concentration 15%, viscosity (Brookfield viscometer: Tokyo gauge system) 12,000mPas) is directly used as polyamic acid solution.To be applied to similarly to Example 2 on sheet glass and to carry out drying and thermal treatment, obtaining the not phosphorous polyimide that thickness is the film morphology of 20 μm.
comparative example 2
Except changing diamine compound into 4, outside 4 '-two (4-amino-benzene oxygen) biphenyl (BAPB) 18.4214g (0.05mol), carry out the operation same with comparative example 1, obtain the not phosphorous polyimide that thickness is the film morphology of 20 μm.
flame retardant resistance is evaluated
The polyimide obtained in embodiment 2 and 3 and comparative example 1 and 2 is evaluated.The results are shown in table 1.
[table 1]
embodiment 4
the manufacture of metal laminate
The phosphorous polyamic acid solution manufactured in embodiment 2 is coated on the Copper Foil (Mitsui Metal Co., Ltd.'s (strain) system, 3EC-VLP) of thickness 18 μm, the thickness of dried resin is made to be 25 μm, after 90 DEG C, 130 DEG C, 180 DEG C at each temperature dry 30 minutes, in Vacuumdrier, at 250 DEG C, carry out the thermal treatment of 1 hour, obtain phosphorous polyimide/metal laminate.
embodiment 5
the manufacture of aromatic polymer duplexer
Phosphorous polyamic acid solution embodiment 2 manufactured is coated on the aromatic polyimide film (デ ュ Port Application (strain) system, カ プ ト Application (registered trademark) H) of thickness 25 μm, dried resin thickness is made to be 25 μm, after 90 DEG C, 130 DEG C, 180 DEG C at each temperature dry 30 minutes, in drying machine, at 250 DEG C, carry out the thermal treatment of 1 hour, obtain phosphorous polyimide/aromatic polymer duplexer.
embodiment 6
the manufacture of aromatic polymer metallic composite laminated body
The phosphorous polyamic acid solution manufactured in embodiment 2 is coated on the Copper Foil (Mitsui Metal Co., Ltd.'s (strain) system, 3EC-VLP) of thickness 18 μm, makes dried resin thickness be 5 μm, drying 3 minutes at the temperature of 160 DEG C.Then, coated face superposes the aromatic polyimide film (デ ュ Port Application (strain) system, カ プ ト Application (registered trademark) EN) of thickness 40 μm, at the temperature of 200 DEG C, carries out lamination.The duplexer obtained is heat-treated at the temperature of 350 DEG C, obtains metal/phosphorous polyimide/aromatic polymer compound stack body.
embodiment 7
the synthesis (manufacture method according to fourth embodiment of the invention) of phosphorous polyimide
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, 4 are loaded in nitrogen gas stream, 4 '-diamino-diphenyl ether (4-ODA) (Wakayama refine society's system) 10.0118g (0.05mol), 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (HCA (registered trademark)) (Sanko Co., Ltd.'s system) 10.8086g (0.05mol), METHYLPYRROLIDONE (NMP) 148.0g, makes it dissolve.Thereafter, load 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) (ダ イ セ Le chemistry society system) 16.1113g (0.05mol), at room temperature stir 12 hours, obtain soltion viscosity 5,000mPas, the polyamic acid of solute concentration 20% and the mixing solutions of phosphorus compound.The mixing solutions obtained is coated with on a glass, dried thickness is made to be 20 μm, after 90 DEG C, 130 DEG C, 180 DEG C at each temperature dry 30 minutes, peel off from sheet glass and be fixed on metal frame, carry out the thermal treatment of 1 hour at 200 DEG C, 250 DEG C at each temperature, obtain the Kapton of the phosphorus atom containing 4.4% (theoretical value) in repeating unit.When measuring IR (based on Shimadzu Seisakusho Ltd. Prestage 21, the ATR method) of Kapton, 1670cm -1benzophenone carbonylic stretching vibration absorption disappear.The second-order transition temperature of film is 255 DEG C, flame retardant resistance is evaluated as zero.
comparative example 3
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, in nitrogen gas stream, load 4,4 '-diamino-diphenyl ether (4-ODA) (Wakayama refine society's system) 10.0118g (0.05mol), METHYLPYRROLIDONE (NMP) 148.0g, make it dissolve.Thereafter, 3,3 ' is loaded, 4,4 '-biphenyl tetracarboxylic dianhydride (BTDA) (ダ イ セ Le chemistry society system) 16.1113g (0.05mol), at room temperature stirs 12 hours, obtain the polyamic acid solution of soltion viscosity 12,500mPas, solute concentration 15%.The polyamic acid solution obtained is coated with on a glass, dried thickness is made to be 20 μm, after 90 DEG C, 130 DEG C, 180 DEG C at each temperature dry 30 minutes, peel off from sheet glass and be fixed on metal frame, carry out the thermal treatment of 1 hour at 200 DEG C, 250 DEG C at each temperature, obtain not phosphorous Kapton.The second-order transition temperature of film is 263 DEG C, flame retardant resistance is evaluated as ×.
comparative example 4
In the four-hole boiling flask possessing thermometer, nitrogen ingress pipe, in nitrogen gas stream, load 4,4 '-diamino-diphenyl ether (4-ODA) 10.0118g (0.05mol), 9,10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (HCA (registered trademark)) (Sanko Co., Ltd.'s system) 21.6172g (0.10mol), METHYLPYRROLIDONE (NMP) 188.6g, makes it dissolve.Thereafter, load 4, the two O-phthalic acid dianhydride 15.5107g (0.05mol) (マ ナツ Network Co., Ltd. system) of 4 '-oxygen, at room temperature stirs 12 hours, obtain soltion viscosity 7,800mPas, the polyamic acid solution of solute concentration 20% and the mixture of phosphorus compound.The mixture obtained is coated with on a glass, dried thickness is made to be 20 μm, after 90 DEG C, 130 DEG C, 180 DEG C at each temperature dry 30 minutes, peel off from sheet glass and be fixed on metal frame, carry out the thermal treatment of 1 hour at 200 DEG C, 250 DEG C at each temperature, obtain Kapton.When measuring IR (the ATR method based on Shimadzu Seisakusho Ltd. Prestage 21) of Kapton, do not find the existence of phosphorus.The second-order transition temperature of film is 228 DEG C, flame retardant resistance is evaluated as ×.
embodiment 8-10, comparative example 5
Similarly to Example 7, change various composition and make Kapton.Its composition and result are shown in Table 2.
[table 2]
Writing a Chinese character in simplified form in table is expressed as follows.
BTDA:3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
DSDA:3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride
APB:1,3-bis-(3-amino-benzene oxygen) benzene
BAPP:2,2-2 [4-(4-amino-benzene oxygen) phenyl] propane
BAPS:2 [4-(4-amino-benzene oxygen) phenyl] sulfone
HCA (registered trademark): 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
DPO: diphenyl phosphine oxide (Aldrich)
Industrial utilization possibility
The phosphorous polyimide using phosphorous tetracarboxylic dianhydride of the present invention to manufacture has the physical property identical with existing polyimide, demonstrate excellent flame-retarding characteristic simultaneously, even if become film also show good thermotolerance, the demand of compactization such as electric power, e-machine therefore can be met.In addition, using the phosphorous polyimide of flame retardant resistance of the present invention, can avoid or reduce and add fire retardant in addition, be therefore for physical environment or the safer flame-retarded technology of human body.
The manufacture method of the phosphorous polyimide described in the 4th embodiment of particularly the application of the invention, can manufacture phosphorous polyimide without the need to special device, step with easy method.Use the phosphorous polyimide of this manufacture method manufacture as requiring that insulating material of filming and flame-retarded heat resistant adhesive or circuit substrate etc. is very useful.

Claims (3)

1. phosphorous tetracarboxylic dianhydride, is represented by following general formula (I),
[changing 24]
(in formula, R 1and R 2can be the same or different, be phenyl or phenoxy group, wherein R 1and R 2at least one hydrogen atom on respective phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group, and/or R 1and R 2a carbon atom on respective phenyl ring can mutually with singly bound).
2. phosphorous tetracarboxylic dianhydride according to claim 1, in general formula (I), R 1and R 2be phenyl or R 1and R 2one of them be phenyl, another is phenoxy group, and its carbon atom separately on phenyl ring is mutually with singly bound (at least one hydrogen atom wherein, on phenyl ring can be substituted by the alkyl of carbon number 1-6 or alkoxyl group).
3. the phosphorous tetracarboxylic dianhydride described in claim 1 or 2, is selected from following formula (Ia):
[changing 25]
With following formula (Ib),
[changing 26]
(in formula, R 1and R 2can be the same or different, alkyl or alkoxyl group for hydrogen, carbon number 1-6).
CN201410643564.7A 2009-12-04 2010-12-03 Phosphorous polyimides and manufacture method thereof Active CN104478932B (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2009-276066 2009-12-04
JP2009276067A JP5489682B2 (en) 2009-12-04 2009-12-04 Method for producing phosphorus-containing polyimide
JP2009276066A JP5570793B2 (en) 2009-12-04 2009-12-04 Phosphorus-containing tetracarboxylic dianhydride and flame retardant polyimide
JP2009-276067 2009-12-04

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CN201080054983.7A Division CN102639547B (en) 2009-12-04 2010-12-03 Phosphorus-containing polyimide and method for producing same

Publications (2)

Publication Number Publication Date
CN104478932A true CN104478932A (en) 2015-04-01
CN104478932B CN104478932B (en) 2017-01-04

Family

ID=

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3222373A (en) * 1963-06-06 1965-12-07 Union Oil Co Derivatives of ferrocene
CN1136817A (en) * 1994-10-10 1996-11-27 托马斯·P·阿本德 Cross-linking agents for polymers with acid anhydride groups
WO2002092654A2 (en) * 2001-05-17 2002-11-21 The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) Space environmentally durable polyimides and copolyimides
JP2006251715A (en) * 2005-03-14 2006-09-21 Kaneka Corp Photosensitive resin composition having flame resistance and photosensitive dry film resist
CN101291990A (en) * 2005-10-21 2008-10-22 日本化药株式会社 Thermosetting resin composition and use thereof
JP2009221309A (en) * 2008-03-14 2009-10-01 Manac Inc Tetracarboxylic acid containing phosphorus-containing ester group or its dianhydride and phosphorus-containing polyester imide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3222373A (en) * 1963-06-06 1965-12-07 Union Oil Co Derivatives of ferrocene
CN1136817A (en) * 1994-10-10 1996-11-27 托马斯·P·阿本德 Cross-linking agents for polymers with acid anhydride groups
WO2002092654A2 (en) * 2001-05-17 2002-11-21 The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) Space environmentally durable polyimides and copolyimides
JP2006251715A (en) * 2005-03-14 2006-09-21 Kaneka Corp Photosensitive resin composition having flame resistance and photosensitive dry film resist
CN101291990A (en) * 2005-10-21 2008-10-22 日本化药株式会社 Thermosetting resin composition and use thereof
JP2009221309A (en) * 2008-03-14 2009-10-01 Manac Inc Tetracarboxylic acid containing phosphorus-containing ester group or its dianhydride and phosphorus-containing polyester imide

Also Published As

Publication number Publication date
CN102639547B (en) 2014-12-03
CN102639547A (en) 2012-08-15
WO2011068207A1 (en) 2011-06-09

Similar Documents

Publication Publication Date Title
JP6350526B2 (en) Polyimide precursor and polyimide
TWI342323B (en) Thermoset resin modified polyimide resin composition
CN101490175B (en) Thermocurable polyimide resin composition
CN103240936A (en) Transparent flexible laminate and laminate roll
CN104769013A (en) Polyimide precursor, polyimide, varnish, polyimide film, and substrate
CN104797632B (en) Polyimide resin film and the electronic device substrate comprising polyimide resin film
TWI612077B (en) Polyimide precursor, polyimide, varnish, polyimide film, and substrate
JP5510545B2 (en) Method for producing polyimide film laminate, polyimide film laminate
CN106062037B (en) The manufacturing method of display base plate resin combination, display base plate resin film and display base plate resin film
WO2008096967A1 (en) Method for preparing polyimide and polyimide prepared using the same
CN101679632A (en) Aromatic polyimide and process for production thereof
KR101922417B1 (en) Diamine compounds, and polyimide compounds and moldings using the same
KR20140051405A (en) Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same
Gao et al. A novel low colored and transparent shape memory copolyimide and its durability in space thermal cycling environments
CN102027044A (en) Polyester-imide precursor and polyester-imide
CN106519685B (en) A kind of polyimide material, preparation method and application
Bae et al. Synthesis and characterization of polyimides from 4‐(diphenyl phosphine oxide) phenyl pyrromellitic dianhydride
JP6790756B2 (en) Polyimide, polyimide precursor, and polyimide film
CN101563395A (en) Polyimide, diamine compound and method for producing the same
CN102639547B (en) Phosphorus-containing polyimide and method for producing same
JP5418114B2 (en) Polyimide material, polyimide resin composition, film and method for producing the same
CN104478932B (en) Phosphorous polyimides and manufacture method thereof
JP5555007B2 (en) Phosphorus-containing diamine compound and flame retardant polyimide
JP2005314630A (en) Aromatic polyamic acid and polyimide
JP5570793B2 (en) Phosphorus-containing tetracarboxylic dianhydride and flame retardant polyimide

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant