CN103788651B - Polyamic acid solution of low apparent viscosity and preparation method thereof - Google Patents
Polyamic acid solution of low apparent viscosity and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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Abstract
The preparation method of the polyamic acid solution of low apparent viscosity disclosed by the invention, specifically comprise: (1) adopts diamine monomer and dianhydride monomer polymerization to obtain polyamic acid solution, then add the trim,ethylchlorosilane of polyamic acid quality 5～40%, under room temperature, stir and within 1～5 hour, obtain the polyamic acid solution that apparent viscosity is 0.2～1.5 ten thousand centipoise, or (2) first obtain the solution containing polyamic acid by the dianhydride monomer polymerization of the diamine monomer of whole consumptions and whole consumption 60～90wt%, then add trim,ethylchlorosilane and remaining dianhydride monomer, under room temperature, stir 1～5 hour, wherein the mol ratio of diamine monomer and dianhydride monomer is 1:1, the addition of trim,ethylchlorosilane is 5～25% of polyamic acid gross mass. the present invention also provides the polyamic acid solution of the low apparent viscosity that said method makes, time prepared by employing method (1), the apparent viscosity of this solution is 0.2 ten thousand～1.5 ten thousand centipoises, and time prepared by employing method (2), the apparent viscosity of this solution is 0.1 ten thousand～1.1 ten thousand centipoises.
Description
Technical field
The invention belongs to polyimide precursor polyamic acid and preparing technical field thereof, particularly a kind of low apparent viscosity is poly-Amic acid solution and preparation method thereof.
Background technology
Polyimides is the polymer of a class taking imide ring as architectural feature, because of its have excellent mechanical property, hot property,Dimensional stability, chemical resistance, radioresistance, lower temperature resistance and electrical property etc., be widely used in automobile, national defense construction,The fields such as novel building, microelectronics, diffusion barrier, medical appliance and nanometer. The product form of polyimides is varied, has treeFat, composite, film, fiber, foam etc.
Polyimides adopts " two-step method " synthetic conventionally, first in polar non-solute, adds dianhydride and diamines to carry out low temperaturePolycondensation obtains presoma polyamic acid solution, then obtains polyimide material by chemical imidization or hot-imide, orUsing polyamic acid solution as matrix and other materials compound. Visible presoma polyamic acid solution is polyimides and composite wood thereofCritical materials in material preparation. But owing to having the very strong hydrogen bond of interaction in polyamic acid, thereby its viscosity is very large, makesWhen polyamic acid directly uses as high-performance composite materials matrix, cannot carry out good infiltration to reinforcing materials such as fibers,Cannot prepare composite, thereby limit its application in high-performance composite materials field.
At present, for avoiding the high viscosity problem of polyamic acid solution, when polyimides uses as resin conventionally, be to adopt PMR sidePrepared by method. As Chinese patent CN1230560 discloses " a kind of thermoset polyimide resin and its preparation method and application ",The method be first will react dianhydride used and end-capping reagent nadic anhydride in ethanol, reflux generate corresponding diacid two fat andMonoester, then joins both low temperature stirring in the alcohol solvent that has dissolved diamines and obtains low-molecular-weight oligomer, then soakStain fiber and fabric etc., then after etoh solvent volatilizees completely by high-temperature heat treatment again cross-linked polymeric obtain polyimide resin.The method not only processing step is many, complicated operation, and main is that the extent of reaction is little in liquid phase, molecular weight is low, the consolidating of later stagePhase cross-linked polymeric is also difficult to obtain higher molecular weight, thereby the polyimide resin mechanical strength of preparation is not high. In addition, though logicalCross the technical measures that reduce polymer solids level in polyamic acid solution, can to a certain degree reduce polyamic acid solution apparent viscosity,But it is low that low viscous efficiency falls in this measure, need increase considerably solvent load, thereby increase production cost, increase hot acid imideThe energy consumption of changing, and low solid content can obviously reduce production efficiency.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, first a kind of preparation side of low apparent viscosity polyamic acid solution is providedMethod.
Another object of the present invention is to provide a kind of polyamic acid solution of the low apparent viscosity of being prepared by said method.
The preparation method of the polyamic acid solution of low apparent viscosity provided by the invention, the method is mainly in polyamic acid solutionAdd the trim,ethylchlorosilane of following structure,
Reduce its apparent viscosity by the hydrogen bond destroying wherein, specifically comprise following two kinds of methods:
(1) adopt solid content that diamine monomer and dianhydride monomer obtain taking the mol ratio polymerization of 1:1 as 8～20%, apparent viscosityBe the polyamic acid solution of 3～850,000 centipoises, then in gained polyamic acid solution, add three of polyamic acid quality 5～40%Methylchlorosilane, stirs under room temperature and within 1～5 hour, obtains the polyamic acid solution that apparent viscosity is 0.2～1.5 ten thousand centipoise, or
(2) first by the diamine monomer of whole consumptions and all the dianhydride monomer polymerization of consumption 60～90wt% obtain containing polyamic acidSolution, then adds trim,ethylchlorosilane and remaining dianhydride monomer, stirs 1～5 hour under room temperature, obtain solid content and be 12～30% polyamic acid solution, its apparent viscosity is 0.1～1.1 ten thousand centipoise, wherein the mol ratio of diamine monomer and dianhydride monomer is 1:1, the addition of trim,ethylchlorosilane is 5～25% of polyamic acid gross mass.
Described in above method, diamine monomer is preferably 4,4 '-diphenyl ether diamines (ODA), p-phenylenediamine (PPD) (PDA), 2-(4-aminobenzeneBase)-5-amino benzoxazole (BOA), 2-(4-aminophenyl)-5-aminobenzimidazole (PABZ), m-phenylene diamine (MPD) (MDA) and 4,4 ' ,-At least one in diaminobenzene anilid (DABA), its structural formula is as follows respectively:
Dianhydride monomer described in above method is preferably pyromellitic acid dianhydride (PMDA), BPDA (BPDA), hexicholEther tetracarboxylic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), terphenyl tetracarboxylic dianhydride (TPDA) and bis trifluoromethylAt least one in tetracarboxylic dianhydride (6FDA), its structural formula is as follows respectively:
Diamine monomer described in above method and dianhydride monomer polymerisation obtain the concrete grammar of superpolyamide acid solutionFor: under nitrogen atmosphere, first diamines is dissolved in polar non-solute, stirring at room temperature, adds until its dissolving or after being uniformly dispersedEnter dianhydride, continue to stir and within 1～5 hour, complete reaction, wherein polar non-solute used be 1-METHYLPYRROLIDONE (NMP),N, N '-dimethylacetylamide (DMAC), N, in N '-dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO)Any.
In above method (1), the addition of trim,ethylchlorosilane is preferably 10～30% of polyamic acid quality, in method (2)The addition of trim,ethylchlorosilane is 10～25% of polyamic acid gross mass.
Mixing time in above method preferably 2.5～5 hours.
If the polyamic acid solution of gained in above method need to be prepared into polyimides, can be in the usual way by its hot acyl AsiaAmination, its concrete steps are: gained polyamic acid solution, successively 100 DEG C of insulations 1 hour, is incubated to 1 hour at 200 DEG C,At 300 DEG C, be incubated 1 hour, finally at 350 DEG C, be incubated 1 hour and can obtain polyimides. The technique of this hot-imide alsoCan do some adjustment according to prior art.
The polyamic acid solution of the low apparent viscosity that above method provided by the invention prepares, when time prepared by employing method (1),The apparent viscosity of this solution is 0.2 ten thousand～1.5 ten thousand centipoises, and fall is 50～98%, and time prepared by employing method (2), this is moltenThe apparent viscosity of liquid is 0.1 ten thousand～1.1 ten thousand centipoises, and fall is 70～99%.
Above-mentioned low apparent viscosity polyamic acid solution, when employing method (1) preparation, the addition of trim,ethylchlorosilane is 10～30%Time, the fall of the apparent viscosity of this solution is 90～98%, employing method (2) preparation, the addition of trim,ethylchlorosilaneBe 10～25% when above, the apparent viscosity fall of this solution is 91～99%.
Compared with prior art, the present invention has following beneficial effect:
1, because the inventive method has added trim,ethylchlorosilane after the polymerisation of preparing polyamic acid completes or in process, shouldTrim,ethylchlorosilane destroyed the very strong hydrogen bond that interacts in polyamic acid solution, thereby greatly reduces polyamic acid solutionApparent viscosity, makes apparent viscosity fall up to 50～98% and 70～99%, and this just makes polyamic acid solution at direct workWhile use for high-performance composite materials matrix, material (reinforcing material such as fiber) that can be compound to it well carries out good soakingProfit, expands its application in field of compound material.
2, because the present invention is in the time adopting the acid of conventional method synthesizing polyamides, be 1:1 by setting diamines and dianhydride mol ratio,Thereby synthetic polyamic acid solution has higher molecular weight, the mechanical property after hot-imide and hot property all can keepDo not adding the more than 90% of polyimide material of trim,ethylchlorosilane.
3, because the inventive method can reduce polyamic acid apparent viscosity, and reduction amplitude is larger, thereby in synthesizing polyamides acid mistakeIn journey, suitably increase in advance the immersional wetting also can not affect it directly as high-performance composite materials matrix after its solid content time, fromAnd can enhance productivity.
4, the inventive method technological operation is simple, and cost is low, is conducive to suitability for industrialized production.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, is necessary to be pointed out that at this following examples are only for to thisInvention is further described, and can not be interpreted as limiting the scope of the invention, and the person skilled in the art in this field is according to upperState some nonessential improvement and adjustment that content of the present invention is made, still belong to protection scope of the present invention.
In addition, what deserves to be explained is:
(1), in following examples, percentage composition all refers to quality percentage composition;
(2), in following examples, described usual manner hot-imide concrete steps are: by gained polyamic acid solution in glass plateUpper painting film forming, the employing stage heats up, and 100 DEG C of insulations 1 hour, is incubated 1 hour at 200 DEG C, is incubated 1 hour at 300 DEG C,After at 350 DEG C, be incubated 1 hour and can obtain polyimides;
(3) hot property is to adopt 10% thermal weight loss temperature to evaluate, and adopts thermal weight loss (TGA) method test thermal weight loss temperature(under nitrogen atmosphere 30～800 DEG C, 10 DEG C/min of heating rate); Mechanical property is evaluated by hot strength, is specificallyAdopt the hot strength (fixture 20mm, rate of extension 5mm/min) of film stretching test.
Embodiment 1
Under nitrogen atmosphere, first 15.9490gODA is dissolved in 300gN-methyl pyrrolidone, then add rapidly17.3844gPMDA, under room temperature, stirring and after 3 hours, obtaining solid content 10%, apparent viscosity is that the polyamide of 450,000 centipoises is acid-solubleLiquid adds thereafter the trim,ethylchlorosilane of polyamic acid quality 30% in the polyamic acid solution of gained, stirs 3 little under room temperatureTime, obtain the polyamic acid solution that apparent viscosity is 0.9 ten thousand centipoises, then hot-imide in the usual way.
Embodiment 2
According to the method for embodiment 1, the PDA that is 1:1 by mol ratio and BPDA, with N, N '-dimethylacetylamide is solventMaking solid content is 12%, and apparent viscosity is the polyamic acid solution of 850,000 centipoises. Then in the polyamic acid solution of gained, addEnter the trim,ethylchlorosilane of polyamic acid quality 40%, under room temperature, stir 5 hours, obtain the polyamides that apparent viscosity is 1.5 ten thousand centipoisesAmino acid solution, then hot-imide in the usual way.
Embodiment 3
According to the method for embodiment 1, the MDA that is 1:1 by mol ratio and OPDA, with N, N '-dimethyl formamide is solventMaking solid content is 20%, and apparent viscosity is the polyamic acid solution of 100,000 centipoises. Then in the polyamic acid solution of gained, addEnter the trim,ethylchlorosilane of polyamic acid quality 20%, under room temperature, stir 1 hour, obtain the polyamides that apparent viscosity is 10,000 centipoisesAmino acid solution, then hot-imide in the usual way.
Embodiment 4
According to the method for embodiment 1, the DABA that is 1:1 by mol ratio and 6FDA, make solid taking dimethyl sulfoxide (DMSO) as solventContent is 15%, and apparent viscosity is the polyamic acid solution of 30,000 centipoises. Then in the polyamic acid solution of gained, add polyamidesThe trim,ethylchlorosilane of amino acid quality 5%, stirs under room temperature 2.5 hours, obtains the polyamic acid that apparent viscosity is 1.5 ten thousand centipoisesSolution, then hot-imide in the usual way.
Embodiment 5
According to the method for embodiment 1, the ODA that is 1:1 by mol ratio and TPDA, with N, N '-dimethyl formamide is solventMaking solid content is 8%, and apparent viscosity is the polyamic acid solution of 40,000 centipoises. Then in the polyamic acid solution of gained, addThe trim,ethylchlorosilane of polyamic acid quality 10%, stirs under room temperature 3.5 hours, obtains the polyamides that apparent viscosity is 0.2 ten thousand centipoisesAmino acid solution, then hot-imide in the usual way.
Embodiment 6
First 6.5008gPABZ is joined in 110gN-methyl pyrrolidone, after it dissolves, add the whole consumptions of 6.8250g(85%) BPDA, stirring reaction 3 hours under nitrogen atmosphere, then add 1.5g(be polyamic acid gross mass 10%)Trim,ethylchlorosilane, then add the whole consumptions of remaining 1.7063g(15%) the mol ratio of two kinds of monomers of BPDA(be BPDA:PABZ=1:1), stir 5 hours under room temperature, obtain solid content and be 12% polyamic acid solution, its apparent viscosity is 1.1 ten thousandCentipoise, thereafter hot-imide in the usual way.
Embodiment 7
Equimolar PDA and PABZ are joined in 1-METHYLPYRROLIDONE, then add 90% of the whole consumptions of BTDAThe mol ratio of tri-kinds of monomers of BTDA(be BTDA:PDA:PABZ=2:1:1), stirring reaction 5 hours under nitrogen atmosphere,The apparent viscosity of gained solution is 4.5 ten thousand centipoises, then adds the trim,ethylchlorosilane of polyamic acid gross mass 20%, then more than addingUnder 10% BTDA, under room temperature, stir 3 hours, obtain the polyamic acid solution of solid content 16%, its apparent viscosity is 0.1Ten thousand centipoises, thereafter hot-imide in the usual way.
Embodiment 8
Equimolar PDA and BOA joined in 1-METHYLPYRROLIDONE, after it dissolves, add 85% of whole consumptionsThe mol ratio of tri-kinds of monomers of BPDA(is BPDA:PDA:BOA=2:1:1), stirring reaction 1 hour under nitrogen atmosphere,The apparent viscosity of gained solution is 8.5 ten thousand centipoises, then adds the trim,ethylchlorosilane of polyamic acid gross mass 25%, then more than addingUnder 15% BPDA, under room temperature, stir 4 hours, obtain solid content and be 20% polyamic acid solution, its apparent viscosity is0.6 ten thousand centipoises, thereafter hot-imide in the usual way.
Embodiment 9
ODA is joined in 1-METHYLPYRROLIDONE, after it dissolves, add 60% PMDA(two of the whole consumptions of PMDAThe mol ratio of planting monomer is PMDA:ODA=1:1), stirring reaction 2 hours under nitrogen atmosphere, the apparent viscosity of gained solutionBe 300,000 centipoises, then add the trim,ethylchlorosilane of polyamic acid gross mass 15%, then add remaining 40% PMDA,Under room temperature, stir 1 hour, obtain solid content and be 30% polyamic acid solution, its apparent viscosity is 0.3 ten thousand centipoises, can press thereafterUsual manner hot-imide.
Embodiment 10
The MDA of whole consumptions, all BTDA of consumption 80% and the 6FDA of whole consumptions 80% are joined to N-methyl pyrroleIn pyrrolidone, the mol ratio of three kinds of monomers is BTDA:6FDA:MDA=1:1:2, stirring reaction 2 hours under nitrogen atmosphere,The apparent viscosity of gained solution is 3.3 ten thousand centipoises, then adds the trim,ethylchlorosilane of polyamic acid gross mass 5%, then more than addingUnder 20%BTDA and 20% 6FDA, under room temperature, stir 5 hours, obtain the polyamic acid solution of solid content 18%, its tableSeeing viscosity is 1.0 ten thousand centipoises, thereafter hot-imide in the usual way.
Comparative example 1
Under nitrogen atmosphere, first 15.9490gODA is dissolved in 300gN-methyl pyrrolidone, then add rapidly17.3844gPMDA, under room temperature, stirring and after 3 hours, obtaining solid content 10%, apparent viscosity is that the polyamide of 450,000 centipoises is acid-solubleLiquid, thereafter hot-imide in the usual way.
Comparative example 2
First 6.5008gPABZ is joined in 110gN-methyl pyrrolidone, after it dissolves, add the whole consumptions of 6.8250g(85%) BPDA, stirring reaction 3 hours under nitrogen atmosphere, then add the whole consumptions of remaining 1.7063g(15%)The mol ratio of two kinds of monomers of BPDA(be BPDA:PABZ=1:1), under room temperature, stir 5 hours, obtain solid content and be12% polyamic acid solution, its apparent viscosity is 120,000 centipoises, thereafter hot-imide in the usual way.
For the correlated performance of the polyimides of investigating the apparent viscosity amplitude of variation of gained polyamic acid solution of the present invention and make,The inventor is except by above-described embodiment and comparative example gained polyamic acid solution hot-imide in the usual way, also according to comparative example1 method, by embodiment 2～5, prepares hot acyl Asia according to the method for comparative example 2 by the comparative sample of embodiment 7～10 correspondencesAfter amination, carried out the contrast of correlated performance Measurement and Computation, it the results are shown in following table.
Table 1
Table 2
Claims (10)
1. the preparation method of low apparent viscosity polyamic acid solution, is characterized in that the processing step of the method and condition are as follows:
(1) adopt solid content that diamine monomer and dianhydride monomer obtain taking the mol ratio polymerization of 1:1 as 8～20%, apparent viscosityBe the polyamic acid solution of 3～850,000 centipoises, then in gained polyamic acid solution, add three of polyamic acid quality 5～40%Methylchlorosilane, stirs under room temperature and within 1～5 hour, obtains the polyamic acid solution that apparent viscosity is 0.2～1.5 ten thousand centipoise, or
(2) first by the diamine monomer of whole consumptions and all the dianhydride monomer polymerization of consumption 60～90wt% obtain containing polyamic acidSolution, then adds trim,ethylchlorosilane and remaining dianhydride monomer, stirs 1～5 hour under room temperature, obtain solid content and be 12～30% polyamic acid solution, its apparent viscosity is 0.1～1.1 ten thousand centipoise, wherein the mol ratio of diamine monomer and dianhydride monomer is 1:1, the addition of trim,ethylchlorosilane is 5～25% of polyamic acid gross mass.
2. the preparation method of low apparent viscosity polyamic acid solution according to claim 1, is characterized in that described method (1)The addition of middle trim,ethylchlorosilane is 10～30% of polyamic acid quality, and in method (2), the addition of trim,ethylchlorosilane is10～25% of polyamic acid gross mass.
3. according to the preparation method of low apparent viscosity polyamic acid solution described in claim 1 or 2, it is characterized in that in the methodMixing time be 2.5～5 hours.
4. according to the preparation method of low apparent viscosity polyamic acid solution described in claim 1 or 2, it is characterized in that in the methodDescribed diamine monomer is 4,4 '-diphenyl ether diamines, p-phenylenediamine (PPD), the amino benzoxazole of 2-(4-aminophenyl)-5-, 2-(4-aminobenzeneBase)-5-aminobenzimidazole, m-phenylene diamine (MPD) and 4, at least one in 4 '-diaminobenzene anilid; Described dianhydride monomer is equalBenzenetetracarboxylic acid dianhydride, BPDA, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and two trifluoroAt least one in methyl tetracarboxylic dianhydride.
5. the preparation method of low apparent viscosity polyamic acid solution according to claim 3, is characterized in that described in the methodDiamine monomer is 4,4 '-diphenyl ether diamines, p-phenylenediamine (PPD), the amino benzoxazole of 2-(4-aminophenyl)-5-, 2-(4-aminophenyl)-5-Aminobenzimidazole, m-phenylene diamine (MPD) and 4, at least one in 4 '-diaminobenzene anilid.
6. according to the preparation method of low apparent viscosity polyamic acid solution described in claim 1 or 2, it is characterized in that in the methodDescribed dianhydride monomer is pyromellitic acid dianhydride, BPDA, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenylAt least one in tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
7. the preparation method of low apparent viscosity polyamic acid solution according to claim 3, is characterized in that described in the methodDianhydride monomer is pyromellitic acid dianhydride, BPDA, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracidAt least one in dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
8. the preparation method of low apparent viscosity polyamic acid solution according to claim 5, is characterized in that described in the methodDianhydride monomer is pyromellitic acid dianhydride, BPDA, diphenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracidAt least one in dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
9. the polyamic acid solution of the low apparent viscosity that according to claim 1 prepared by method, is characterized in that when employing method(1) while preparation, the apparent viscosity of this solution is 0.2 ten thousand～1.5 ten thousand centipoises, and fall is 50～98%, employing method (2)When preparation, the apparent viscosity of this solution is 0.1 ten thousand～1.1 ten thousand centipoises, and fall is 70～99%.
10. the polyamic acid solution of low apparent viscosity according to claim 9, is characterized in that when employing method (1) preparationTime, the fall of the apparent viscosity of this solution is 90～98%, time prepared by employing method (2), under the apparent viscosity of this solutionRange of decrease degree is 91～99%.
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| CN102492297A (en) * | 2011-11-30 | 2012-06-13 | 舟山维特新材料科技有限公司 | Polyimide material for preparing two-layer flexible copper clad laminate |
| CN102534858A (en) * | 2012-01-09 | 2012-07-04 | 东华大学 | Method for preparing graphene/polyimide composite fibers |
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