CN103788651A - Low-apparent-viscosity polyamide acid solution and preparation method thereof - Google Patents
Low-apparent-viscosity polyamide acid solution and preparation method thereof Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a preparation method of a low-apparent-viscosity polyamide acid solution. The preparation method comprises the following specific steps: (1) polymerizing diamine monomers with dianhydride monomers to obtain a polyamide acid solution, adding trimethylchlorosilane with the mass accounting for 5-40wt% of polyamide acid, and stirring at room temperature for 1-5 hours to obtain a polyamide acid solution with the apparent viscosity of 2,000-15,000 centipoises; or (2) polymerizing all the diamine monomers with 60wt%-90wt% of the dianhydride monomers to obtain the polyamide acid solution, adding the trimethylchlorosilane and the rest dianhydride monomers, and stirring at room temperature for 1-5 hours, wherein the molar ratio of the diamine monomers to the dianhydride monomers is 1:1 and the additive amount of the trimethylchlorosilane is 5%-25% of the total mass of the polyamide acid. The invention further provides the low-apparent-viscosity polyamide acid solution prepared by the method. When the polyamide acid solution is prepared by the method (1), the apparent viscosity of the solution is 2,000-15,000 centipoises; when the polyamide acid solution is prepared by the method (2), the apparent viscosity of the solution is 1,000-11,000 centipoises.
Description
Technical field
The invention belongs to polyimide precursor polyamic acid and preparing technical field thereof, particularly polyamic acid solution of a kind of low apparent viscosity and preparation method thereof.
Background technology
Polyimide is the polymkeric substance of a class take imide ring as constitutional features, because it has excellent mechanical property, thermal characteristics, dimensional stability, chemical resistant properties, radioresistance, lower temperature resistance and electrical property etc., be widely used in the fields such as automobile, national defense construction, novel building, microelectronics, separatory membrane, medical appliance and nanometer.The product form of polyimide is varied, has resin, matrix material, film, fiber, foam etc.
Polyimide adopts " two-step approach " synthetic conventionally, first in polar aprotic solvent, add dianhydride and diamines to carry out low-temperature polycondensation and obtain presoma polyamic acid solution, then obtain polyimide material by chemical imidization or hot-imide, or using polyamic acid solution as matrix and other materials compound.Visible presoma polyamic acid solution is the critical materials in polyimide and matrix material preparation thereof.But owing to thering is the very strong hydrogen bond of interaction in polyamic acid, thereby its viscosity is very large, when polyamic acid is directly used as high performance composite matrix, cannot carry out good infiltration to strongtheners such as fibers, cannot prepare matrix material, thereby limit its application in high performance composite field.
At present, for avoiding the high viscosity problem of polyamic acid solution, conventionally polyimide as resin with time employing PMR method prepare.As Chinese patent CN1230560 discloses " a kind of thermoset polyimide resin and its preparation method and application ", the method is first will react dianhydride used and end-capping reagent nadic anhydride in ethanol, to reflux and generate corresponding diacid two fat and monoester, then both are joined to low temperature stirring in the alcohol solvent that has dissolved diamines and obtain low-molecular-weight oligomer, impregnation of fibers and fabric etc. again, then after etoh solvent volatilizees completely by high-temperature heat treatment again crosslinking polymerization obtain polyimide resin.The method not only processing step is many, complicated operation, and main is that level of response is little in liquid phase, and molecular weight is low, and the solid phase crosslinking polymerization in later stage is also difficult to obtain higher molecular weight, thereby the polyimide resin mechanical strength of preparation is not high.In addition, though by reducing the technical measures of 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, the energy consumption of increase hot-imide, 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 method of low apparent viscosity polyamic acid solution is provided.
Another object of the present invention is to provide a kind of polyamic acid solution of the low apparent viscosity of being prepared by aforesaid method.
The preparation method of the polyamic acid solution of low apparent viscosity provided by the invention, the method is mainly the trimethylchlorosilane that adds following structure in polyamic acid solution,
Reduce its apparent viscosity by the hydrogen bond destroying wherein, specifically comprise following two kinds of methods:
(1) solid content that employing diamine monomer and dianhydride monomer obtain take the mol ratio polymerization of 1:1 is as 8～20%, apparent viscosity is the polyamic acid solution of 3～850,000 centipoises, then in gained polyamic acid solution, add the trimethylchlorosilane 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 the dianhydride monomer polymerization of the diamine monomer of whole consumptions and whole consumption 60～90wt% is obtained to the solution containing polyamic acid, then add trimethylchlorosilane and remaining dianhydride monomer, under room temperature, stir 1～5 hour, 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, and the add-on of trimethylchlorosilane is 5～25% of polyamic acid total mass.
Described in above method, diamine monomer is preferably 4,4 '-phenyl ether diamines (ODA), Ursol D (PDA), 2-(4-aminophenyl)-5-amino benzoxazole (BOA), 2-(4-aminophenyl)-5-aminobenzimidazole (PABZ), mphenylenediamine (MDA) and 4,4 ', at least one in-diaminobenzene anilide (DABA), its structural formula is as follows respectively:
Dianhydride monomer described in above method is preferably at least one in pyromellitic acid dianhydride (PMDA), BPDA (BPDA), phenyl ether tetracarboxylic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), terphenyl tetracarboxylic dianhydride (TPDA) and bis trifluoromethyl tetracarboxylic dianhydride (6FDA), and its structural formula is as follows respectively:
The concrete grammar that diamine monomer described in above method and dianhydride monomer polyreaction obtain superpolyamide acid solution is: under nitrogen atmosphere, first diamines is dissolved in polar aprotic solvent, stirring at room temperature, add dianhydride until its dissolving or after being uniformly dispersed, continue to stir and within 1～5 hour, complete reaction, wherein polar aprotic solvent used is N-Methyl pyrrolidone (NMP), N, N '-N,N-DIMETHYLACETAMIDE (DMAC), N, any in N '-dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) (DMSO).
In above method (1), the add-on of trimethylchlorosilane is preferably 10～30% of polyamic acid quality, and in method (2), the add-on of trimethylchlorosilane is 10～25% of polyamic acid total mass.
Churning time in above method preferably 2.5～5 hours.
If the polyamic acid solution of gained in above method need to be prepared into polyimide, can be in the usual way by its hot-imide, its concrete steps are: gained polyamic acid solution is incubated to 1 hour at 100 ℃ successively, at 200 ℃, be incubated 1 hour, at 300 ℃, be incubated 1 hour, finally at 350 ℃, be incubated 1 hour and can obtain polyimide.The technique of this hot-imide also can be done 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, fall is 50～98%, time prepared by employing method (2), the apparent viscosity of this solution 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, when the add-on of trimethylchlorosilane is 10～30%, the fall of the apparent viscosity of this solution is 90～98%, employing method (2) preparation, the add-on of trimethylchlorosilane is 10～25% when above, and 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 trimethylchlorosilane after the polyreaction of preparing polyamic acid completes or in process, this trimethylchlorosilane has destroyed the very strong hydrogen bond of interaction in polyamic acid solution, thereby greatly reduce the apparent viscosity of polyamic acid solution, make apparent viscosity fall up to 50～98% and 70～99%, this just makes polyamic acid solution in the time directly using as high performance composite matrix, material (strongthener such as fiber) that can be compound to it well carries out good infiltration, expands its application in field of compound material.
2, because the present invention is in the time adopting the acid of ordinary 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 thermal characteristics all can remain on the more than 90% of polyimide material that does not add trimethylchlorosilane.
3, because the inventive method can reduce polyamic acid apparent viscosity, and reduction amplitude is larger, thereby immersional wetting also can not affect it directly as high performance composite matrix suitably increase its solid content in advance in synthesizing polyamides acid process after time, thereby can enhance productivity.
4, the inventive method technological operation is simple, and cost is low, is conducive to suitability for industrialized production.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the person skilled in the art in this field makes according to the content of the invention described above, 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: gained polyamic acid solution is coated with to film forming on sheet glass, the employing stage heats up, 100 ℃ of insulations 1 hour, at 200 ℃, be incubated 1 hour, at 300 ℃, be incubated 1 hour, finally at 350 ℃, be incubated 1 hour and can obtain polyimide;
(3) thermal characteristics 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 ℃, 10 ℃/min of temperature rise rate); Mechanical property is evaluated by tensile strength, is the tensile strength (fixture 20mm, rate of extension 5mm/min) that adopts film stretching test specifically.
Embodiment 1
Under nitrogen atmosphere, first 15.9490g ODA is dissolved in 300g N-Methyl pyrrolidone, then add rapidly 17.3844g PMDA, under room temperature, stir after 3 hours and obtain solid content 10%, apparent viscosity is the polyamic acid solution of 450,000 centipoises, in the polyamic acid solution of gained add the trimethylchlorosilane of polyamic acid quality 30% thereafter, under room temperature, stir 3 hours, 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 '-N,N-DIMETHYLACETAMIDE be solvent to make solid content be 12%, apparent viscosity is the polyamic acid solution of 850,000 centipoises.Then in the polyamic acid solution of gained, add the trimethylchlorosilane of polyamic acid quality 40%, under room temperature, stir 5 hours, obtain the polyamic acid solution that apparent viscosity is 1.5 ten thousand centipoises, 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 be solvent to make solid content be 20%, apparent viscosity is the polyamic acid solution of 100,000 centipoises.Then in the polyamic acid solution of gained, add the trimethylchlorosilane of polyamic acid quality 20%, under room temperature, stir 1 hour, obtain the polyamic acid solution that apparent viscosity is 10,000 centipoises, 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 content as 15% take dimethyl sulfoxide (DMSO) as solvent, and apparent viscosity is the polyamic acid solution of 30,000 centipoises.Then in the polyamic acid solution of gained, add the trimethylchlorosilane of polyamic acid quality 5%, under room temperature, stir 2.5 hours, obtain the polyamic acid solution that apparent viscosity is 1.5 ten thousand centipoises, 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 be solvent to make solid content be 8%, apparent viscosity is the polyamic acid solution of 40,000 centipoises.Then in the polyamic acid solution of gained, add the trimethylchlorosilane of polyamic acid quality 10%, under room temperature, stir 3.5 hours, obtain the polyamic acid solution that apparent viscosity is 0.2 ten thousand centipoises, then hot-imide in the usual way.
Embodiment 6
First 6.5008g PABZ is joined in 110g N-Methyl pyrrolidone, until its dissolve after add the whole consumptions of 6.8250g(85%) BPDA, stirring reaction 3 hours under nitrogen atmosphere, then add 1.5g(be polyamic acid total mass 10%) trimethylchlorosilane, add again 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 be 12% polyamic acid solution, its apparent viscosity is 1.1 ten thousand centipoises, thereafter hot-imide in the usual way.
Embodiment 7
Equimolar PDA and PABZ are joined in N-Methyl pyrrolidone, then adding the mol ratio of tri-kinds of monomers of BTDA(of 90% of the whole consumptions of BTDA is 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 add the trimethylchlorosilane of polyamic acid total mass 20%, add again remaining 10% BTDA, under room temperature, stir 3 hours, obtain the polyamic acid solution of solid content 16%, its apparent viscosity is 0.1 ten thousand centipoises, thereafter hot-imide in the usual way.
Embodiment 8
Equimolar PDA and BOA are joined in N-Methyl pyrrolidone, after it dissolves, adding the mol ratio of tri-kinds of monomers of BPDA(of 85% of whole consumptions 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 add the trimethylchlorosilane of polyamic acid total mass 25%, add again remaining 15% BPDA, under room temperature, stir 4 hours, obtain solid content and be 20% polyamic acid solution, its apparent viscosity is 0.6 ten thousand centipoises, thereafter hot-imide in the usual way.
Embodiment 9
ODA is joined in N-Methyl pyrrolidone, after it dissolves, adding the mol ratio of two kinds of monomers of PMDA(of 60% of the whole consumptions of PMDA is PMDA:ODA=1:1), stirring reaction 2 hours under nitrogen atmosphere, the apparent viscosity of gained solution is 300,000 centipoises, then add the trimethylchlorosilane of polyamic acid total mass 15%, add again 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, thereafter hot-imide in the usual way.
Embodiment 10
The MDA of whole consumptions, all BTDA of consumption 80% and the 6FDA of whole consumptions 80% are joined in N-Methyl 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 add the trimethylchlorosilane of polyamic acid total mass 5%, add again remaining 20%BTDA and 20% 6FDA, under room temperature, stir 5 hours, obtain the polyamic acid solution of solid content 18%, its apparent viscosity is 1.0 ten thousand centipoises, thereafter hot-imide in the usual way.
Comparative example 1
Under nitrogen atmosphere, first 15.9490g ODA is dissolved in 300g N-Methyl pyrrolidone, then add rapidly 17.3844g PMDA, under room temperature, stir after 3 hours and obtain solid content 10%, apparent viscosity is the polyamic acid solution of 450,000 centipoises, thereafter hot-imide in the usual way.
Comparative example 2
First 6.5008g PABZ is joined in 110g N-Methyl pyrrolidone, until its dissolve after 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 be 12% polyamic acid solution, its apparent viscosity is 120,000 centipoises, thereafter hot-imide in the usual way.
For the correlated performance of the polyimide of investigating the apparent viscosity rangeability 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 the method for comparative example 1 by embodiment 2～5, according to the method for comparative example 2, the comparative sample of embodiment 7～10 correspondences is prepared after hot-imide, 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) solid content that employing diamine monomer and dianhydride monomer obtain take the mol ratio polymerization of 1:1 is as 8～20%, apparent viscosity is the polyamic acid solution of 3～850,000 centipoises, then in gained polyamic acid solution, add the trimethylchlorosilane 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 the dianhydride monomer polymerization of the diamine monomer of whole consumptions and whole consumption 60～90wt% is obtained to the solution containing polyamic acid, then add trimethylchlorosilane and remaining dianhydride monomer, under room temperature, stir 1～5 hour, 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, and the add-on of trimethylchlorosilane is 5～25% of polyamic acid total mass.
2. the preparation method of low apparent viscosity polyamic acid solution according to claim 1, the add-on that it is characterized in that trimethylchlorosilane in described method (1) is 10～30% of polyamic acid quality, and in method (2), the add-on of trimethylchlorosilane is 10～25% of polyamic acid total 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 the churning time in the method is 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 diamine monomer described in the method is 4,4 '-phenyl ether diamines, Ursol D, the amino benzoxazole of 2-(4-aminophenyl)-5-, 2-(4-aminophenyl)-5-aminobenzimidazole, mphenylenediamine and 4,4 ', at least one in-diaminobenzene anilide; Described dianhydride monomer is at least one in pyromellitic acid dianhydride, BPDA, phenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
5. the preparation method of low apparent viscosity polyamic acid solution according to claim 3, it is characterized in that diamine monomer described in the method is 4,4 '-phenyl ether diamines, Ursol D, the amino benzoxazole of 2-(4-aminophenyl)-5-, 2-(4-aminophenyl)-5-aminobenzimidazole, mphenylenediamine and 4,4 ', at least one in-diaminobenzene anilide.
6. according to the preparation method of low apparent viscosity polyamic acid solution described in claim 1 or 2, it is characterized in that dianhydride monomer described in the method is at least one in pyromellitic acid dianhydride, BPDA, phenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl 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 dianhydride monomer described in the method is at least one in pyromellitic acid dianhydride, BPDA, phenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic 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 dianhydride monomer described in the method is at least one in pyromellitic acid dianhydride, BPDA, phenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, terphenyl tetracarboxylic dianhydride and bis trifluoromethyl tetracarboxylic dianhydride.
9. the polyamic acid solution of the low apparent viscosity that according to claim 1 prepared by method, it is characterized in that when time prepared by employing method (1), the apparent viscosity of this solution is 0.2 ten thousand～1.5 ten thousand centipoises, fall is 50～98%, time prepared by employing method (2), 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, it is characterized in that when time prepared by employing method (1), the fall of the apparent viscosity of this solution is 90～98%, and time prepared by employing method (2), the apparent viscosity fall of this solution is 91～99%.
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| CN105622936B (en) * | 2014-10-27 | 2018-05-11 | 中国石油化工股份有限公司 | The preparation method of polyamic acid solution |
| CN105622936A (en) * | 2014-10-27 | 2016-06-01 | 中国石油化工股份有限公司 | Preparation method for polyamide acid solution |
| CN105312035A (en) * | 2015-11-17 | 2016-02-10 | 四川大学 | Polyimide/silicon dioxide nano heavy metal adsorbing material as well as preparation and regeneration methods |
| CN105312035B (en) * | 2015-11-17 | 2017-12-15 | 四川大学 | Polyimide/silicon dioxide nanometer heavy-metal adsorption material and its preparation and renovation process |
| US11261304B2 (en) | 2016-10-31 | 2022-03-01 | Lg Chem, Ltd. | Polyimide film forming composition and polyimide film produced by using same |
| CN109843980A (en) * | 2016-10-31 | 2019-06-04 | 株式会社Lg化学 | The polyimide film for forming the composition of polyimide film and being manufactured by using it |
| CN109843980B (en) * | 2016-10-31 | 2021-06-15 | 株式会社Lg化学 | Composition for forming polyimide film and polyimide film manufactured by using the same |
| CN106589415A (en) * | 2016-11-21 | 2017-04-26 | 无锡高拓新材料股份有限公司 | Preparation method of polyamide acid solution |
| CN109207116A (en) * | 2017-07-03 | 2019-01-15 | 台虹科技股份有限公司 | Adhesive composition |
| CN109207116B (en) * | 2017-07-03 | 2021-01-01 | 台虹应用材料股份有限公司 | Adhesive composition |
| CN110295026A (en) * | 2018-03-23 | 2019-10-01 | 台虹科技股份有限公司 | It is temporary then temporary to use with constituent and then solution |
| CN110655650A (en) * | 2019-11-11 | 2020-01-07 | 同济大学 | Benzoxazine bridged polyimide precursor and preparation method thereof |
| CN112409612A (en) * | 2020-09-30 | 2021-02-26 | 孙利滨 | Preparation method of high-solid-content low-viscosity polyamic acid solution |
| CN112409612B (en) * | 2020-09-30 | 2023-08-25 | 苏州尊尔光电科技有限公司 | Preparation method of high-solid-content low-viscosity polyamic acid solution |
| WO2022268146A1 (en) * | 2021-06-23 | 2022-12-29 | 中国石油化工股份有限公司 | Polyimide copolymer and film, preparation methods therefor and applications thereof, and system and method for purifying helium |
| CN115999328A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Method and system for preparing ethylene by combining membrane separation with rectification |
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