CN104163923A - Polyimide resin containing maleic anhydride and manufacture method thereof - Google Patents
Polyimide resin containing maleic anhydride and manufacture method thereof Download PDFInfo
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- CN104163923A CN104163923A CN201310183875.5A CN201310183875A CN104163923A CN 104163923 A CN104163923 A CN 104163923A CN 201310183875 A CN201310183875 A CN 201310183875A CN 104163923 A CN104163923 A CN 104163923A
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Abstract
The invention discloses a polyimide resin containing maleic anhydride and a manufacture method thereof. The structural formula of the polyimide resin containing maleic anhydride is represented in the description; wherein the X represents a carbon chain group containing at least 10 carbon atoms, a group containing a phenyl ring, or a structure containing a carbon chain with at least 10 carbon atoms and a phenyl ring group, and the m, n, and l are all integers and are not less than 1.
Description
Technical field
The present invention is relevant with polyimide, is particularly to a kind of polyimide resin containing maleic anhydride.
Background technology
The thermosetting resin synthetics of good heat resistance, thermosetting and low water absorbable is the important materials of industry member development always, and in macromolecule resin, one of material of thermotolerance the best is polyimide compound.The made film of thermosetting polyimide resin constituent can be processed to printing distributing board, face heating element, electromagnetic shielding material, flat cable etc.
Polyimide has the performances such as good thermotolerance, mechanical properties and resistance to chemical reagents, therefore, is extensively used in aerospace field, field of electronic materials etc.Generally by user, be mostly aromatic polyimide at present.Most aromatic polyimide is insoluble to solvent and is non-thermal plasticity, is difficult to processing.The precursor of polyimide is polyamic acid, and it is solvent-soluble, therefore take to become desired shape with polyamic acid solution, then makes the method for its imidization.
Yet, imidization reaction is accompanied by disengaging, the evaporation of water, and the temperature of reaction when hot-imide also reaches more than 300 ℃, and this temperature far surpasses the boiling point of water, when thick film shape molding is shaped, the unfavorable condition relevant with superficiality such as easily heave.Therefore, operational condition such as Temperature Setting during shaping etc. is difficult to suitable selection.Omit the goods of the polyamic acid of this imidization reaction, cannot there is the distinctive thermotolerance of polyimide.Again, polyamic acid solution is easily hydrolysis under water exists, therefore its store method is inconvenient.
Polyimide is useful for being applied in electronic applications, and it can be used in insulating film or the protection be used as on semiconductor device and film.Especially, all aromatic polyimide is due to its excellent thermotolerance, mechanical characteristics, electrical characteristic, large for the contribution of the densification of flexible circuit board or unicircuit etc., many mechanizations etc.
So, when forming the interlayer dielectric of fine circuits or protection and film, be to use polyimide precursor solution in the past.Polyimide precursor solution so, known have polyamic acid (PAA) solution that diamine compound is reacted with tetracarboxylic dianhydride and obtain, or the various solution that contain poly amic acid ester, polyamic acid trimethylsilyl group, polyamic acid two (diethylamide) etc.These polyimide precursor solutions, be the polymers soln of high-polymerization degree, when obtaining polyimide coating film from polymers soln, generally by this polymers soln being coated on the base materials such as copper, glass and heating, and implement removing and imidization of solvent, obtain polyimide coating film.
But, while applying the polymers soln of high-polymerization degree, because its polymerization degree is high, in order to make solution become the viscosity that can be coated with, have the essential problem that reduces solute concentration.Again, if raising productivity and improve solute concentration, the viscosity of solution can increase, and has the problem that cannot be coated with.In addition,, if solute concentration is high and make polymer low-molecular quantize in order to make it have the viscosity that can be coated with, have the problem of filming that cannot obtain mechanicalness, excellent heat resistance.Moreover the polymers soln utmost point is difficult to maintaining preservation for a long time under the state of its polymerization degree.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of polyimide resin containing maleic anhydride, by following structural formula, represented,
Wherein X is for representing X for representing carbochain group containing 10 above carbon atoms, containing the group of phenyl ring or containing 10 above carbochains of carbon atom and the structure of phenyl ring group, m, n and l are all integer and are more than or equal to 1.
The invention provides a kind of polyimide resin containing maleic anhydride, it is to take polymaleic anhydride as main chain, the structure of the pi that side chain contains short chain section.
The manufacture method that the invention provides a kind of polyimide resin containing maleic anhydride, comprises following steps: (a) make dianhydride react in a solvent with diamines, to prepare polyamic acid solution; (b) with polymaleic anhydride, react with the polyamic acid solution that step (a) obtains, to prepare the side chain graft of polymaleic anhydride have-NH-CO-functional group and carboxylic acid group's oligomerization compound; And (c) add catalyzer to carry out chemical cyclization reaction.
As optimal technical scheme, the manufacture method of the above-mentioned polyimide resin containing maleic anhydride, is more contained in step (c) before, and those polymaleic anhydride of side chain graft have-NH-CO-functional group and carboxylic acid group's oligomerization compound are carried out a bridge formation reaction.
Preferably, in the manufacture method of the above-mentioned polyimide resin containing maleic anhydride, this solvent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or diethylene glycol monomethyl ether one of them or two or more arbitrary combination.
Preferably, the catalyzer of step (c) is pyridine or the pyridine of 3-methyl arsenic.
As optimal technical scheme, this step (c) more adds dewatering agent.
Preferably, this dewatering agent is acetic anhydride, propionic anhydride, butyryl oxide or valeric anhydride one of them or its mixture; Aromatic monocarboxylate's acid anhydride; The mixture of aliphatic series acid anhydride and aromatics acid anhydride; Carbodiimide; Or aliphatic ketenes.
The present invention also provides a kind of film, is to be impregnated in above-mentioned should forming containing the polyimide resin of maleic anhydride by a woven fiber glass.
The present invention also provides a kind of copper clad laminate, by least one Copper Foil and above-mentioned film pressing, is formed.
The present invention can reach following technique effect:
The invention provides a kind of polyimide resin containing maleic anhydride, main chain is polymaleic anhydride, side chain makes its end have crosslinkable reactive functional group in the mode of grafting, the structure of the pi that wherein side chain contains short chain section, the short polymerization degree that reduces of side chain, avoid polymers soln excessively sticky, be difficult for the problem of coating film forming.
The invention provides a kind of manufacture method of polyimide resin, by using chemical imidization method, can avoid using the easy phenomenon of heaving in thick film shape molding surface of thermal cyclization method.
The invention provides a kind of film, there is excellent thermotolerance, mechanical characteristics, and can be applicable to the insulating layer material of copper clad laminate and circuit card.
The invention provides a kind of copper clad laminate, there is excellent thermotolerance, mechanical characteristics, after engaging with electronic component under the harsh environment such as high temperature, high humidity operation and can not affect its quality.
Accompanying drawing explanation
Fig. 1 is the manufacture method flow chart of steps of polymaleic anhydride-pi resin of one embodiment of the invention.
Fig. 2 is the manufacture method of the polyimide resin of one embodiment of the invention, and wherein with 4,4 '-oxygen pentanoic reacts to prepare polyamic acid solution with maleic anhydride monomer.
Fig. 3 is the manufacture method of the polyimide resin of another embodiment of the present invention, and wherein with 4,4 '-oxygen pentanoic reacts to prepare polyamic acid solution with maleic anhydride monomer, and diamines and polymaleic anhydride forming section bridging structure.
Fig. 4 is the measurement of the glass transition temp of polymaleic anhydride-pi resin of the present invention.
Fig. 5 is the measurement of the 5wt% thermogravimetric loss temperature of polymaleic anhydride-pi resin of the present invention.
Fig. 6 is used colloid permeation chromatography instrument to measure the molecular weight analyse figure of polymaleic anhydride-pi resin of the present invention.
Fig. 7 represents the IR spectrogram of polymaleic anhydride-pi of the present invention acid.
Fig. 8 represents the IR spectrogram of polymaleic anhydride-polyimide resin of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described, can be implemented, but illustrated embodiment is not as a limitation of the invention so that those skilled in the art can better understand the present invention also.
Please refer to Fig. 1, the manufacture method of the polyimide resin of one embodiment of the invention, comprises following steps: step S10, and the dianhydride dissolving with molal quantity reacts in solvent with diamines, to prepare polyamic acid solution; Step S12, reacts with the polyamic acid solution that step S10 obtains with polymaleic anhydride, to prepare the side chain graft of polymaleic anhydride have-NH-CO-functional group and carboxylic acid group's oligomerization compound; Step S14, makes the reaction of building bridge of the polymaleic anhydride of side chain graft have-NH-CO-functional group and carboxylic acid group's oligomerization compound; And step S16, add catalyzer to carry out chemical cyclization reaction.In another embodiment, can omit step S14, make the polymaleic anhydride of side chain graft have-NH-CO-functional group in step S12 and carboxylic acid group's oligomerization compound carry out the chemical cyclization reaction of step S16 and the reaction of building bridge.
Then, please refer to Fig. 2, Fig. 2 is the manufacture method of the polyimide resin of one embodiment of the invention, and wherein with 4,4 '-oxygen pentanoic reacts to prepare polyamic acid solution with maleic anhydride monomer.In one embodiment, first with 4,4 '-oxygen pentanoic (as structural formula (1)) reacts to prepare polyamic acid solution (as structural formula (3)) with maleic anhydride monomer (as structural formula (2)).Then, add polymaleic anhydride to react with the polyamic acid solution (as structural formula (3)) of acquisition, to prepare the side chain graft of polymaleic anhydride have-NH-CO-functional group and carboxylic acid group's oligomerization compound (as structural formula (4)).Then, add catalyzer, the side chain graft of polymaleic anhydride is had-and NH-CO-functional group and carboxylic acid group's oligomerization compound (as structural formula (4)) carries out chemical cyclization reaction, obtains to take the polyimide resin (as structural formula (5)) that polymaleic anhydride is main chain.
Polyimide resin main chain of the present invention is polymaleic anhydride, side chain makes its end have crosslinkable reactive functional group in grafting mode, the pi structure that wherein side chain contains short chain section, use has the acid anhydrides of two keys as end-blocking, and this pair of key can form in heat-processed the structure of cross-linked network.Wherein, first pi on side chain is used diamines and acid anhydrides, make it be reacted into pi acid, on the side chain due to this resin, contain the reactive functional group of thermally cross-linkable, so cannot adopt general direct heating, to approximately 300 ℃, pi acid cyclization is become to pi.Therefore, the present invention uses chemical imidization method, selects suitable alkali as catalyst and adds dewatering agent, 100 ℃ of reactions approximately 4 hours, can form soluble poly maleic anhydride-pi resin.
In order further to improve thermotolerance, can suitably select end-blocking ratio, part leaves the structure of two diamines, this diamines can with polymaleic anhydride forming section bridging structure, in heat embrittlement process, carry out so-called IPN cross-linked network, as shown in Figure 3.Fig. 3 is the manufacture method of the polyimide resin of another embodiment of the present invention, and wherein with 4,4 '-oxygen pentanoic reacts to prepare polyamic acid solution with maleic anhydride monomer, and diamines and polymaleic anhydride forming section bridging structure.First, as the step of Fig. 2 is manufactured the side chain graft have-NH-CO-functional group of polymaleic anhydride and carboxylic acid group's oligomerization compound (as structural formula (4)).Then, the polymaleic anhydride (as structural formula (4)) of side chain graft have-NH-CO-functional group and carboxylic acid group's oligomerization compound and the polymaleic anhydride (as structural formula (4-1)) of another side chain graft have-NH-CO-functional group and carboxylic acid group's oligomerization compound being built bridge reacts and forms the polymaleic anhydride (as structural formula (4-2)) with the side chain graft have-NH-CO-functional group of bridging structure and carboxylic acid group's oligomerization compound.Then, add catalyzer, the polymaleic anhydride (as structural formula (4-2)) of the side chain graft have-NH-CO-functional group who makes to have bridging structure and carboxylic acid group's oligomerization compound is carried out chemical cyclization reaction, obtains to take the polyimide resin (as structural formula (5-1)) that polymaleic anhydride is main chain.
Because this resin has the two keys containing high crosslink density; wherein part acid anhydrides can form acidic group (COOH) by hydroxy (OH), the hard type protection film that the minus photoresistance polymer that therefore can be widely used in general cold coating, can develop, the resin that the impregnation of printed circuit board (PCB) glass-fiber-fabric is used and flat-panel screens are used.
In the present invention, the method for making of polyamic acid is to make acid anhydrides and diamine reactant form contain-NH-CO-functional group and carboxylic acid group's oligomerization compound, now select suitable acid anhydrides to work as END CAPPED GROUP, this END CAPPED GROUP has two keys and can be used as crosslinked using, then by after polymaleic anhydride and have-NH-CO-functional group and carboxylic acid group's few polymer reaction, carry out again so-called chemical imidization reaction, can form crosslinkable polymaleic anhydride-pi resin, this resin has the features such as thermotolerance, mechanical properties, resistance to chemical reagents after heat embrittlement is processed.And, alleged cyclization in the present invention, be further make this-NH-CO-functional group and this carboxylic acid group carry out dehydrating condensation and form the process of cyclic group, is also called sub-amidate action.
In the present invention, the method for making of polyamic acid is to make acid anhydrides and diamine reactant, prepares polyamic acid and can use dicarboxylic anhydride in the present invention, and the example is such as but not limited to following compound, maleic anhydride, the maleic anhydride being substituted, Tetra Hydro Phthalic Anhydride, the Tetra Hydro Phthalic Anhydride being substituted, methylene Tetra hydro Phthalic anhydride, the methylene Tetra hydro Phthalic anhydride being substituted etc., the two acid anhydrides of aromatics are pyromellitic acid dianhydride (PMDA) for example, 4,4-, bis-phthalandione dianhydrides (BPDA), 4,4-hexafluoroisopropyli,ene, two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P3FDA), Isosorbide-5-Nitrae-bis-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P6GDA), 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, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid dianhydride, 2,6-dichloronaphtalene-Isosorbide-5-Nitrae, 5,8-tetracarboxylic dianhydride, 2,7-dichloronaphtalene-Isosorbide-5-Nitrae, 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, pyrazine-2,3,5,6-tetracarboxylic dianhydride etc., maleic anhydride preferably wherein, pyromellitic acid dianhydride (PMDA), 4,4-, bis-phthalandione dianhydrides (BPDA), 4,4-hexafluoroisopropyli,ene, two phthalandione dianhydrides (6FDA), 1-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P3FDA), Isosorbide-5-Nitrae-bis-(trifluoromethyl)-2,3,5,6-benzene tertacarbonic acid dianhydride (P6GDA).
The diamines example of preparing polyamic acid in the present invention can be given an example as (but being not limited to) aromatics diamine for example 4,4'-oxygen base pentanoic (ODA), 5-amido-1-(4'-aminocarbonyl phenyl)-1,3,3-trimethylammonium indane, 6-amido-1-(4'-aminocarbonyl phenyl)-1,3,3-trimethylammonium indane, 4,4'-methylene-bis (o-chloroaniline), 3,3'-dichloro diphenylamine, 3,3'-sulfonyldianiline, 4,4'-, bis-aminobenzophenones, 1,5-, bis-amido naphthalenes, two (4-aminocarbonyl phenyl) diethylsilane, two (4-aminocarbonyl phenyl) diphenyl silane, two (4-aminocarbonyl phenyl) ethyl phosphine oxide, N-(two (4-aminocarbonyl phenyl))-N-methylamine, N-(two (4-aminocarbonyl phenyl))-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-phenol), 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'-bis-aminobenzophenones, 3,3'-dimethoxy-4 ', 4'-bis-aminobenzophenones, 3,3'-bis-is chloro-4,4'-bis-aminobenzophenones, 4,4'-benzidine, m-phenylenediamine, p-phenylenediamine, 4,4'-methylene dianiline (MDA), 4,4'-sulfenyl pentanoic, 4,4'-sulfonyldianiline, 4,4'-isopropylidene pentanoic, 3,3'-tolidine, 3,3'-dimethoxy benzidine, 3,3'-dicarboxylate biphenyl amine, 2,4-tolyl diamines, 2,5-tolyl diamines, 2,6-tolyl diamines, m-xylyl diamines, 2,4-, bis-amidos-5-toluene(mono)chloride, 2,4-, bis-amidos-6-toluene(mono)chloride etc.Preferably 4,4'-oxygen base pentanoic (ODA).
The polyimide precursor resin solution of the present embodiment is that the polyimide precursor resin representing with above formula (1) is dissolved in to the person of forming in solvent.At this, solvent if can dissolve with the resin of formula (1) expression without particular limitation of, such as non-proton property polar compound, ether based compound, water-soluble alcohol based compound, water-insoluble alcohol based compound, ketone based compound etc.
Non-proton property polar compound, particularly, such as: N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), hexamethyl phosphoric triamide etc.
Ether based compound is for example: 2-methyl cellosolve, cellosolvo, 2-(methoxymethoxy) ethoxy ethanol, 2-isopropoxide ethanol, butoxy ethanol, tetrahydrofurfuryl alcohol, Diethylene Glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, Triethylene glycol ethyl ether, TEG, 1-methoxy-2-propanol, 1-oxyethyl group-2-propyl alcohol, dipropylene glycol, dipropylene glycol monomethyl ether, DPE, Tripropylene glycol monomethyl Ether, polyoxyethylene glycol, polypropylene glycol, tetrahydrofuran (THF), 1, 2-glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether etc.
Water-soluble alcohol based compound, for example: methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, the 3rd butanols, ethylene glycol, 1,2-PD, 1,3-PD, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,3-butanediol, 1,5-PD, 2-butylene-1,4-glycol, 2-methyl-2,4-pentanediol, 1,2,6-hexanetriol, diacetone alcohol etc.Water-insoluble alcohol based compound such as phenylcarbinol etc.
Ketone based compound for example 1,5,5-trimethylammonium-3-pimelinketone etc.Moreover, other solvents such as gamma-butyrolactone etc.Above-mentioned solvent can be used separately also and can be use mixing two or more.
Above solvent, with regard to independent solvent, better use is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide, diethylene glycol monomethyl ether for example; With regard to mixed solvent, combinations such as N-Methyl pyrrolidone and diethylene glycol monomethyl ether, N-Methyl pyrrolidone and methyl alcohol, N-Methyl pyrrolidone and 2-methyl cellosolve of better use.
The content of solvent is that 70 ~ 90 quality % are better for the resinous principle that contains polyimide precursor resin.By using content, be the solvent of 70 ~ 90 quality %, can become the varnish viscosity of coating excellence.
" dianhydride " used herein refers to comprise its precursor or derivative, and it can non-ly be dianhydride technically, but can be with diamine reactant to form polyamic acid (polyamic acid), and polyamic acid can be then through being converted into polyimide." diamines " used herein refers to comprise its precursor or derivative, and it can non-ly be diamines technically, but with two anhydride reactants to form polyamic acid, polyamic acid can be then through being converted into polyimide.
" polyamic acid " used herein refers to comprise any polyimide precursor material, and it is derived from the combination of dianhydride and diamine monomer or its functionality equivalent, and can be converted into polyimide via chemical conversion program.
" prepolymer " used herein censures relatively low-molecular-weight polyamic acid solution, and it is prepared by excessive diamines that this solution is used in stoichiometry, take to obtain viscosity and moor the solution of (Poise) as about 50-100.
It is polyimide that " chemical conversion " used herein or " through chemical conversion " representative is used catalyzer (accelerator) or dewatering agent (or both all use) to transform this polyamic acid, and refers to comprise the polyimide through part chemical conversion.
" conversion chemical " used herein or " imidization chemical " representative can change into polyamic acid the catalyzer (accelerator) of polyimide and/or polyamic acid can be changed into the dewatering agent of polyimide.
When specifying content, concentration or other numerical value or parameter to be enumerating of a scope, preferred range or upper preferred values and lower preferred values, should be understood as specific exposure by the formed all scopes of any pairing of any range limit or preferred values and any scope lower limit or preferred values, no matter whether those scopes disclose respectively.If narrate a numerical range herein, except as otherwise noted, this scope is intended to comprise end points and all integers and the mark in it of this scope.Category of the present invention is also not intended to be defined as definition described particular value during one scope.
In certain embodiments, this polyimide through chemical conversion is made by polyamic acid solution and being changed into polyamic acid to the catalyzer of polyimide or step that dewatering agent mixes.In chemical conversion program, this polyamic acid solution impregnated in or be mixed in conversion (imidization (imidization)) chemical.In one embodiment, this conversion chemical is triamine catalyst (accelerator) and acid anhydride dehydrating material.In this embodiment, this acid anhydride dehydrating material is acetic anhydride, and it is everlasting and uses with molar excess with respect to the amido acid in this polyamic acid (amide acid) group, and every equivalent polyamic acid is generally approximately 1.2 to 2.4 moles.In one embodiment, use the triamine catalyst of a great deal of.
Surrogate as the acetic anhydride of this acid anhydride dehydrating material comprises: other aliphatic acid anhydrides of i., for example propionic anhydride, butyryl oxide, valeric anhydride and its mixture; Ii. aromatic monocarboxylate's acid anhydride; Iii. the mixture of aliphatic acid anhydride and aromatics acid anhydride; Iv. carbodiimide (carbodimides); And v. aliphatic series ketenes (ketenes can be considered the extremely derivative carboxylic acid anhydride of acid of dehydration).
In one embodiment, this triamine catalyst is pyridine and 3-methyl arsenic pyridine (beta-picoline), and its consumption is similar to the mole number of acid anhydride dehydrating material conventionally.Can use lower or higher amount, this depends on desired transformation efficiency and catalyzer used.Also can use and have and the rough identical active tertiary amine of this pyridine and Beta picoline.These tertiary amines comprise 2-picoline (alpha picoline); 3,4-, bis-picolins; 3,5-, bis-picolins; 4-picoline; 4-isopropyl pyridine; N, N-dimethyl benzyl amine; Isoquinoline 99.9; 4-benzyl-pyridine, N, N-dimethyl amino dodecane, triethylamine and fellow.For other different catalysts of imidization, in this technical field, be prior art, imidazoles for example, and can use according to the present invention.
This conversion chemical is conventionally in about room temperature or react higher than room temperature, so that polyamic acid is converted into polyimide.In one embodiment, this chemical conversion occurs in 15 ℃ to 120 ℃ of temperature, and this reaction at comparatively high temps for being relatively slow at lesser temps very fast.
In one embodiment, this polyamic acid is made by follow procedure, by the dianhydride that dissolves rough same molal quantity with diamines in solvent, and the solution generating in the temperature condition stirring through regulation and control, until the polymerization of this dianhydride and this diamines completes formation prepolymer.Typically, make the one (being generally diamines) of monomer excessive in a little initial control molecular weight and viscosity, then can molecular weight and viscosity be increased via extra a small amount of not enough monomer.
(embodiment)
By 7.35g maleic anhydride (MAH) capacity of inserting, be the three-necked bottle of 1 liter, this three-necked bottle leads to nitrogen, makes to have condensation effect, and adopts churned mechanically device.Then, add solvent 200g N,N-DIMETHYLACETAMIDE (DMAc) to dissolve 10 minutes, now oil bath pan temperature maintains approximately 40 ~ 50 ℃.Then, by 8g 4,4'-oxygen base pentanoic (ODA) is inserted three-necked bottle and is reacted with maleic anhydride, reaction maintain 40 ~ 50 ℃ approximately 1 hour.
Afterwards, be warming up to 80 ℃.Then, 100g polymaleic anhydride is inserted to three-necked bottle, in 80 ℃ of reactions 1 hour.Then, using (Pyridine) 10.012g of the pyridine as catalyzer and as acetic anhydride (Acetic anhydride) 11g of dewatering agent, insert in three-necked bottle, and oil bath pan temperature is risen to 100 ℃, and react 2 hours, obtain polymaleic anhydride-pi resin.
Polymaleic anhydride-pi resin to gained carries out characteristic measurement, and the Tg of polymaleic anhydride-pi resin is about 150 ℃, 5wt% thermogravimetric loss temperature and is about 319 ℃, and the Gao Yuekeda 2,000,000 of molecular weight, as shown in Fig. 4 to Fig. 8.Fig. 7 represents the IR spectrogram of polymaleic anhydride-pi of the present invention acid, and Fig. 8 represents the IR spectrogram of polymaleic anhydride-polyimide resin of the present invention.Wave number 1453cm in Fig. 7
-1and 1601cm
-1for N-H in polyamic acid (PAA) structure crooked (N-H bending) and C=O stretching, extension (C=O stretching) absorption peak.After PAA cyclisation, form after polyimide (PI) structure, above two absorption peaks disappear, and new absorption peak forms, wherein wave number 1400cm
-1for the absorption peak of tertiary amine in PI structure, wave number 704 cm
-1with 1777 cm
-1for the absorption peak of C=O in PI structure, as shown in Figure 8.
In addition, the invention provides a kind of film, is that a woven fiber glass is impregnated in the aforesaid polyimide resin containing maleic anhydride and forms.This film has excellent thermotolerance, mechanical characteristics, and can be applicable to the insulating layer material of copper clad laminate and circuit card.
The invention provides a kind of copper clad laminate, is to be formed by a Copper Foil and aforesaid film pressing.This copper clad laminate has excellent thermotolerance, mechanical characteristics, after engaging with electronic component under the harsh environment such as high temperature, high humidity operation and can not affect its quality.
The above embodiment is only the preferred embodiment for absolutely proving that the present invention lifts, and protection scope of the present invention is not limited to this.Being equal to that those skilled in the art do on basis of the present invention substitutes or conversion, all within protection scope of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. containing a polyimide resin for maleic anhydride, it is characterized in that, by following structural formula, represented,
Wherein X is for the carbochain group containing 10 above carbon atoms, containing the group of phenyl ring or containing 10 above carbochains of carbon atom and the structure of phenyl ring group, m, n and l are all integer and are more than or equal to 1.
2. containing a polyimide resin for maleic anhydride, it is characterized in that, it is to take polymaleic anhydride as main chain, the structure of the pi that side chain contains short chain section.
3. contain a manufacture method for the polyimide resin of maleic anhydride, it is characterized in that, comprise following steps: (a) make dianhydride react in a solvent with diamines, to prepare polyamic acid solution; (b) with polymaleic anhydride, react with the polyamic acid solution that step (a) obtains, to prepare the side chain graft of polymaleic anhydride have-NH-CO-functional group and carboxylic acid group's oligomerization compound; And (c) add catalyzer to carry out chemical cyclization reaction.
4. the manufacture method of the polyimide resin containing maleic anhydride as claimed in claim 3, it is characterized in that, more be contained in step (c) before, those polymaleic anhydride of side chain graft have-NH-CO-functional group and carboxylic acid group's oligomerization compound are carried out a bridge formation reaction.
5. the manufacture method of the polyimide resin containing maleic anhydride as claimed in claim 3, it is characterized in that, this solvent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide or diethylene glycol monomethyl ether one of them or two or more arbitrary combination.
6. the manufacture method of the polyimide resin containing maleic anhydride as claimed in claim 3, is characterized in that, the catalyzer of this step (c) is pyridine or the pyridine of 3-methyl arsenic.
7. the manufacture method of the polyimide resin containing maleic anhydride claimed in claim 3, is characterized in that, this step (c) more adds dewatering agent.
8. the manufacture method of the polyimide resin containing maleic anhydride claimed in claim 7, is characterized in that, this dewatering agent is acetic anhydride, propionic anhydride, butyryl oxide or valeric anhydride one of them or its mixture; Aromatic monocarboxylate's acid anhydride; The mixture of aliphatic series acid anhydride and aromatics acid anhydride; Carbodiimide; Or aliphatic ketenes.
9. a film, is characterized in that, is to be impregnated in claimed in claim 1 should forming containing the polyimide resin of maleic anhydride by a woven fiber glass.
10. a copper clad laminate, is characterized in that, by least one Copper Foil and film pressing claimed in claim 9, is formed.
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| CN201310183875.5A CN104163923A (en) | 2013-05-17 | 2013-05-17 | Polyimide resin containing maleic anhydride and manufacture method thereof |
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| CN201310183875.5A CN104163923A (en) | 2013-05-17 | 2013-05-17 | Polyimide resin containing maleic anhydride and manufacture method thereof |
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Cited By (1)
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