CN102617857B - Polyimide and preparation process thereof - Google Patents
Polyimide and preparation process thereof Download PDFInfo
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- CN102617857B CN102617857B CN201210109580.9A CN201210109580A CN102617857B CN 102617857 B CN102617857 B CN 102617857B CN 201210109580 A CN201210109580 A CN 201210109580A CN 102617857 B CN102617857 B CN 102617857B
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Abstract
The invention relates to a polyimide containing a structure represented by the following formula and a preparation process thereof. The preparation process includes using a rapid two-step polymerization process, subjecting di-anhydride and a mixture of two kinds of diisocyanate to co-condensation and polymerization to obtain the polyimide. A solvent containing low toxicity is used as a reaction medium in the process of reaction so that fewer by-products are produced, separation purification is absent, and the reaction process is simple. The post-treatment of the final products is very easy, and the purity of the products is high. The polyimide has wide application fields and can be used in the fields of filter screens for high-temperature filtering, protective clothing, heat insulation materials and aerospace, and also in various high-temperature extreme environments. The formula is shown in the desctiption.
Description
Technical field
The present invention relates to chemical field of polymer material preparing technology, particularly a kind of high-performance polyimide and preparation method thereof.
Background technology
The polyimide being made by aromatic anhydride and aromatic isocyanate reaction, has excellent thermostability and is difficult for melting, and vitrifying surface temperature is 315 ℃.And the fiber carbonization temperature of this material is at 370 ℃.Meanwhile, due to the existence of aromatic ring structure, this polyimide material just has high fire resistance, nonflammable.Oxygen index is 38.Generally, can at 260 ℃, use.The resistance to multiple organic reagent of this polyimide, as alcohols, ethers, halogenated hydrocarbon.But strong polarity, protic solvent can be by its dissolving.As N, N'-dimethyl formamide (DMF), N, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), the vitriol oil etc.Due to its excellent chemical property, its Application Areas is very extensive, can be used in the filter screen of high temperature filtration, protective clothing, lagging material and aerospace field, and the extreme environment of various high temperature.
Traditional synthetic method (US5066760) is that benzophenone tetracarboxylic dianhydride (BTDI) is joined in solvent; mechanical stirring; pass into nitrogen protection; heat 80 ℃ of dissolvings; after dissolving; drip two kinds of vulcabond---the mixture of 4,4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI).Wherein the mol ratio of TDI and MDI is 4:1.Dropping process, for being controlled at more than 6 hours, is reacted more than 1 hour after being added dropwise to complete.Stopped reaction afterwards, is poured into water by mixture, and acetone washes away solvent in methyl alcohol etc., and shortcoming is to be more than 7 hours in the reaction times, time-consuming power consumption.
Summary of the invention
The object of the invention is to, for the technological line of synthetic this high-performance polyimide, this synthetic route has been saved the reaction times greatly, has energy-conservation and effect that enhance productivity.
For realizing this purpose, the invention provides a kind of polyimide and preparation method thereof, adopt condensation polymerization method, by the synthetic polyimide of mixture copolycondensation of dicarboxylic anhydride and two kinds of vulcabond, in reaction process, use the solvent that toxicity is little to make reaction medium, by product generates less, do not need separation and purification, reaction process is simple, and speed is fast, the aftertreatment of final product is also very easy, and product purity is very high.
Technical solution of the present invention is as follows:
A kind of polyimide, has following repeating structure formula:
Wherein the structure of R is:
n=1,2,3……。
Prepare a method for described polyimide, the mixture that comprises the benzophenone tetracarboxylic dianhydride shown in chemical formula (1) and two kinds of isocyanic acids in molar ratio 1:0.97-1.101 is raw material, and alkali and water, as catalyzer, carry out polycondensation;
The mixture of two kinds of described isocyanic acids is 4 shown in the tolylene diisocyanate shown in chemical formula (2) and chemical formulas (3), and 4`-diphenylmethanediisocyanate in molar ratio 4:1 mixes.
The whole reaction equation that the present invention prepares polyimide can be expressed as:
Wherein the structure of R is:
n=1,2,3……。
The preparation method's of polyimide concrete steps are as follows:
In the organic solvent that benzophenone tetracarboxylic dianhydride is joined, add alkali and water as catalyzer; Mechanical stirring, passes into nitrogen protection, heats 60-120 ℃ of dissolvings, after dissolving, first by disposable the mixture of two kinds of isocyanic acids of the 70%-80% reaction system that adds, stirring reaction 1 hour; Then in 1 hour, drip the mixture of two kinds of isocyanic acids of remaining 20%-30%, then react 1-2 hour, after reaction finishes, except desolventizing.
Described organic solvent is, N, N'-dimethyl formamide, N, N'-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, toluene or dimethylbenzene.
Described alkali is alkali-metal alkoxy compound or alkali-metal oxyhydroxide, and the add-on of alkali adds the alkali of 0.0001-0.2mol with respect to the mixture of every 1mol isocyanic ester.
The alkali of every g is corresponding to the water of 0.5-2g.
Beneficial effect of the present invention is as follows:
Compare different being from traditional synthetic technology: the first, to be divided into two steps be that the disposable 80% isocyanic ester mixed solution that adds of the first step carries out prepolymerization in reaction; The second, 20% isocyanic ester of remainder is added dropwise in system.By two-step approach, prepare the polyimide spinning slurry of high molecular.And traditional reaction system is single stage method, isocyanic ester is added dropwise in reaction system, time for adding is conventionally at 6-8 hours.Compared with traditional reaction process, this patent designs owing to reaction being divided into two steps, has greatly shortened time for adding, has improved production efficiency, has saved the energy.The prepared polyimide of the present invention, performance, intensity can meet the application requiring in current various fields, has wide prospect in practical application, profound significance and impact and considerable economic worth.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described, but does not limit the scope of the invention with this.
Embodiment 1
80.5 benzophenone tetracarboxylic dianhydrides (BTDI) are joined to the N of 250ml, in N'-dimethyl formamide (DMF), add 0.075gNaOH, be dissolved in 0.2ml water.Mechanical stirring; pass into nitrogen protection; heat 80 ℃ of dissolvings; after dissolving; disposablely add two kinds of vulcabond---4; mixture (wherein the mol ratio of TDI and MDI the is 4:1) 37.88g of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI), reacts 1 hour, and temperature is controlled at 80 ℃.Then, by 9.47g mixtures of diisocyanates by being added dropwise in reaction system, time for adding 1 hour, temperature is controlled at 80 ℃.After being added dropwise to complete, react 1 hour.Mixture is poured into and in acetone, washes away solvent.It is solvent that reduced viscosity test result is about 0.8(NMP, C=0.005g/ml).
Embodiment 2
161g benzophenone tetracarboxylic dianhydride (BTDI) is joined to the N of 500ml, in N'-N,N-DIMETHYLACETAMIDE (DMAc), add 0.15gNaOH, be dissolved in 0.4ml water.Mechanical stirring; pass into nitrogen protection; heat 120 ℃ of dissolvings; after dissolving; once add two kinds of vulcabond---4; mixture (wherein the mol ratio of TDI and MDI the is 4:1) 66.29g of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI), reacts 45 minutes, and temperature is controlled at 120 ℃.By 28.41g mixtures of diisocyanates by being added dropwise in reaction system, time for adding 1 hour, temperature is controlled at 120 ℃.After being added dropwise to complete, react 2 hours.Stopped reaction afterwards, is poured into mixture in acetone, to wash away solvent.It is solvent that reduced viscosity test result is about 0.8(NMP, C=0.005g/ml).
Embodiment 3
322g benzophenone tetracarboxylic dianhydride (BTDI) is joined to the N of 500ml, in N'-N,N-DIMETHYLACETAMIDE (DMAc), add 0.3gNaOH, be dissolved in 0.8ml water.Mechanical stirring; pass into nitrogen protection; heat 60 ℃ of dissolvings; after dissolving; once add two kinds of vulcabond---4; mixture (wherein the mol ratio of TDI and MDI the is 4:1) 151.52g of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI), reacts 1 hour, and temperature is controlled at 60 ℃.By 37.88g mixtures of diisocyanates by being added dropwise in reaction system, time for adding 1 hour, temperature is controlled at 60 ℃.After being added dropwise to complete, react 1.5 hours.Stopped reaction afterwards, is poured into mixture in acetone, to wash away solvent.It is solvent that reduced viscosity test result is about 0.8(NMP, C=0.005g/ml).
comparative example:
161g benzophenone tetracarboxylic dianhydride (BTDI) is joined to the N of 500ml, in N'-N,N-DIMETHYLACETAMIDE (DMAc), add 0.15gNaOH, be dissolved in 0.4ml water.Mechanical stirring, passes into nitrogen protection, heats 60-120 ℃ of dissolvings, after dissolving, drips two kinds of vulcabond---the mixture 94.7g of 4,4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI).Wherein the mol ratio of TDI and MDI is 4:1.Dropping process is 7 hours.After being added dropwise to complete, react 1 hour.Stopped reaction afterwards, is poured into mixture in acetone, to wash away solvent.It is solvent that reduced viscosity test result is about 0.8(NMP, C=0.005g/ml).
Find out thus, the present invention shortened after the reaction times, still can reach good result.Polymericular weight still can reach requirement, has greatly saved the energy and cost has improved efficiency.
Find out thus, the present invention shortened after the reaction times, still can reach good result.Polymericular weight still can reach requirement, has greatly saved the energy and cost has improved efficiency.
Claims (2)
1. prepare a method for polyimide, the mixture that comprises the benzophenone tetracarboxylic dianhydride shown in chemical formula (1) and two kinds of isocyanic ester in molar ratio 1:0.97 1.101 is raw material, and alkali and water, as catalyzer, carry out polycondensation;
The mixture of two kinds of described isocyanic ester is tolylene diisocyanate and the chemistry shown in chemical formula (2)
Shown in formula (3) 4,4` diphenylmethanediisocyanate ester in molar ratio 4:1 mix
Described polyimide, has following repeating structure formula:
Wherein the structure of R is:
n=1,2,3……；
Concrete steps are as follows:
In the organic solvent that benzophenone tetracarboxylic dianhydride is joined, add alkali and water as catalyzer; Mechanical stirring, passes into nitrogen protection, heats 60-120 ℃ of dissolvings, after dissolving, first by disposable the mixture of two kinds of isocyanic ester of the 70%-80% reaction system that adds, stirring reaction 1 hour; Then in 1 hour, drip the mixture of two kinds of isocyanic ester of remaining 20% 30%, then react 1 2 hours, after reaction finishes, except desolventizing; Wherein, described alkali is alkali-metal alkoxy compound or alkali-metal oxyhydroxide, and the add-on of alkali adds the alkali of 0.0001-0.2mol with respect to the mixture of every 1mol isocyanic ester ester; The alkali of every g corresponding to 0.5 the water of 2g.
2. the preparation method of polyimide according to claim 1, is characterized in that described organic solvent is, N, N' dimethyl formamide, N, N' N,N-DIMETHYLACETAMIDE, N methyl-2-pyrrolidone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), benzene, toluene or dimethylbenzene.
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| CN201210109580.9A CN102617857B (en) | 2012-04-16 | 2012-04-16 | Polyimide and preparation process thereof |
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| KR20150095881A (en) * | 2012-12-17 | 2015-08-21 | 바스프 에스이 | Porous branched/highly branched polyimides |
| CN103628172B (en) * | 2013-11-04 | 2016-08-17 | 东华大学 | A kind of preparation method of ternary copolyimide fiber |
| CN105175739A (en) * | 2015-09-25 | 2015-12-23 | 哈尔滨工程大学 | Preparation method of organic silicon and polyimide material |
| CN109251600A (en) * | 2018-08-27 | 2019-01-22 | 江苏吉庆管材有限公司 | A kind of metal pipe internal wall high-temperature resistant anti-corrosive anti-static coatings and preparation method thereof |
| CN110698726A (en) * | 2019-10-22 | 2020-01-17 | 株洲时代新材料科技股份有限公司 | Modified filler, polyamide acid resin and preparation method |
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| US3708458A (en) * | 1971-03-16 | 1973-01-02 | Upjohn Co | Copolyimides of benzophenone tetracarboxylic acid dianhydride and mixture of diisocyanates |
| AT392974B (en) * | 1989-07-13 | 1991-07-25 | Chemiefaser Lenzing Ag | MIXED POLYIMIDES AND METHOD FOR THE PRODUCTION THEREOF |
| WO2011147723A1 (en) * | 2010-05-27 | 2011-12-01 | Basf Se | Materials, process for production thereof and components therefor |
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