CN1028028C - Imide type prepolymer compositions and processes for preparing same - Google Patents
Imide type prepolymer compositions and processes for preparing same Download PDFInfo
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- CN1028028C CN1028028C CN 88108508 CN88108508A CN1028028C CN 1028028 C CN1028028 C CN 1028028C CN 88108508 CN88108508 CN 88108508 CN 88108508 A CN88108508 A CN 88108508A CN 1028028 C CN1028028 C CN 1028028C
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Abstract
Compositions containing an unsaturated bisimide component (A) and a diamine component (B) at the (A)/(B) molar ratio of 0.9-1.5 and (C) 0.01-4.0% by weight, based on the sum of (A) and (B), of at least one compound selected from radical polymerization inhibitors, carboxylic acids and acid anhydrides provide, upon heating, imide type prepolymer compositions which can be cured to provide products which are tough and have excellent adhesive strength to glass cloths and metals and heat resistance.
Description
The present invention relates to prepare the method for the thermofixation product that the imide-type prepolymer forms and prepare the method for imide-type prepolymer composition, more particularly, the method that relates to the thermofixation product of the preparation imide-type prepolymer composition that can obtain the flexible solidifying product thus, said solidifying product has good adhesive strength, flexible and thermotolerance for woven fiber glass and metal, and the invention still further relates to the preparation method that said prepolymer is formed.
Knew already, be to have disclosed in 7875/1973 the Japanese Patent by at high boiling solvent as publication number, in N-Methyl pyrrolidone, make the double imide and the diamine reactant that are solution state, or heat above-mentioned reactant and prepare the imide-type prepolymer to produce a kind of fused mixture that can react.
When such imide-type prepolymer that obtains is heating and curing, can obtain the good solidifying product of thermotolerance, still, there is such problem in the solidifying product that is obtained, and promptly they are brittle.In addition, their tensile strength, tensile elongation or beam type (izod) shock strength is also not always satisfactory.
Have such problem by the laminate for preparing with lamination lacquer (resin) impregnated glass-fiber cloth that contains this prepolymer, promptly this prepolymer only presents low bond strength for woven fiber glass or metal (as copper).
In addition, when this polymers is dissolved in polar solvent, as in dimethyl formamide, N-Methyl pyrrolidone and the N,N-DIMETHYLACETAMIDE time, the insoluble part of a large amount of relatively its has just been separated out, and the amount of insoluble part wherein promptly increases along with the rising of the softening temperature of this prepolymer.In this case, have such problem, promptly in the presence of above-mentioned polar solvent, the imines type prepolymer that preparation has high softening-point has some difficulties.
In these cases, except raw-material unsaturated double imide and diamines as preparation imide-type prepolymer, present inventors have carried out big quantity research at following each face, for example free type initiated polymerization inhibitor, carboxylic acid or acid anhydrides is added in the reactive system, with and pattern and blending ratio, the reaction conditions that can adopt descends or the like for this reason, finding by adopting a certain proportion of said components, on the basis that can quickly solve the above problems, finally finished the present invention.
The present invention is intended to solve existing these problems in the aforesaid prior art, the purpose of this invention is to provide the imide-type prepolymer forms and preparation method thereof, said imide-type prepolymer is formed the fragility and the adhesion characteristic that can improve the thermofixation product that is obtained thus, and resulting finished product is a flexible, for woven fiber glass and or metal (as copper) have good adhesive strength, its thermotolerance also is gratifying.
The method of the thermofixation product that preparation imide-type prepolymer of the present invention is formed, be characterised in that and use curable composition, it comprises following component (A) and (B), (A)/(B) mol ratio is 0.9/1-1.5/1, with described component (A) and (B) component of the 0.01-5.0% of gross weight (C) and (D), component (C) is at least a radical polymerization inhibitor of 2.5-di-tert-butyl hydroquinone or tertiary butylated hydroquinone, and component (D) is for being selected from least a arbitrarily compound of carboxylic acid and acid anhydrides.
Component (A): component (A) comprises by the represented unsaturated double imide of following logical formula I:
Wherein the D representative contains the divalent group of carbon-to-carbon double bond, and the A representative contains the divalent group of at least 2 carbon atoms.
Component (B): component (B) comprises by molecular formula H
2N-B-NH
2Represented diamines, wherein the B representative contains the divalent group less than 30 carbon atoms.
The method for preparing imide-type prepolymer composition of the present invention is characterised in that with (A)/(B) mol ratio to be component (A) and mixture (B) and the 0.01-5.0%(weight of 0.9-1.5) with said component (A) and total amount (B) component (C) and component (D) blending of benchmark, component (C) is 2, at least a radical polymerization inhibitor of 5-di-tert-butyl hydroquinone or tertiary butylated hydroquinone, component (D) is for being selected from least a arbitrarily compound of carboxylic acid and acid anhydrides, component (C) and total amount (D) be no more than component (A) and (B) gross weight 5%, and resulting mixture heating up reacted.
Component (A): component (A) comprises by the represented unsaturated double imide of following logical formula I:
Wherein the D representative contains the divalent group of carbon-to-carbon double bond, and the A representative contains the divalent group of at least 2 carbon atoms.
Component (B): component (B) comprises by molecular formula H
2N-B-NH
2Represented diamines, wherein the B representative contains the divalent group less than 30 carbon atoms.
The present invention prepares the method and the method for preparing imide-type prepolymer composition of the thermofixation product of imide-type prepolymer composition, will itemize below.
By the represented unsaturated double imide (A) of above-mentioned molecule formula I, one of component that it is formed as imide-type prepolymer of the present invention, it specifically comprises some compounds like this, for example, below cited.
N, N '-ethylenebis maleimide, N, N '-hexa-methylene bismaleimides, N, N '-meta-phenylene bismaleimide, N, N '-TOPOT 2,2 maleimide, N, N '-4,4 '-diphenylmethyl (base) bismaleimides, N, N '-4,4 '-phenyl ether bismaleimides, N, N '-3,4 '-the phenyl ether bismaleimides, N, N '-4,4 '-sulfobenzide bismaleimides, N, N '-m-xylene (base) bismaleimides, N, N '-4,4 '-the cyclohexyl bismaleimides, N, two citraconic acid imides of N '-4,4 '-diphenylmethyl (base) or the like.
Above-mentioned component (B) also is used as a component of imide-type prepolymer of the present invention, and it specifically comprises like this some compounds, for example, below cited.
4,4 '-diamino-dicyclohexyl methane, 1,4 '-diamino-cyclohexane, m-phenylenediamine, P-pHENYLENE dI AMINE, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminodiphenyl sulfide, m-xylene (base) diamines, p-Xylol (base) diamines, 1, two (to the amino-cumene base) benzene of 3-, 1, two (to the amino-cumene base) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 2,2 '-two (4-(4-amino-benzene oxygen) phenyl) propane, hexamethylene-diamine or the like.
Being used for radical polymerization inhibitor of the present invention is 2,5 di tert butylhydroquinone or tertiary butylated hydroquinone.
The consumption of these radical polymerization inhibitor is a 0.01-5.0%(weight), be benchmark with the total amount of unsaturated double imide and diamines.
These radical polymerization inhibitor are used to improve the fragility of the solidifying product that obtains by heating imide-type prepolymer and to the adhesion characteristic of woven fiber glass or analogue.By these radical polymerization inhibitor of above-mentioned scope being mixed in the imide-type prepolymer composition, the tensile strength of the product that is obtained, tensile elongation and cantilever-type impact strength all are improved thus.
Employed carboxylic acid specifically comprises following these cited compounds in of the present invention.
The one dollar aromatic carboxylic acid, as phenylformic acid, ortho-toluic acid and its isomer, o-tert-butyl phenylformic acid and its isomer, o-Carboxynitrobenzene and its isomer, 0-chloro-benzoic acid and its isomer, orthodichlorobenzene formic acid and its isomer, o-bromobenzoic acid and its isomer, salicylic acid and its isomer, o-methoxybenzoic acid and its isomer, anthranilic acid and its isomer, aromatic dicarboxylic acid, as phthalic acid and its isomer.The aromatic tricarboxylic acid, as 1,2,4-benzenetricarboxylic acid, and aromatic acid, as 1,2,4,5-pyromellitic acid and hexichol (first) ketone tetracarboxylic acid.The aliphatic monocarboxylic acid, as formic acid, acetate, propionic acid, toluylic acid, silicic acid, glyconic acid, lactic acid and tartrate, and silicic acid.Aliphatic dicarboxylic acid is as propanedioic acid, succsinic acid, pentanedioic acid, toxilic acid and fumaric acid.
Acid anhydrides used in the present invention specifically comprises following those listed compounds.
Diacetyl oxide, propionic anhydride, succinyl oxide, maleic anhydride, tetrahydroxy phenol dicarboxylic acid anhydride, tetrakis hydroxymethyl phosphonium phthalate anhydride, suitable-Nei-5-norbornylene-2,3-dicarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride, 1,2,4,5-pyromellitic acid dianhydride and 3,3 ', 4,4 '-hexichol (first) ketone tetracarboxylic acid dianhydride.
Above-mentioned radical polymerization inhibitor, the use total amount of carboxylic acid and acid anhydrides are no more than 5% of above-mentioned unsaturated double imide (A) and diamines (B) gross weight.
In order to prepare imide-type prepolymer of the present invention, above-mentioned starting material must heat to react.This reaction realized by heating several minutes to a few hours under 100-200 ℃ one suitable temperature.
When carrying out this reaction, said components (B) toward wherein adding said components (A), is reacted so two kinds of components all are heated in molten state then at first by heating and melting, and then this reaction can successfully be carried out.
Because imide-type prepolymer of the present invention is dissolved in the polar solvent, as dimethyl formamide, N-Methyl pyrrolidone, N,N-DIMETHYLACETAMIDE etc., when above-mentioned starting material heat in these solvents when reacting, reaction can successfully be carried out, and can obtain to have the imide-type prepolymer of superperformance.
The imide-type polymers that will obtain in above-mentioned mode is dissolved in polar solvent, in dimethyl formamide, N-Methyl pyrrolidone and N,N-DIMETHYLACETAMIDE, and such imide-type pre-polymerization is dissolved in the lamination lacquer (resin) that solution in the said solvent is extremely useful prepared layer laminated sheet.
Prepared like this prepolymer foregoing can the solvent solution form for using.Or also can be after they be converted into powder again, with powder type for using.
The imide-type prepolymer that is obtained like this can directly solidify by heating under about 180-250 ℃ temperature, if necessary, handles 10 minutes to 2 hours under certain pressure.
For the solidifying product that makes this imide-type prepolymer presents its inherent physicals, must be with this solidifying product under about 180-250 ℃ temperature the about 4-48 of post curing treatment hour.
If necessary, by the prepared imide-type prepolymer of method of the present invention can with lubricant described below or releasing agent fusion.
Fatty acid ester is as carnauba wax, beeswax, rice wax, stearate, butyl ester etc.; Fatty acid amide is as the ethylenebis stearic amide; Lipid acid is as montanic acid, stearic acid etc. and their metallic salt; Petroleum wax, polyethylene wax, Poly Propylene Wax and their oxide compound; And silicon (oxygen alkane) oil, as polymethyl siloxane, PSI etc.
These lubricants that added or the amount of releasing agent preferably are 0.1-5.0%(weight), be benchmark with the total amount of above-mentioned unsaturated double imide and diamines.
If necessary, by the prepared imide-type prepolymer of method of the present invention can also and rubber components, as the paracril (ATBN) of amine end etc., phase fusion such as teflon (Teflon), silicon (oxygen) alkane resin, phenolic resin, aniline resin.The amount of these additives that add is preferably 10-200%(weight), be benchmark with the total amount of above-mentioned unsaturated double imide and diamines.
In addition, if necessary, by the prepared imide-type prepolymer of method of the present invention also can with as the following inorganic of filler component or organic substance fusion mutually.
Ground silica, calcined bauxite in powder, glass powder, mica, talcum powder, barium sulfate, titanium oxide, molybdenumdisulphide, aluminium powder, iron powder, copper powder, metal hydroxides (as aluminium hydroxide and magnesium hydroxide), the fine hollow body of silica, alumina, glass, phenolic resin etc., with the reinforcement fiber, as glass fibre, sapphire whisker, carbon fiber, aromatic poly (Aramide) fiber, silicon carbide fiber, aluminum fiber, copper fiber etc.
The amount of these filler components that added is preferably 50-500%(weight), be benchmark with the total amount of above-mentioned unsaturated double imide and diamines.
The imide-type prepolymer that makes by method of the present invention has such characteristics, promptly when this prepolymer is dissolved in inert polar solvents, as in dimethyl formamide, N-Methyl pyrrolidone and the N,N-DIMETHYLACETAMIDE time, left amount of not dissolving part with the comparing of the prepared imide-type prepolymer of usual way, be very little.Therefore, when the prepolymer of the inventive method is pressed in preparation, make and might adopt a kind of like this method, the starting material that are about to be dissolved in these solvents react through heating.In addition, even the resin of high softening-point also can easily be processed lacquering.By utilizing these performances of above-mentioned prepolymer of the present invention, be easy to obtain around property height and the good solidifying product of thermotolerance.So the solidifying product that is obtained can be used for various purposes, as friction resistant material, bearing, gear, laminate, tackiness agent, insullac etc.
Compare with the solidifying product that the prepolymer that is obtained by usual way by being heating and curing obtains by the solidifying product that obtains by the inventive method imide-type prepolymer that is heating and curing, have higher anti-around intensity, tensile elongation and cantilever-type impact strength.
Further, in the time will being used as the tackiness agent of laminate by the prepared imines type of the inventive method prepolymer, can observe a kind of like this effect, promptly the T-of Copper Foil peels off T-between stripping strength or lamination and the lamination and peels off stripping strength and increased.
The present invention will be in conjunction with the embodiments, enumerates explanation following, still, should think that the present invention is not limited to these examples:
Embodiment 1
The 35.6g4 that packs in the separatory flask, 4 '-diaminodiphenyl-methane, 1.0g tertiary butylated hydroquinone and 0.5g P-hydroxybenzoic acid, this flask is immersed in oil bath, keep 150 ℃.When 4,4 '-diaminodiphenyl-methane dissolving and when forming the solution of a homogeneous, in stirring down, in 2 minutes, in resulting solution, add 64.4gN, N '-4,4 '-hexichol first (base) bismaleimides.Under agitation, with resulting mixture reaction 15 minutes, then, in the big basin of material suction in the flask.Should big basin put into the ventilation baking oven, remain on 160 ℃, and, pulverize then and obtain the imide-type prepolymer through aging 45 minutes.
Have found that such imide-type prepolymer that obtains can be dissolved in the dimethyl formamide in fact.
Adopt extrusion forming method (compression molding) that this prepolymer is shaped to the square rod of the thick flat board of 2mm and cross-sectional area 12.7mm * 12.7mm (at 200 ℃ and 150kgf/cm
2Condition under carried out 30 minutes), then the forming composition that obtained is obtained moulded products 200 ℃ of following post curing treatment 24 hours.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 1
Repeat the process of example 1,, can obtain the similar moulded products that the imide-type prepolymer is arranged to example 1 except not using tertiary butylated hydroquinone.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 2
Repeat the process of example 1,, can obtain moulded products to the similar imide-type prepolymer of example 1 except replacing 1.0g tertiary butylated hydroquinone and 0.5g P-hydroxybenzoic acid with the 0.5g phenylformic acid.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 3
Adopt compression moulding method (compression molding), under the condition identical with example 1, but only use the commercial available polyimide resin (product of Nippon Polyimiole K.K., the sales trademark name is called Chelimide 1000), can obtain similar moulded products to example 1.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Embodiment 2
But the 33.4g4 that packs in the flask of a separatory, 4 '-diaminodiphenyl-methane, this flask is immersed in oil bath, keep 150 ℃.4,4 '-the diaminodiphenyl-methane dissolving after, with 0.5g3,3 ', 4,4 '-hexichol (first) ketone tetracarboxylic dianhydride is dissolved in this solution, allows blended solution react.Then, under agitation, the 1.0g tertiary butylated hydroquinone is dissolved in this solution, and in 2 minutes toward wherein adding 66.6gN, N '-4,4 '-diphenylmethyl (base) bismaleimides.This mixture was under agitation reacted 20 minutes, then with in the big basin of material suction in the flask.Then, should big basin place the ventilation baking oven, keep 160 ℃, reactor product was worn out 60 minutes, and pulverize then and obtain the imide-type prepolymer.
By such prepolymer that obtains, adopt extrusion forming method (compression molding), under the condition identical, can obtain similar moulded products to example 1 with example 1.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 4
But in the flask of a separatory, add 35.6g4,4 '-diaminodiphenyl-methane, this flask is immersed in the oil bath, keep 150 ℃.4,4 '-the diaminodiphenyl-methane dissolving after, under agitation, with 1g3,3, ' 4,4 '-hexichol (first) ketone tetracarboxylic dianhydride is dissolved in this solution.Under agitation, in 2 minutes, in resulting solution, add 64.4gN, N '-4,4 '-diphenylmethyl (base) bismaleimides.Allow resulting mixture under agitation react 15 minutes, with reactor product from flask in big basin of suction.All the other steps are identical with example 1, can obtain the moulded products to the similar imide-type prepolymer of example 1.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 5
Repeat the process of example 1, except replacing 1.0g tertiary butylated hydroquinone and 0.5g P-hydroxybenzoic acid with the 0.5g quinhydrones, and the time of extrusion forming become 20 minutes, can obtain the moulded products of imide-type prepolymer.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 6
Repeat the process of example 1, except not using tertiary butylated hydroquinone and P-hydroxybenzoic acid, and the time of extrusion forming become 20 minutes, can obtain moulded products to the similar imide-type prepolymer of example 1.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Embodiment 3
Repeat the process of example 1, except using 0.25g2, the 5-di-tert-butyl hydroquinone replaces 1.0g tertiary butylated hydroquinone and 0.5g P-hydroxybenzoic acid, and digestion time becomes 50 minutes, the extrusion forming time becomes 20 minutes, can obtain the moulded products to the similar imide-type prepolymer of example 1.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Comparative examples 7
Repeat the process of example 1, except using 0.5g1,1-phenylbenzene-2-picrylhydrazyl replaces 1.0g tertiary butylated hydroquinone and 0.5g P-hydroxybenzoic acid, and the extrusion forming time become 20 minutes, can obtain moulded products to the similar imide-type prepolymer of example 1.
The physicals of the moulded products that is obtained is listed in the table 1 like this.
Embodiment 4
But pack in the flask of a separatory 150g dimethyl formamide, 50.2g4,4-diaminodiphenyl-methane and 0.75g3,3 ', 4,4 '-hexichol (first) ketone tetracarboxylic acid, and it is immersed in oil bath.When the temperature of liquid in the flask reached 100 ℃, the content in flask added 1.5g tertiary butylated hydroquinone and 99.8gN, N-4 again, 4 '-diphenylmethyl (base) bismaleimides, and under agitation, mixture is maintained 100 ℃, and allow it react 3 hours.
With such lacquer impregnated glass-fiber cloth that obtains, will descend dry 5 minutes at 160 ℃ through the woven fiber glass of dipping, and make a kind of preimpregnation (stain) material base.9 this preimpregnation (stain) material base is stacked togather a kind of laminate of formation, the Copper Foil of 28g is placed the top and the bottom of resulting laminate, with resulting laminate 180 ℃ of following extrusion formings 60 minutes, 200 ℃ of following post curing treatment 24 hours, make the laminate of a kind of deposited copper (paper tinsel) thus then.
The T-that such laminate that obtains is carried out Copper Foil peels off the mensuration that T-between stripping strength and the laminate peels off stripping strength.
Measurement result is listed in the table 2.
Comparative examples 8
Under the condition identical with embodiment 4, adopt the product of commercial available polyimide resin * Nippon Polyimide K.K, the sales trademark name is called Chelimide601), can make preimpregnation (stain) material base, thus, can make deposited copper (paper tinsel) laminate.The physicals of deposited copper (paper tinsel) laminate that makes like this is through measuring.
It is resulting that the results are shown in Table 2.
Comparative examples 9
But in the flask of a separatory that contains the 150g dimethyl formamide, add 53.4g4,4 '-diaminodiphenyl-methane, 96.6gN, N '-4,4 '-diphenylmethyl (base) bismaleimides and 0.75g P-hydroxybenzoic acid.Mixture in the stirred flask, with the temperature maintenance of liquid in 100 ℃, and experience reaction 3 hours.
With such lacquer impregnated glass-fiber cloth that obtains, will make a kind of preimpregnation (stain) material base 160 ℃ of dryings 5 minutes through the woven fiber glass of dipping.Nine this preimpregnation (stain) material base is laminated together to form a kind of laminate, 1 ounce copper foil is placed the top and the bottom of this laminate, with resulting laminate 180 ℃ of extrusion formings 60 minutes, 200 ℃ of post curing treatment 24 hours, can make the laminate of deposited copper (paper tinsel) thus then.
Such laminate that obtains is carried out the mensuration that T-between Copper Foil and the laminate peels off stripping strength.
The results are shown in Table 2 for mensuration
Comparative examples 10
Under the condition identical with comparative examples 9, adopt the commercial available polyimide resin (product of Nippon Polyimide K.K, the sales trademark name is called Chelim-ide 601), can make preimpregnation (stain) material base, can make the laminate of deposited copper (paper tinsel) thus.The physical property of the laminate of the deposited copper (paper tinsel) that is obtained like this is determined.
Obtain that the results are shown in Table 2.
Comparative examples 11
Repeat the process of comparative examples 9, replace the 0.75g P-hydroxybenzoic acid except adopting the 0.75g quinhydrones, and the time of extrusion forming change into 30 minutes, can make deposited copper (paper tinsel) laminate.So deposited copper (paper tinsel) laminate that obtains is carried out the mensuration that T-between Copper Foil and the laminate peels off stripping strength.
Resulting measurement result is listed in the table 2.
Comparative examples 12
Repeat the process of comparative examples 9,, can make deposited copper (paper tinsel) laminate except replacing employed lacquer with the commercial polyimide resin of buying (product of Nippon Polyimide K.K, the sales trademark name is called Chelimide601).Resulting so deposited copper (paper tinsel) laminate is carried out the mensuration that T-between Copper Foil and the laminate peels off stripping strength.
Resulting measurement result is listed in the table 2.
Table 1
Beam type
Tensile strength tensile elongation shock strength Tg DMF is not
(kgf/mm
2) (%) (nicked) (℃) molten part (%)
（kgf.cm/cm）
Embodiment 1 10.1 3.6 3.6 200 0
Comparative examples 1 9.5 3.0 3.1 214
Comparative examples 2 9.0 2.5 3.1 210
Comparative examples 3 5.0 1.1 0.9 225 58
Embodiment 2 10.9 4.2 4.0 218
Comparative examples 4 9.0 2.7 3.0
Comparative examples 5 9.0 2.7 3.0 214 0
Comparative examples 6 6.0 1.7 2.0 218 68
Embodiment 3 9.5 3.2 3.0 208
Comparative examples 7 9.0 2.9 3.2 211
* be under 10 ℃/minute in heating rate, adopt TMA to measure Tg.
Table 2
The T-that Copper Foil T-peels off between the laminate peels off Tg
The stripping strength stripping strength (℃)
（kg/cm） （kgf/cm）
Embodiment 4 1.8 2.0
Comparative examples 8 1.1 1.0
Comparative examples 9 1.8 1.8
Comparative examples 10 1.1 1.0
Comparative examples 11 1.8 1.8 205
Comparative examples 12 1.0 1.0
* be under 10 ℃/minute in heating rate, adopt TMA to measure Tg.
Claims (15)
1, a kind of method for preparing the thermofixation product of imide-type prepolymer composition is characterized in that: may further comprise the steps successively:
Prepare a kind of curable composition, this composition contains following component (A) and (B), (A)/(B) mol ratio is 0.9/1-1.5/1, with described component (A) and (B) component of the 0.01-5.0% of gross weight (C) and component (D) arbitrarily, component (C) is 2, at least a radical polymerization inhibitor of 5-di-tert-butyl hydroquinone or tertiary butylated hydroquinone is to make a kind of curable composition, component (D) is for being selected from least a compound of carboxylic acid and acid anhydrides, component (C) and gross weight (D) be no more than component (A) and (B) gross weight 5%;
Component (A): by the represented unsaturated double imide of following logical formula I;
Wherein the D representative contains the divalent group of carbon-to-carbon double bond, and the A representative contains the divalent group of at least 2 carbon atoms;
Component (B): by H
2N-B-NH
2The diamines of representative, wherein the B representative contains the divalent group less than 30 carbon atoms;
Described curable composition heating is made described component (A) and (B) react, make imide-type prepolymer composition;
Under temperature 180-250 ℃ and normal pressure, heat described imide-type prepolymer and form 10 minutes to 2 hours, make the solidifying product that described imide-type prepolymer is formed.
2, the method of claim 1, it is characterized in that: wherein component (A) is N, N '-ethylenebis maleimide, N, N '-hexa-methylene bismaleimides, N, N '-meta-phenylene bismaleimide, N, N '-TOPOT 2,2 maleimide, N, N '-4,4 '-diphenylmethyl (base) bismaleimides, N, N '-4,4 '-the phenyl ether bismaleimides, N, N '-3,4 '-phenyl ether bismaleimides, N, N '-4,4 '-the sulfobenzide bismaleimides, N, N '-m-xylene (base) bismaleimides, N, N '-4,4 '-cyclohexyl bismaleimides or N, the two citraconic acid imides of N '-4,4 '-diphenylmethyl (base).
3, the method of claim 1, it is characterized in that: wherein component (B) is 4,4 '-diamino-dicyclohexyl methane, 1,4 '-diamino-cyclohexane, m-phenylenediamine, P-pHENYLENE dI AMINE, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminodiphenyl sulfide, m-xylene (base) diamines, p-Xylol (base) diamines, 1, two (to the amino-cumene base) benzene of 3-, 1, two (to the amino-cumene base) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 2,2 '-two (4-(4-amino-benzene oxygen) phenyl) propane or hexamethylene-diamine.
4, the method of claim 1, it is characterized in that: wherein component (D) is a kind of carboxylic acid, it is selected from phenylformic acid, ortho-toluic acid or its isomer, o-tert-butyl phenylformic acid or its isomer, 0-chloro-benzoic acid or its isomer, orthodichlorobenzene formic acid or its isomer, o-bromobenzoic acid or its isomer, o-Carboxynitrobenzene or its isomer, salicylic acid or its isomer, o-methoxybenzoic acid or its isomer, anthranilic acid or its isomer, phthalic acid or its isomer, 1,2, the 4-benzenetricarboxylic acid, 1,2,4, the 5-pyromellitic acid, hexichol (first) ketone tetracarboxylic acid, formic acid, acetate, propionic acid, toluylic acid, glyconic acid, lactic acid, tartrate, propanedioic acid, succsinic acid, pentanedioic acid, toxilic acid or fumaric acid.
5, the method for claim 1 is characterized in that:
Wherein component (D) is a kind of acid anhydrides, be selected from diacetyl oxide, propionic anhydride, succinyl oxide, maleic anhydride, tetrahydroxy phenol dicarboxylic acid anhydride, tetrakis hydroxymethyl phosphonium phthalate anhydride, suitable-Nei-5-norbornylene-2,3-dicarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride, 1,2,4,5-pyromellitic acid dianhydride or 3,3 ', 4,4 '-hexichol (first) ketone tetracarboxylic acid dianhydride.
6, the method for claim 1 is characterized in that:
Further be included in 180-250 ℃ of step of described solidified product being carried out post curing treatment 4-48 hour.
7, a kind of method for preparing imide-type prepolymer composition is characterized in that: comprise the following steps: successively
Mix with (A)/(B) mol ratio 0.9/1-1.5/1 with following component (A) with (B);
Component (A): by the represented unsaturated double imide of following logical formula I;
Wherein the D representative contains the divalent group of carbon-to-carbon double bond, and the A representative contains the divalent group of at least 2 carbon atoms;
Component (B): by H
2N-B-NH
2The diamines of representative, wherein the B representative contains the divalent group less than 30 carbon atoms;
Described component (A) and (B) component of gross weight 0.01-5.0% (C) and component (D) are arbitrarily gone in fusion in described component (A) and mixture (B); Component (C) is 2, at least a radical polymerization inhibitor of 5-di-tert-butyl hydroquinone or tertiary butylated hydroquinone is to make a kind of curable composition, component (D) is for being selected from least a compound of carboxylic acid and acid anhydrides, component (C) and gross weight (D) be no more than component (A) and (B) gross weight 5%;
Temperature 100-200 ℃ with described curable composition heating several minutes to several hours, make described component (A) and (B) react.
8, method as claimed in claim 7 is characterized in that:
Wherein component (A) is
N, N '-ethylenebis maleimide, N, N '-hexa-methylene bismaleimides, N, N '-TOPOT 2,2 maleimide, N, N '-4,4 '-diphenylmethyl (base) bismaleimides, N, N '-4,4 '-phenyl ether bismaleimides, N, N '-3,4 '-phenyl ether bismaleimides, N, N '-4,4 '-sulfobenzide bismaleimides, N, N '-m-xylene (base) bismaleimides, N, N '-4,4 '-cyclohexyl bismaleimides or N, the two citraconic acid imides of N '-4,4 ' diphenylmethyl (base).
9, method as claimed in claim 7, it is characterized in that: wherein component (B) is 4,4 '-diamino-dicyclohexyl methane, 1,4 '-diamino-cyclohexane, m-phenylenediamine, P-pHENYLENE dI AMINE, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diamino diphenyl sulfone, 4,4 '-diaminodiphenyl sulfide, m-xylene (base) diamines, p-Xylol (base) diamines, 1, two (to the amino-cumene base) benzene of 3-, 1, two (to the amino-cumene base) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 4-, 2,2 '-two (4-(4-amino-benzene oxygen) phenyl) propane or hexamethylene-diamine.
10, method as claimed in claim 7, it is characterized in that: wherein component (D) is a kind of carboxylic acid, it is selected from phenylformic acid, ortho-toluic acid or its isomer, o-tert-butyl phenylformic acid or its isomer, 0-chloro-benzoic acid or its isomer, orthodichlorobenzene formic acid or its isomer, o-bromobenzoic acid or its isomer, o-Carboxynitrobenzene or its isomer, salicylic acid or its isomer, o-methoxybenzoic acid or its isomer, anthranilic acid or its isomer, phthalic acid or its isomer, 1,2, the 4-benzenetricarboxylic acid, 1,2,4, the 5-pyromellitic acid, hexichol (first) ketone tetracarboxylic acid, formic acid, acetate, propionic acid, toluylic acid, glyconic acid, lactic acid, tartrate, propanedioic acid, succsinic acid, pentanedioic acid, toxilic acid or fumaric acid.
11, method as claimed in claim 7 is characterized in that:
Wherein component (D) is a kind of acid anhydrides, be selected from diacetyl oxide, propionic anhydride, succinyl oxide, maleic anhydride, tetrahydroxy phenol dicarboxylic acid anhydride, tetrakis hydroxymethyl phosphonium phthalate anhydride, suitable-Nei-5-norbornylene-2,3-dicarboxylic anhydride, 1,2,4-benzenetricarboxylic anhydride, 1,2,4,5-pyromellitic acid dianhydride or 3,3 ', 4,4 '-hexichol (first) ketone tetracarboxylic acid dianhydride.
12, method as claimed in claim 7, it is characterized in that: wherein further comprise: continuous heating steps, promptly heating make component (A) and the step of (B) reacting before in turn with component (B) fusion, fused component (B) mixed making component (A) and mixture melt (B) with component (A).
13, method as claimed in claim 7 is characterized in that: wherein, form by adding heat solidifiable at temperature 100-200 ℃, finish the step that makes component (A) and (B) react.
14, method as claimed in claim 7 is characterized in that: wherein, heating make component (A) and (B) carry out reactions steps before, further comprise the step of curable composition being dissolved in a kind of inert polar solvent.
15, method as claimed in claim 14 is characterized in that: wherein, the inert polar solvent is dimethyl formamide, N-Methyl pyrrolidone or N,N-DIMETHYLACETAMIDE.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP310598/87 | 1987-12-08 | ||
| JP62310597A JPH01152125A (en) | 1987-12-08 | 1987-12-08 | Imide prepolymer composition and its production |
| JP310599/87 | 1987-12-08 | ||
| JP310597/87 | 1987-12-08 | ||
| JP62310599A JPH01152127A (en) | 1987-12-08 | 1987-12-08 | Imide prepolymer composition and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034557A CN1034557A (en) | 1989-08-09 |
| CN1028028C true CN1028028C (en) | 1995-03-29 |
Family
ID=26566385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108508 Expired - Lifetime CN1028028C (en) | 1987-12-08 | 1988-12-06 | Imide type prepolymer compositions and processes for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1028028C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3952196B2 (en) * | 2003-06-25 | 2007-08-01 | 信越化学工業株式会社 | Method for producing flexible metal foil polyimide laminate |
| CN105348530B (en) * | 2015-12-02 | 2017-08-25 | 河北麦格尼菲复合材料股份有限公司 | A kind of preparation method of bimaleimide resin prepolymerization system for liquid condition shaping technology |
| CN109280169A (en) * | 2018-10-31 | 2019-01-29 | 陕西硕博电子材料有限公司 | Low mixture of bismaleimide and preparation method thereof, Bismaleimides resin pre-polymer |
| CN109438705A (en) * | 2018-10-31 | 2019-03-08 | 陕西硕博电子材料有限公司 | The low mixture of bismaleimide, preparation method and Bismaleimides resin pre-polymer |
| CN112358612A (en) * | 2020-08-06 | 2021-02-12 | 上海大学 | Polyimide film containing gem-difluoro methylene and preparation method thereof |
-
1988
- 1988-12-06 CN CN 88108508 patent/CN1028028C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1034557A (en) | 1989-08-09 |
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