CN102617857A - Polyimide and preparation process thereof - Google Patents
Polyimide and preparation process thereof Download PDFInfo
- Publication number
- CN102617857A CN102617857A CN2012101095809A CN201210109580A CN102617857A CN 102617857 A CN102617857 A CN 102617857A CN 2012101095809 A CN2012101095809 A CN 2012101095809A CN 201210109580 A CN201210109580 A CN 201210109580A CN 102617857 A CN102617857 A CN 102617857A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- alkali
- mixture
- kinds
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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.
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
A kind of polyimide that is made by aromatic anhydride and aromatic isocyanate reaction has excellent thermostability and is difficult for fusing property, and the vitrifying surface temperature is 315 ℃.And the fiber carbonization temperature of this material is at 370 ℃.Simultaneously, because the existence of aromatic ring structure, this polyimide material just has high fire resistance, and is nonflammable.Oxygen index is 38.Generally speaking, can use down at 260 ℃.The anti-multiple organic reagent of this polyimide, like alcohols, ethers, halogenated hydrocarbon.But strong polarity, protic solvent are can be with its dissolved.Like N, N'-N (DMF), N, N'-N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), the vitriol oil etc.Because 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 various pyritous extreme environment.
Traditional compound method (US5066760) is that benzophenone tetracarboxylic dianhydride (BTDI) is joined in the solvent; Mechanical stirring; Feed nitrogen protection, heat 80 ℃ of dissolvings, after the dissolving; Drip two kinds of vulcabond---4, the mixture of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI).Wherein the mol ratio of TDI and MDI is 4:1.The dropping process is reacted more than 1 hour after being added dropwise to complete for being controlled at more than 6 hours.Stopped reaction is poured into water with mixture afterwards, and the flush away solvent gets final product in the acetone, 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 objective of the invention is to, supply 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 present invention provides a kind of polyimide and preparation method thereof, adopts condensation polymerization method; By the mixture copolycondensation synthesis of polyimides of dicarboxylic anhydride and two kinds of vulcabond, use the little solvent of toxicity to make reaction medium in the reaction process, by product generates less; Do not need separation and purification, reaction process is simple, and speed is fast; Also very easily, product purity is very high for post-treatment of final products.
Technical solution of the present invention is following:
A kind of polyimide has following repeating structure formula:
Wherein the structure of R is:
n=1,2,3……。
A kind of method for preparing described polyimide, the mixture that comprises the benzophenone tetracarboxylic dianhydride shown in the chemical formula (1) and two kinds of isocyanic acids 1:0.97-1.101 in molar ratio is a raw material, alkali and water carry out polycondensation as catalyzer;
（1）
The mixture of described two kinds of isocyanic acids is 4 shown in the tolylene diisocyanate shown in the chemical formula (2) and chemical formulas (3), and 4`-diphenylmethanediisocyanate 4:1 in molar ratio mixes.
The entire reaction equation that the present invention prepares polyimide can be expressed as:
Wherein the structure of R is:
[0009] n=1,2,3……。
The preparing method's of polyimide concrete steps are following:
In the organic solvent that benzophenone tetracarboxylic dianhydride is joined, add alkali and water as catalyzer; Mechanical stirring feeds nitrogen protection, heats 60-120 ℃ of dissolvings, after the dissolving, and at first with the disposable adding reaction system of mixture of two kinds of isocyanic acids of 70%-80%, stirring reaction 1 hour; In 1 hour, drip the mixture of two kinds of isocyanic acids of remaining 20%-30% then, reacted 1-2 hour again, after reaction finished, removing desolvates got final product.
Described organic solvent is N, N'-N, N, N'-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, THF, DMSO 99.8MIN., benzene, toluene or YLENE.
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 following:
Compare different being with traditional synthetic technology: the first, to be divided into for two steps be that the disposable adding 80% isocyanic ester mixed solution of the first step carries out prepolymerization reaction in reaction; The second, 20% isocyanic ester with remainder is added dropwise in the system.Through two-step approach, prepared high-molecular weight polyimide spinning slurry.And traditional reaction system is a single stage method isocyanic ester is added dropwise in the reaction system, the dropping time is usually at 6-8 hours.Compare with traditional reaction process, this patent design has been shortened the dropping time greatly because reaction was divided into for two steps, has improved production efficiency, has practiced thrift the energy.The prepared polyimide of the present invention, performance, intensity can both satisfy the application requiring in present various fields, and wide prospect is arranged in practical application, profound significance and influence and considerable economic value.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described, but do not limit protection scope of the present invention with this.
Embodiment 1
80.5 benzophenone tetracarboxylic dianhydrides (BTDI) are joined the N of 250ml, in the N'-N (DMF), add 0.075gNaOH, be dissolved in the 0.2ml water.Mechanical stirring; Feed nitrogen protection, heat 80 ℃ of dissolvings, after the dissolving; Two kinds of vulcabond of disposable adding---4; The mixture of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI) (wherein the mol ratio of TDI and MDI is 4:1) 37.88g reacted 1 hour, and temperature is controlled at 80 ℃.Then, through being added dropwise in the reaction system, 1 hour dropping time, temperature is controlled at 80 ℃ with the 9.47g mixtures of diisocyanates.Reacted 1 hour after being added dropwise to complete.Mixture is poured into flush away solvent in the acetone.The reduced viscosity test result is about 0.8, and (NMP is a solvent, C=0.005g/ml).
Embodiment 2
161g benzophenone tetracarboxylic dianhydride (BTDI) is joined the N of 500ml, in the N'-N,N-DIMETHYLACETAMIDE (DMAc), add 0.15gNaOH, be dissolved in the 0.4ml water.Mechanical stirring; Feed nitrogen protection, heat 120 ℃ of dissolvings, after the dissolving; Once add two kinds of vulcabond---4; The mixture of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI) (wherein the mol ratio of TDI and MDI is 4:1) 66.29g reacted 45 minutes, and temperature is controlled at 120 ℃.Through being added dropwise in the reaction system, 1 hour dropping time, temperature is controlled at 120 ℃ with the 28.41g mixtures of diisocyanates.Reacted 2 hours after being added dropwise to complete.Stopped reaction is poured into flush away solvent in the acetone with mixture afterwards.The reduced viscosity test result is about 0.8, and (NMP is a solvent, C=0.005g/ml).
Embodiment 3
322g benzophenone tetracarboxylic dianhydride (BTDI) is joined the N of 500ml, in the N'-N,N-DIMETHYLACETAMIDE (DMAc), add 0.3gNaOH, be dissolved in the 0.8ml water.Mechanical stirring; Feed nitrogen protection, heat 60 ℃ of dissolvings, after the dissolving; Once add two kinds of vulcabond---4; The mixture of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI) (wherein the mol ratio of TDI and MDI is 4:1) 151.52g reacted 1 hour, and temperature is controlled at 60 ℃.Through being added dropwise in the reaction system, 1 hour dropping time, temperature is controlled at 60 ℃ with the 37.88g mixtures of diisocyanates.Reacted 1.5 hours after being added dropwise to complete.Stopped reaction is poured into flush away solvent in the acetone with mixture afterwards.The reduced viscosity test result is about 0.8, and (NMP is a solvent, C=0.005g/ml).
The comparative example:
161g benzophenone tetracarboxylic dianhydride (BTDI) is joined the N of 500ml, in the N'-N,N-DIMETHYLACETAMIDE (DMAc), add 0.15gNaOH, be dissolved in the 0.4ml water.Mechanical stirring feeds nitrogen protection, heats 60-120 ℃ of dissolvings, after the dissolving, drips two kinds of vulcabond---and 4, the mixture 94.7g of 4`-diphenylmethanediisocyanate (MDI) and toluene diisocynate (TDI).Wherein the mol ratio of TDI and MDI is 4:1.The dropping process is 7 hours.Reacted 1 hour after being added dropwise to complete.Stopped reaction is poured into flush away solvent in the acetone with mixture afterwards.The reduced viscosity test result is about 0.8, and (NMP is a solvent, C=0.005g/ml).
Find out that thus the present invention still can reach result preferably after having shortened the reaction times.Polymericular weight still can reach requirement, has practiced thrift the energy greatly and cost has improved efficient.
Find out that thus the present invention still can reach result preferably after having shortened the reaction times.Polymericular weight still can reach requirement, has practiced thrift the energy greatly and cost has improved efficient.
Claims (6)
1. polyimide has following structural formula:
Wherein the structure of R is:
n=1,2,3……。
2. method for preparing polyimide as claimed in claim 1, the mixture that comprises the benzophenone tetracarboxylic dianhydride shown in the chemical formula (1) and two kinds of isocyanic acids 1:0.97-1.101 in molar ratio is a raw material, alkali and water carry out polycondensation as catalyzer;
（1）
The mixture of described two kinds of isocyanic acids is 4 shown in the tolylene diisocyanate shown in the chemical formula (2) and chemical formulas (3), and 4`-diphenylmethanediisocyanate 4:1 in molar ratio mixes
3. the preparation method of polyimide according to claim 2, concrete steps are following:
In the organic solvent that benzophenone tetracarboxylic dianhydride is joined, add alkali and water as catalyzer; Mechanical stirring feeds nitrogen protection, heats 60-120 ℃ of dissolvings, after the dissolving, and at first with the disposable adding reaction system of mixture of two kinds of isocyanic acids of 70%-80%, stirring reaction 45 minutes-1 hour; In 1 hour, drip the mixture of two kinds of isocyanic acids of remaining 20%-30% then, reacted 1-2 hour again, after reaction finished, removing desolvates got final product.
4. according to the preparation method of claim 2 or 3 described polyimide, it is characterized in that described organic solvent does, N, N'-N, N, N'-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, THF, DMSO 99.8MIN., benzene, toluene or YLENE.
5. according to the preparation method of claim 2 or 3 described polyimide; It is characterized in that described alkali is alkali-metal alkoxy compound or alkali-metal oxyhydroxide, the add-on of alkali adds the alkali of 0.0001-0.2mol with respect to the mixture of every 1mol isocyanic ester.
6. the preparation method of polyimide according to claim 5 is characterized in that the water of the alkali of every g corresponding to 0.5-2g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210109580.9A CN102617857B (en) | 2012-04-16 | 2012-04-16 | Polyimide and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210109580.9A CN102617857B (en) | 2012-04-16 | 2012-04-16 | Polyimide and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102617857A true CN102617857A (en) | 2012-08-01 |
| CN102617857B CN102617857B (en) | 2014-05-14 |
Family
ID=46558096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210109580.9A Expired - Fee Related CN102617857B (en) | 2012-04-16 | 2012-04-16 | Polyimide and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102617857B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103628172A (en) * | 2013-11-04 | 2014-03-12 | 东华大学 | Preparation method of ternary copolyimide fiber |
| CN105073813A (en) * | 2012-12-17 | 2015-11-18 | 巴斯夫欧洲公司 | Porous branched/highly branched polyimides |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708458A (en) * | 1971-03-16 | 1973-01-02 | Upjohn Co | Copolyimides of benzophenone tetracarboxylic acid dianhydride and mixture of diisocyanates |
| US5066760A (en) * | 1989-07-13 | 1991-11-19 | Lenzing Aktiengesellschaft | Mixed polyimides and process for preparing them |
| WO2011147723A1 (en) * | 2010-05-27 | 2011-12-01 | Basf Se | Materials, process for production thereof and components therefor |
-
2012
- 2012-04-16 CN CN201210109580.9A patent/CN102617857B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708458A (en) * | 1971-03-16 | 1973-01-02 | Upjohn Co | Copolyimides of benzophenone tetracarboxylic acid dianhydride and mixture of diisocyanates |
| US5066760A (en) * | 1989-07-13 | 1991-11-19 | Lenzing Aktiengesellschaft | Mixed polyimides and process for preparing them |
| WO2011147723A1 (en) * | 2010-05-27 | 2011-12-01 | Basf Se | Materials, process for production thereof and components therefor |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105073813A (en) * | 2012-12-17 | 2015-11-18 | 巴斯夫欧洲公司 | Porous branched/highly branched polyimides |
| CN103628172A (en) * | 2013-11-04 | 2014-03-12 | 东华大学 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102617857B (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617857B (en) | Polyimide and preparation process thereof | |
| EP2832768B1 (en) | Preparation method of polyimide | |
| CN110563678A (en) | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride | |
| CN105085281A (en) | Diamine monomer containing diphenylamine-fluorene, preparation method and application of same in polyimide preparation | |
| CN101487190B (en) | Polyimide carbon fiber sizing agent and method for producing the same | |
| CN112275147B (en) | Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof | |
| CN101870693B (en) | Bismaleimide containing 1,3,4-oxadiazole structure and preparation method thereof | |
| CN109293648A (en) | Benzoxazine monomer containing ethynyl and norbornene, preparation method and application thereof | |
| CN103342812A (en) | Aromatic polyamide sulfamide and preparation method thereof | |
| CN115490657B (en) | Preparation method of 3,3', 4' -benzophenone tetracarboxylic dianhydride | |
| CN115301287B (en) | Preparation method of high-purity p-phenylene-bis (trimellitate) dianhydride | |
| CN102644128A (en) | Polyimide fiber spinning solution based on 2, 2-double [4-(2, 4-diaminophenoxy) phenyl group] hexafluoropropane and preparation method thereof | |
| CN113336943B (en) | Alicyclic group-containing polyamide-imide and preparation method thereof | |
| CN105503775A (en) | Diamine monomer with triphenylamine structure containing p-substituted cyclic amine, preparation method and application of diamine monomer | |
| CN105753824B (en) | A kind of two anhydride phthalic acid green preparation process of 4,4 '-(hexafluoroisopropyli,ene) | |
| CN113636955A (en) | Preparation method of diamine containing phthalonitrile group | |
| CN113667119B (en) | Polyacetamide-imide film and preparation method thereof | |
| CN101250149A (en) | Method for preparing 4,4-di(3-dimaleoyl imino-4-(4-cyano phenoxy) triphenylmethane | |
| CN101250151A (en) | Method for preparing 2,2-di(3-maleoyl imino-4-(4-nitryl phenoxy) phenyl] propane | |
| CN101717374B (en) | Compound comprising fork biphenyl center and preparation method thereof | |
| CN116102438A (en) | Preparation method of bis (4-aminophenyl) terephthalate | |
| CN117164857A (en) | Intrinsic high-dielectric-property phosphine oxide polyimide and preparation method thereof | |
| CN102677214A (en) | Polyimide fiber spinning stock solution based on 2,2-bis[4-(2,4-diaminophenoxy) phenyl] propane and preparation method thereof | |
| CN117903467A (en) | Polyimide film with high transparency and high heat resistance and preparation method thereof | |
| CN108976419A (en) | A kind of aromatic series super-branched polyimide and its preparation method and application containing naphthalene structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140514 Termination date: 20200416 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |