CN101698704B - Polyimide precursor composition and application thereof - Google Patents
Polyimide precursor composition and application thereof Download PDFInfo
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- CN101698704B CN101698704B CN2009101747980A CN200910174798A CN101698704B CN 101698704 B CN101698704 B CN 101698704B CN 2009101747980 A CN2009101747980 A CN 2009101747980A CN 200910174798 A CN200910174798 A CN 200910174798A CN 101698704 B CN101698704 B CN 101698704B
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Abstract
The invention provides a polyimide precursor composition, which comprises amic acid oligomer shown as a formula (1) and benzophenonetetracarboxylic dianhydride derivatives of which the end is provided with an ester group (-C(O)OR) and a carboxyl (-C(O)OH) and which is shown as a formula (2), wherein R, G, G1, P and m are defined as the description. The polyimide synthesized by the polyimide precursor composition has good operating characteristics and good physical and chemical properties.
Description
Technical field
This case is dividing an application of one Chinese patent application 200610162485.X.The present invention relates to a kind of polyimide precursor composition of (polyimide is called for short PI), the present invention also uses in the preparation of polyimide about said composition.
Background technology
Polyimide is the first-selection of high performance polymer material owing to having excellent heat-resistant quality and favorable mechanical, electric and chemical property always.In addition, because semi-conductor requiring on characteristic is increasingly high, and traditional inorganic materials has its limit and shortcoming of using, and the characteristic of polyimide just can remedy its weak point of traditional inorganic materials in some aspects.Therefore, after the aromatic polyimide technological development of E.I.Du Pont Company, promptly receive widely and to note, and develop and the multiduty polyimide of many tools.
On semi-conductor industry, polyimide is widely used in aspects such as passive film, stress buffer film, alpha-particle shielding film, dry-etching shield cap, micro electronmechanical and interlayer dielectric, and develops other new purposes just successively.Wherein, with as the protection integrated circuit component film be applied as the master, because of polyimide material can be through the test of integrated circuit component safety.And the application of polyimide is not only in integrated circuit industry, and it is all quite important on electronic packaging, enameled wire, printed substrate, sensing element, separatory membrane and structured material, is playing the part of the role of key material.
Generally with the polymerization condensation reaction mode of two-stage with synthesis of polyimides.Wherein, diamine monomer is dissolved in polarity like N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), N (DMF) or DMSO 99.8MIN. (DMSO), the aprotic solvent in the fs usually, adds nearly equimolar dicarboxylic anhydride monomer again., in low temperature or normal temperature under carry out condensation reaction, form polyimide precursor (precursor) thereafter, that is, and polyamic acid (poly (amic acid); Abbreviate PAA as).
Then, carry out subordinate phase,, carry out the reaction of condensation cyclodehydration, change polyamic acid into polyimide through the imidization (thermal imidization) of type of heating or the imidization (chemical imidization) of chemical mode.
The reaction process of preparation polyimide can be summarized as follows at present:
In above-mentioned preparation method, do not reach certain standard (that is, molecular weight is too small) like the polyamic acid molecular weight of fs gained, behind imidization (imidization), can't obtain the polyimide film of tool good physical properties.Yet if the molecular weight of fs gained polyamic acid is too high, its viscosity just can be too big, so that the operability variation, shortcomings such as leveling characteristics is bad arranged when being easy to be coated with.One example it, in being rotated when coating, be easy to generate convexity and webbing etc. and be difficult for the levelling phenomenon.In addition, too high polyamic acid molecular weight will be when carrying out the imidization of subordinate phase, and the shortening because of intermolecular interaction and molecular chain bond distance produces very big internal stress, causes institute's substrates coated flexural deformation.Therefore, for exempting foregoing problems, extensively inquired into the heating gradient curve and the internal stress relation of subordinate phase imidization on the document already, and worked out the mode of various reduction internal stress.Yet aforementioned leveling characteristics and internal stress problem are traced it to its cause, all from fs gained polyamic acid molecular weight too high due to.In other words, if can properly control the polyamic acid molecular weight, the polyimide film of the good rerum natura of tool can be provided just.
In addition, polyamic acid moisture absorption quite easily, and then polyamic acid is degraded with water molecule reaction, so need be stored in-20 ℃ of deepfreezes usually, carry out with reduction polymer DeR.
The problems referred to above continue perplexing the personage who is engaged in polyimide research for many years.Material behavior and operability, general just as fish and bear's paw, can't get both.The research and development achievement that the present invention promptly does to foregoing problems through special synthesis mode, can provide the polyimide film of the required rerum natura of tool, to meet the demand of industry under the situation of taking into account operability.
Summary of the invention
One object of the present invention is to provide a kind of precursor composition of polyimide, and it comprises the formed compound of dicarboxylic anhydride derivatives reaction that amido acid oligopolymer and an end have an ester group (C (O) OR) and a carboxyl (C (O) OH).
Another object of the present invention provides a kind of polyimide, and it utilizes the precursor composition polymerization of polyimide of the present invention and gets.
In first aspect of the present invention, provide a kind of in order to the precursor composition of polyimide to be provided, it comprises
(a) the amido acid oligopolymer of tool following formula (1)
(b) compound of tool following formula (2)
Wherein R is a unsaturated group for straight or branched alkyl, phenolic group or the ethene of 1 to 14 carbon atom of tool independently separately;
G and G
1Can be identical or different and independently be 4 valency organic groups separately;
P is the divalent organic group; And
M is 1 to 100 integer; And
Wherein component (a) is 0.8: 1 to 1.2: 1 with the mole ratio of component (b).
Another aspect of the present invention provides a kind of polyimide, and it utilizes the compsn of following ingredients to be polymerized:
(a) the amido acid oligopolymer of tool following formula (1)
(b) compound of tool following formula (2)
Wherein component (a) is 0.8: 1 to 1.2: 1 with the mole ratio of component (b); And R, G, G
1, P and m as stated.
Embodiment
A kind of precursor composition of polyimide, it comprises:
(a) the amido acid oligopolymer of a tool following formula (1)
and
(b) compound of a tool following formula (2)
Wherein
R is a unsaturated group for straight or branched alkyl, phenolic group or the ethene of 1 to 14 carbon atom of tool independently separately;
G and G
1Can be identical or different and independently be 4 valency organic groups separately;
P is the divalent organic group;
M is 1 to 100 integer, is preferably 5 to 50 integer; And
Wherein component (a) is 0.8: 1 to 1.2: 1 with the mole ratio of component (b), is preferably 0.9: 1 to 1.1: 1.
The straight or branched alkyl of 1 to 14 carbon atom of tool that is suitable for the substituent R of following formula (2) compound comprises:
Wherein n is 0 to 10 integer.One example it (but not as limit), the straight or branched alkyl of 1 to 14 carbon atom of this tool can be methyl, ethyl, n-propyl, sec.-propyl, 1-methyl-propyl, 2-methyl-propyl, normal-butyl, isobutyl-, new butyl, 1-methylbutyl, 2-methylbutyl, amyl group, hexyl, heptyl or octyl group etc.R can be a phenolic group independently separately also,
Like
or ethene is unsaturated group; This ethene is that unsaturated group is selected from: vinyl, allyl group, ethenylphenyl, allyl phenyl, propenyloxy group methyl, propenyloxy group ethyl, propenyloxy group propyl group, propenyloxy group butyl, propenyloxy group amyl group, propenyloxy group hexyl, metacryloxy methyl, metacryloxy ethyl, metacryloxy propyl group, metacryloxy butyl, metacryloxy amyl group, metacryloxy hexyl, like the group of tool following formula (7), and the group of tool following formula (3)
R wherein
1C for phenylene (claiming to stretch phenyl again), straight or branched
1-C
8The C of alkylidene group (claiming to stretch alkyl again), straight or branched
2-C
8Alkenylene (claiming to stretch thiazolinyl again), C
3-C
8The C of cycloalkylidene (claiming to stretch naphthenic base again) or straight or branched
1-C
8Hydroxyl alkylidene group (claim again hydroxyl stretch alkyl); And R
2Be hydrogen or C
1-C
4Alkyl.
Preferably, the substituent R of the contained formula of this precursor composition (2) compound independently does separately
According to the present invention, G and G
1Can be 4 identical or different valency organic groups, preferablely independently do separately
Wherein Y independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; And B is-CH
2-,-O-,-S-,-CO-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-.More preferably, this 4 valency organic group G and G
1Independently do separately
The contained divalent organic group P of the amido acid oligopolymer of formula of the present invention (1) does not have particular restriction, and generally speaking, this divalent organic group P is an aromatic group, preferablely independently does separately
Wherein, X independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl, and A be-O-,-S-,-CO-,-CH
2-,-OC (O)-or-CONH-.More preferably, this divalent organic group P independently does separately
Wherein, X such as preamble definition; And respectively do for oneself 1 to 3 integer of w and z, preferably, this divalent organic group P does
Optionally, the present composition further comprises a polar aprotic solvent.Preferably, this aprotic solvent is selected from: N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), N (DMF), DMSO 99.8MIN. (DMSO), toluene, YLENE and combination thereof.
The present composition can optionally comprise the known additive that can be used for preparing polyimide of those skilled in the art, one example it (but not as limit): leveling agent, skimmer, coupler, and light trigger etc.
Be applicable to that light trigger of the present invention can be (but not as limit) and is selected from following group: UVNUL MS-40, bitter almond oil camphor, 2-hydroxy-2-methyl-1-Propiophenone, 2; 2-dimethoxy-1; 2-phenylbenzene second-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide and combination thereof.
Coupler commonly used is selected from: 3-TSL 8330 (APrTMOS), 3-triamino propyl-triethoxysilicane (APrTEOS), 3-aminophenyl Trimethoxy silane (APTMOS), 3-aminophenyl triethoxyl silane (APTEOS) and combination thereof.
This case contriver finds; Be different from the precursor composition of prior art in order to the preparation polyimide, precursor composition of the present invention since the less and acidic group of molecular weight reduce, therefore more can moisture absorption; Even moisture absorption; Also more stable, so can under room temperature, preserve subsequent usely, need not to be stored in low temperature (as: subzero 20 ℃).
The method of can this technical field knowing prepares precursor composition of the present invention.One example it (but not as limit).Formula in the precursor composition of the present invention (1) amido acid oligopolymer can make tool formula H through following mode
2N-P-NH
2Diamines and the dicarboxylic anhydride of tool following formula (4), mix and react and get
Wherein G such as preamble definition.Preferably; Molecular weight big or small (promptly determining the m value) according to desires amido acid oligopolymer calculates required diamines consumption, and the diamines of this metering is dissolved in formation one solution in the polar aprotic solvent earlier; Add an amount of dicarboxylic anhydride again, react and make this formula (1) amido acid oligopolymer.One example it (but not as limit) can be dissolved in polarity, the aprotic solvent that is selected from diamines earlier: N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), N (DMF), DMSO 99.8MIN. (DMSO), toluene, YLENE and combination thereof.In this, the mole ratio of this diamines and this dicarboxylic anhydride is at 1: 0.8 to 1: 1.2, in preferable 1: 0.9 to 1: 1.1 scope.In 0 to 100 ℃ usually of the reaction of diamines and dicarboxylic anhydride is preferably under 0 to 50 ℃ the temperature and carries out, and lasts 5 to 12 hours usually.
In the step of above-mentioned preparation formula (1) amido acid oligopolymer, generally adopting the aromatic diacid acid anhydride is the acid of formula (4) dianhydride, and the example comprises (but being not limited to) pyromellitic dianhydride (PMDA), 4,4-two phthalandione dianhydrides (BPDA), 4,4-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5; 6-benzene tertacarbonic acid dianhydride (P3FDA), 1, two (trifluoromethyl)-2,3,5 of 4-, 6-benzene tertacarbonic acid dianhydride (P6FDA), 1-(3 ', 4 '-dicarboxyl phenyl)-1,3; 3-trimethylammonium indane-5,6-dicarboxylic acid dianhydride, 1-(3 ', 4 '-dicarboxyl phenyl)-1,3,3-trimethylammonium indane-6,7-dicarboxylic acid dianhydride, 1-(3 ', 4 '-dicarboxyl phenyl)-3-methyl indan-5; 6-dicarboxylic acid dianhydride, 1-(3 ', 4 '-dicarboxyl phenyl)-3-methyl indan-6,7-dicarboxylic acid dianhydride, 2,3,9,10-perylene tetracarboxylic dianhydride, 1,4; 5,8-naphthalene tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-1; 4,5,8-tetracarboxylic dianhydride, 2,3,6,7-Tetrachloronaphthalene-2,4; 5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 3,3 ', 4; 4 '-benzophenone tetracarboxylic dianhydride, 1,2 ', 3,3 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4; 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2,2 ', 3; 3 '-biphenyl tetracarboxylic dianhydride, 4,4 '-isopropylidene, two phthalandione dianhydrides, 3,3 '-isopropylidene, two phthalandione dianhydrides, 4,4 '-oxygen base, two phthalandione dianhydrides, 4,4 '-alkylsulfonyl, two phthalandione dianhydrides, 3,3 '-oxygen base, two phthalandione dianhydrides, 4; 4 '-methylene radical, two phthalandione dianhydrides, 4,4 '-sulfenyl, two phthalandione dianhydrides, 4,4 '-ethylene phthalandione dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1; 2,4,5-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, benzene-1; 2,3,4-tetracarboxylic dianhydride, pyridine-2,3,5,6-tetracarboxylic dianhydride and combination thereof.
Preferably, employing is selected from the aromatic diacid acid anhydride: pyromellitic dianhydride (PMDA), 4,4-two phthalandione dianhydrides (BPDA), 4; 4-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5; 6-benzene tertacarbonic acid dianhydride (P3FDA), 1, two (trifluoromethyl)-2,3 of 4-; 5,6-benzene tertacarbonic acid dianhydride (P6FDA) and combination thereof.In an embodiment, adopt pyromellitic dianhydride (PMDA).
Can adopt aromatic diamine that this technical field knows as formula H in aforesaid method
2N-P-NH
2(wherein P such as preamble definition) diamines.One example it (but not as limit) can adopt and be selected from diamines: 4, and 4 '-diaminodiphenyl oxide (ODA), Ursol D (pPDA), a dimethyl-benzidine (DMDB), two (trifluoromethyl) benzidine (TFMB), 3,3 '-dimethyl--4,4 '-benzidine (oTLD), 4; 4 '-octafluoro p-diaminodiphenyl (OFB), tetrafluoro-p-phenylenediamine (TFPD), 2,2 '-5,5 '-tetrachloro benzidine (TCB), 3,3 '-dichlorobenzidine (DCB), 2; 2 '-two (3-aminophenyl) HFC-236fa, 2,2 '-two (4-aminophenyl) HFC-236fa, 4,4 '-oxygen base-two [3-(trifluoromethyl) aniline, 3,5-diamino-phenylfluoroform (3; 5-diaminobenzotrifluoride), tetrafluoro-1,4-phenylenediamine (tetrafluorophenylenediamine), tetrafluoro--phenylenediamine, 1, two (4-the amino-benzene oxygen)-2-tributyl benzene (BATB) of 4-, 2,2 '-dimethyl--4; 4 '-two (4-amino-benzene oxygen) biphenyl (DBAPB), 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa (BAPPH), 2,2 '-two [4-(4-amino-benzene oxygen) phenyl] the norborneol alkane (BAPN) of 2-, 5-amino-1-(4 '-aminophenyl)-1,3; 3-trimethylammonium indane, 6-amino-1-(4 '-aminophenyl)-1,3,3-trimethylammonium indane, 4,4 '-methylene-bis (neighbour-chloroaniline), 3; 3 '-dichloro diphenylamine, 3,3 '-alkylsulfonyl pentanoic, 4,4 '-diaminobenzophenone, 1,5-diaminonaphthalene, two (4-aminophenyl) diethylsilane, two (4-aminophenyl) diphenyl silane, two (4-aminophenyl) ethyl phosphine oxide, N-(two (4-aminophenyl))-N-methylamine, N-(two (4-aminophenyl))-N-phenyl amine, 4; 4 '-methylene-bis (2-aminotoluene), 4,4 '-methylene-bis(2methoxyaniline), 5,5 '-methylene-bis (2-amino-phenol), 4; 4 '-methylene-bis (2-aminotoluene), 4,4 '-oxygen base two (2-anisidine), 4,4 '-oxygen base two (2-chloroaniline), 2; 2 '-two (4-amino-phenols), 5,5 '-oxygen base two (2-amino-phenol), 4,4 '-sulfenyl two (2-aminotoluene), 4; 4 '-sulfenyl two (2-anisidine), 4,4 '-sulfenyl two (2-chloroaniline), 4,4 '-alkylsulfonyl two (2-aminotoluene), 4; 4 '-alkylsulfonyl two (2-phenetidine), 4,4 '-alkylsulfonyl two (2-chloroaniline), 5,5 '-alkylsulfonyl two (2-amino-phenol), 3; 3 '-dimethyl--4,4 '-diaminobenzophenone, 3,3 '-dimethoxy-4 '; 4 '-diaminobenzophenone, 3,3 '-two chloro-4,4 '-diaminobenzophenone, 4; 4 '-benzidine ,-phenylenediamine, 4,4 '-methylene dianiline (MDA) (MDA), 4,4 '-sulfenyl pentanoic, 4; 4 '-alkylsulfonyl pentanoic, 4,4 '-isopropylidene pentanoic, 3,3 '-dimethoxy benzidine, 3; 3 '-dicarboxylate biphenyl amine, 2,4-tolyl diamines, 2,5-tolyl diamines, 2; 6-tolyl diamines ,-xylyl diamines, 2,4-diamino--5-toluene(mono)chloride, 2,4-diamino--6-toluene(mono)chloride and the combination.Preferably; Adopt 4; 4 '-diaminodiphenyl oxide (ODA), Ursol D (pPDA), a dimethyl-benzidine (DMDB), two (trifluoromethyl) benzidine (TFMB), 3; 3 '-dimethyl--4,4 '-benzidine (oTLD), 4,4 '-methylene dianiline (MDA) (MDA) or its combination.Wherein, in an embodiment, adopt 4,4 '-diaminodiphenyl oxide (ODA).
Can be as follows, the dicarboxylic anhydride through making a tool following formula (5) and the compound reaction of tool hydroxyl, with formula (2) compound that precursor composition of the present invention is provided:
G wherein
1Such as preamble definition.Preferably, earlier dicarboxylic anhydride is dissolved in the polar aprotic solvent, adds the compound of tool hydroxyl again, form formula (2) has ester group (C (O) OR) and carboxyl (C (O) OH) in dual-side compound with reaction.One example it (but not as limit) can be dissolved in dicarboxylic anhydride earlier and is selected from polarity, aprotic solvent: N-N-methyl 2-pyrrolidone N-(NMP), N,N-DIMETHYLACETAMIDE (DMAC), N (DMF), DMSO 99.8MIN. (DMSO), toluene, YLENE and combination thereof.In this, the consumption of the compound of dicarboxylic anhydride and tool hydroxyl is preferably in 1: 1.9 to 1: 2.1 the scope between mole ratio 1: 1.8 to 1: 2.5.Carry out under the temperature that this reaction is general in 50 to 90 ℃, preferable in 50 to 60 ℃ are carried out; Reaction lasts 1 to 3 hours usually.
Can be used for the compound of tool hydroxyl of the present invention, comprise alcohols, for example monohydroxy-alcohol, divalent alcohol or polyvalent alcohol are preferably monohydroxy-alcohol.Can be used for monohydroxy-alcohol of the present invention and do not have special limitation, can be chain hydrocarbon alcohol, aryl chain hydrocarbon alcohol or aryl alcohol.One example it (but not as limit), this monohydroxy-alcohol can be the straight or branched alkyl alcohol of 1 to 14 carbon atom of tool.For example:
Wherein, n is 1 to 10 integer.In this, the straight or branched alkyl alcohol of 1 to 14 carbon atom of this tool comprises that (but being not limited to) methylol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, 1-methyl-propyl alcohol, 2-methyl-propyl alcohol, normal-butyl are pure, isobutyl alcohol, new butyl alcohol, 1-methylbutyl alcohol, 2-methylbutyl alcohol, amyl group is pure, hexyl is pure, heptyl is pure, and octyl group alcohol.
The compound that can be used for the tool hydroxyl in the inventive method also can be dihydroxy-benzene; Like
or have can light sensitive group; This can light sensitive group can be ethene is unsaturated group, is preferably tool following formula (6) person:
Wherein, R
1C for phenylene, straight or branched
1-C
8The C of alkylidene group, straight or branched
2-C
8Alkenylene, C
3-C
8The C of cycloalkylidene or straight or branched
1-C
8Hydroxyl alkylidene group, and R
2Be hydrogen or C
1-C
4Alkyl.Preferably, this formula (6) compound is selected from: 2-hydroxyethyl vinylformic acid (HEA), 2-hydroxyethyl methylacrylic acid (HEMA), 2-hydroxypropyl vinylformic acid, 2-hydroxypropyl methylacrylic acid and combination thereof.More preferably, this formula (6) compound adopts 2-hydroxyethyl vinylformic acid (HEA), 2-hydroxyethyl methylacrylic acid (HEMA) and combination thereof.
Used formula (5) dicarboxylic anhydride in preparation formula (2) compound generally adopts the aromatic diacid acid anhydride, its described formula of optional preamble freely (4) dicarboxylic anhydride.In an embodiment, this formula (5) dicarboxylic anhydride is a pyromellitic dianhydride.
The contriver finds that prior art for preparing forms the method for the precursor composition of polyimide, needs the bigger polyamic acid of first synthetic molecular weight, in water or solvent, heats and degrades, and utilizes viscosity to control the molecular weight of being wished to get.This kind method often makes that water ratio is too high in the compsn, so need be stored in (as: subzero 20 ℃) under the low temperature, proceeds to slow down degraded, avoids molecular weight too small.And the present invention need not utilize the mode of degraded can effectively control the molecular weight of being wished to get, and is also more stable, can under room temperature, preserve subsequent use.
The present invention provides a kind of polyimide in addition, and the compsn that its utilization contains following ingredients is polymerized:
(a) the amido acid oligopolymer of tool following formula (1)
(b) compound of tool following formula (2)
Wherein R, G, G
1, P and m all such as preamble definition, and the mole ratio of the component in the said composition (a) and component (b) is 0.8: 1 to 1.2: 1, is preferably 0.9: 1 to 1.1: 1.
Under the situation of bound by theory not, polyimide of the present invention can be via making with method shown in the following formula:
In the compound method of existing polyimide, all need the polyamic acid of first synthetic macromolecule amount to be used as precursor, but because molecular weight is too high, and viscosity is too big, so that the operability variation, shortcomings such as leveling characteristics is bad are arranged when being easy to be coated with.In addition, tool is crossed the high-molecular weight polyamic acid when imidization, is prone to the shortening because of intermolecular interaction and molecular chain bond distance, produces great internal stress, causes institute's substrates coated film buckling deformation.In addition, the related solidification value of existing method needs up to 300 to 350 ℃ usually.On the other hand, existing polyimide is synthetic, the solid content when its polyreaction forms polyamic acid; Only approximately between 10% to 30%; So volumetric shrinkage is bigger than (shrinkable) after cyclisation, need repeatedly coating can reach the thickness of product requirement, increase the processing procedure difficulty.Moreover the precursor of existing polyimide is in the end during cyclodehydration, because of its viscosity is high, carrying out softly when roasting, and solvent and moisture are not volatile, so be prone to the generation bubble when in the end being roasted into film firmly.
Relatively; Polyimide of the present invention utilizes the dicarboxylic anhydride verivate polymerization of amido acid oligopolymer and formula (2), is characterized in the dicarboxylic anhydride verivate tool ester group (C (O) OR) of formula (2) and the end group of carboxyl (C (O) OH), is in the steady state (meta stable status) that is situated between; The amido acid oligopolymer generation reaction that therefore at room temperature can't have diamines with end; And because of amido acid oligomer molecules amount is low, so handling good, coating can reach smooth effect.When final curing (post cure); When being warming up to more than 100 ℃; The amido acid oligopolymer can begin to produce intramolecular cyclization, and the diamines of amido acid oligomer end also can be reduced into acid anhydrides simultaneously with the end group of ester group (C (O) OR) and carboxyl (C (O) OH); The molecule of further reactive polymeric Cheng Gengda, and then condensation provides the polyimide of tool excellent heat character, mechanical properties and tensile property.Compared to prior art, because containing amido acid oligopolymer (viscosity is less), use works as precursor, viscosity is less, but not the bigger high molecular polyamic acid of viscosity, so when coating, can appear than high-leveling and operability.
In addition; Because the molecule of the contained component of the present composition is less, so when carrying out imidization, can avoid because of the high internal stress due to interaction between polymer and molecular chain bond distance's the shortening; And contained amido acid oligopolymer is earlier through intramolecular cyelization; Carry out intermolecular polymerization and cyclic action again,, have the not advantage of warpage so can effectively reduce the remaining internal stress of polyimide.In addition, the present composition can be cured reaction (about 250 ℃ to 300 ℃) under low relatively temperature, more can reduce running cost.
Polyimide of the present invention; Because its precursor composition has high solids content (high solidcontent); Approximately between 25% to 50%; So can reduce the consumption of solvent, shorten the soft roasting time and reduce soft roasting temperature, and it is fast and be reduced to and reach the required advantages such as coating number of times of product requirement thickness to have drying and forming-film speed.
Moreover general high molecular polymerization all can add some monomers or short chain oligomer, makes molecule and intermolecular energy form interlinkage (crosslinking).When precursor composition formula of the present invention (2) but compound contains the sensitization polymer-based group, and because molecule is little, thus can the oneself when solidifying crosslinked, form stable and the stronger reticulated structure of toughness.Therefore, the present invention need not to use extra unsaturated monomer or oligomer, and this is another advantage that the present invention and prior art are compared.
As after attach shown in the embodiment, polyimide provided by the present invention is compared technological in the past obtained person, can represent preferable thermal properties, mechanical properties and tensile property.
Below in conjunction with specific embodiment, further illustrate the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Ratio and per-cent are based on weight, unless stated otherwise.
Embodiment
Embodiment 1
The pyromellitic dianhydride (pyromellitic dianhydride, hereinafter referred is PMDA) of 2.181 grams (0.01 mole) is dissolved in the N-methyl Pyrrolidine ketone (N-methyl-2-pyrrolidinone of 200 grams; This paper is designated hereinafter simply as NMP) in, heating gained mixture to 50 ℃ and reaction were stirred two hours.Splash into the 2-hydroxyethyl vinylformic acid (2-Hydroxyethyl acrylate, hereinafter referred is HEA) of 2.322 grams (0.02 mole), react stirring two hours down for 50 ℃ in holding temperature.Thereafter, with 4 of 20.024 grams (0.1 mole), 4 '-diaminodiphenyl oxide (4; 4 '-Diamino-diphenyl ether, hereinafter referred is ODA) add in the solution, after treating to dissolve fully; The PMDA that adds 18.0216 grams (0.09 mole) again reacts stirring six hours down for 50 ℃ in holding temperature.
Comparative example 1
The ODA of 20.024 grams (0.1 mole) is dissolved among the NMP of 200 grams; Ice bath to 0 ℃ and reaction were stirred one hour; Thereafter the anhydride phthalic acid (phthalicanhydride) that adds 0.29 gram (0.002 mole); Question response stirred after one hour, slowly added the PMDA of 21.59 grams (0.099 mole) again, held temperature reaction stirring and got final product in 12 hours.
Embodiment 2
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into 2-hydroxyethyl methylacrylic acid (the 2-hydroxyethyl methacrylate of 2.60 grams (0.02 mole); Hereinafter referred is HEMA), hold temperature and react stirring two hours down for 50 ℃.ODA with 20.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, holds to react under warm 50 ℃ and stirs six hours.
Embodiment 3
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.Ursol D (para-phenylenediamine, hereinafter referred is pPDA) with 10.814 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, holds to react under warm 50 ℃ and stirs six hours.
Embodiment 4
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.PPDA with 10.814 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, holds to react under warm 50 ℃ and stirs six hours.
Embodiment 5
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reacts stirring two hours down.Slowly splash into the HEA of 2.322 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.Again with dimethyl-benzidine (dimethyl-dibenzilidene between 21.23 grams (0.1 mole); Hereinafter referred is DMDB) add in the solution; After treating to dissolve fully, add the PMDA of 18.0216 grams (0.09 mole) again, hold temperature and react stirring six hours down for 50 ℃.
Embodiment 6
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.DMDB with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, holds to react under warm 50 ℃ and stirs six hours.
Embodiment 7
The PMDA of 2.181 grams (0.1 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.Again with 21.23 the gram (0.1 mole) adjacent dimethyl-benzidine (o-Tolidine; Hereinafter referred is oTLD) add in the solution, after treating to dissolve fully, add the PMDA of 18.0216 grams (0.09 mole) again, hold temperature and react stirring six hours down for 50 ℃.
Embodiment 8
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.602 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.OTLD with 21.23 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, holds to react under warm 50 ℃ and stirs six hours.
Embodiment 9
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEA of 2.322 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.Again with two (trifluoromethyl) benzidine (meta-bis (trifluoromethyl)-benzilidine between 32.024 grams (0.1 mole); Hereinafter referred is TFMB) add in the solution; After treating to dissolve fully; The PMDA that adds 18.0216 grams (0.09 mole) again holds temperature and reacts stirring six hours down for 50 ℃.The TFMB that adds 3.202 grams (0.01 mole) at last again stirs after one hour and gets final product.
Embodiment 10
The PMDA of 2.181 grams (0.01 mole) is dissolved among the NMP of 200 grams, is heated to 50 ℃ and reaction and stirred two hours.Slowly splash into the HEMA of 2.60 grams (0.02 mole), hold temperature and react stirring two hours down for 50 ℃.TFMB with 32.024 grams (0.1 mole) adds in the solution again, after treating to dissolve fully, adds the PMDA of 18.0216 grams (0.09 mole) again, holds to react under warm 50 ℃ and stirs six hours.
The polyimide physical property measurement
At first utilize the molecular weight related data of the HT-GPC apparatus measures gained polyimide of Waters Model:2010, as shown in table 1 below:
Table 1
| Test product | M n | M w | MP (1) | PD (2) |
| The present invention (embodiment 1) | 29,846 | 55,182 | 38,041 | 1.848880 |
| Prior art (comparative example 1) | 106,828 | 263.324 | 266,462 | 2.464926 |
(1)Peak molecular weight
(2)Polymer dispersed property (polydispersity)
Can be known that by table 1 data the inventive method can provide tool the polyimide dispersed than low-grade polymer, that is the molecular weight ranges narrow distribution of obtained polyimide, height molecular weight differences be apart from less, its quality is preferable.
Get embodiment 1 and comparative example 1 resulting composition, after giving solidification treatment and obtaining polyimide film, macromolecular material is made film with the mode of rotary coating.Further toast again, and heating curve is divided into three sections with baking oven.Be respectively 150 ℃/60min, 250 ℃/60min and 350 ℃/120min, after its heat-up rate was 2 ℃/min, cooling was risen again and is promptly carried out physical property measurement.
Then, utilize omnipotent puller system (the hot bending determinator Model 9102 that HTC produces) to carry out the test of polyimide film mechanical properties.The gained polyimide film is cut into the size of 12cm * 10cm * 0.25mm; Be placed on this omnipotent puller system; Under 23 ℃ of temperature, carry out, speed setting is 10mm/min, respectively to making tensile test by embodiment 1 compsn and comparative example 1 compsn gained polyimide film; To measure different tensile strength, the result is as shown in table 2:
Table 2
| Test product | Draw anti-intensity (MPa) | Extended length per-cent (%) |
| The present invention (embodiment 1) | 92.2 | 13.31％ |
| Prior art (comparative example 1) | 74.3 | 5.415％ |
Show and to know that polyimide film provided by the present invention can represent comparatively excellent tensile strength and elongation by table 2 result.
The above embodiments only are used for the embodiment of the present invention of giving an example, and explain technical characterictic of the present invention, are not to be used for limiting protection category of the present invention.Any those skilled in the art can unlabored change or the arrangement of the isotropism scope that all belongs to the present invention and advocated, and rights protection scope of the present invention should be as the criterion with claim.
Claims (12)
1. one kind in order to provide the precursor composition of polyimide, and it comprises
(a) the amido acid oligopolymer of tool following formula (1)
(b) compound of tool following formula (2)
Wherein R independently does separately---CH
3,---CH
2CH
3,---CH
2CH
2CH
3,
G and G
1Can be identical or different and independently be 4 valency organic groups separately;
P is the divalent organic group; And
M is 1 to 100 integer; And
Wherein component (a) is 0.8: 1 to 1.2: 1 with the mole ratio of component (b).
2. compsn as claimed in claim 1 is characterized in that, this 4 valency organic group is selected from:
Wherein Y independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; And B is-CH
2-,-O-,-S-,-CO-,-SO
2-,-C (CH
3)
2-or-C (CF
3)
2-.
3. compsn as claimed in claim 2 is characterized in that, this 4 valency organic group is selected from:
4. compsn as claimed in claim 1 is characterized in that, this divalent organic group is selected from:
Wherein X independently is hydrogen, halogen, C separately
1-C
4Alkyl or C
1-C
4Perfluoroalkyl; A is-O-,-S-,-CO-,-CH
2-,-OC (O)-or-CONH-; And respectively do for oneself 1 to 3 integer of w and z.
5. compsn as claimed in claim 4 is characterized in that, this divalent organic group is selected from:
6. compsn as claimed in claim 1 is characterized in that, m is 5 to 50 integer.
7. compsn as claimed in claim 1 is characterized in that, component (a) is 0.9: 1 to 1.1: 1 with the mole ratio of component (b).
8. compsn as claimed in claim 1 is characterized in that, also comprises a polar aprotic solvent, and this solvent is selected from: N-N-methyl 2-pyrrolidone N-, N,N-DIMETHYLACETAMIDE, N, DMSO 99.8MIN., toluene, YLENE and combination thereof.
9. compsn as claimed in claim 1; It is characterized in that; Also comprise a coupler, this coupler is selected from: 3-TSL 8330,3-triamino propyl-triethoxysilicane, 3-aminophenyl Trimethoxy silane, and 3-aminophenyl triethoxyl silane and combination thereof.
10. compsn as claimed in claim 1; It is characterized in that also comprise a light trigger, this light trigger is selected from: UVNUL MS-40, bitter almond oil camphor, 2-hydroxy-2-methyl-1-Propiophenone, 2; 2-dimethoxy-1; 2-phenylbenzene second-1-ketone, 1-hydroxyl-cyclohexyl-phenyl ketone, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide and combination thereof.
11. a polyimide, it utilizes the compsn of following ingredients to be polymerized:
(a) the amido acid oligopolymer of tool following formula (1)
(b) compound of tool following formula (2)
Wherein component (a) is 0.8: 1 to 1.2: 1 with the mole ratio of component (b); And R, G, G
1, P and m such as claim 1 definition.
12. polyimide as claimed in claim 11 is characterized in that, the mole ratio of the mole number of component (a) and component (b) is 0.9: 1 to 1.1: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127268A (en) * | 1995-01-18 | 1996-07-24 | 中国科学院长春应用化学研究所 | Preparation method of polyimide and precursor solution thereof |
| CN1206724A (en) * | 1997-07-24 | 1999-02-03 | 中国科学院长春应用化学研究所 | Process for preparing ester type photosensitive polyimide |
| CN1301779A (en) * | 1999-12-29 | 2001-07-04 | 中国科学院长春应用化学研究所 | Method for preparing special biphenyl polyimide plastic for super high temperature engineering |
| CN1389494A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院化学研究所 | Thermosetting polyimide base resin and its prepn. |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127268A (en) * | 1995-01-18 | 1996-07-24 | 中国科学院长春应用化学研究所 | Preparation method of polyimide and precursor solution thereof |
| CN1206724A (en) * | 1997-07-24 | 1999-02-03 | 中国科学院长春应用化学研究所 | Process for preparing ester type photosensitive polyimide |
| CN1301779A (en) * | 1999-12-29 | 2001-07-04 | 中国科学院长春应用化学研究所 | Method for preparing special biphenyl polyimide plastic for super high temperature engineering |
| CN1389494A (en) * | 2001-06-04 | 2003-01-08 | 中国科学院化学研究所 | Thermosetting polyimide base resin and its prepn. |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平11-100443A 1999.04.13 |
| JP特开平11-15152A 1999.01.22 |
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