CN104530429A - High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof - Google Patents
High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof Download PDFInfo
- Publication number
- CN104530429A CN104530429A CN201410853090.9A CN201410853090A CN104530429A CN 104530429 A CN104530429 A CN 104530429A CN 201410853090 A CN201410853090 A CN 201410853090A CN 104530429 A CN104530429 A CN 104530429A
- Authority
- CN
- China
- Prior art keywords
- preparation
- polyimide prepolymer
- process window
- high workability
- wide process
- 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
- 0 O=C(*1)C(CC=C(C2)OC(C3C(O4)=O)C=CC=C3C4=O)[C@@]2C1=O Chemical compound O=C(*1)C(CC=C(C2)OC(C3C(O4)=O)C=CC=C3C4=O)[C@@]2C1=O 0.000 description 1
Abstract
The invention relates to a high-fluidity wide-processing-widow polyimide pre-polymer and a preparation method thereof. A structural formula is shown in the description, wherein n is 1-20 and is an integer. The preparation method comprises the steps of dissolving 3,4'-diaminodiphenyl ether 3,4'-ODA in an organic solvent under the nitrogen protection condition, adding 2,3,3',4'-tetracarboxydiphthalic ether dianhydride a-ODPA after complete dissolution, meanwhile adding the organic solvent to enable the solid content of a solution to be 10%-40%, adding an end-capping reagent during reaction at the room temperature to continue to perform reaction, dropwise adding a dehydrating agent to perform reaction, washing, drying and smashing. The pre-polymer can be formed through compression molding, is well applicable to a resin transfer forming process and has potential application value on the aspect of preparation of high-performance composite materials, high-temperature-resisting adhesives and the like.
Description
Technical field
The invention belongs to thermoset performed polymer material and preparation field thereof, particularly the polyimide prepolymer and preparation method thereof of a kind of high workability and wide process window.
Background technology
In the past in more than 30 year, polyimide is owing to having the mechanical property etc. of very high thermo-oxidative stability, excellent chemical and brilliance, make it in novel material and high-tech area etc., serve very important effect, be prepared to various product, comprise film, fiber, sizing agent, engineering plastics, coating and advanced composite material etc.
In order to the solubleness solving high-performance polymer is low, the high processing difficult problem of melt viscosity, meet aerospace and microelectronic to the demand of novel material, the research and development of the polyimide prepolymer containing reactive group cause scientists and pay close attention to widely simultaneously.The processing characteristics of thermoplastic material excellence and the good thermal characteristics of thermosetting material and mechanical property are organically united by this kind of material, during the low molecule performed polymer made, there is good processibility, become the resistant to elevated temperatures thermosetting material of high-performance after cross-linking, its composite material combination property is excellent, can under the environment of very severe life-time service.
The eighties in 20th century, the research institution being representative with U.S. NASA develops phenylacetylene-capped polyimide (PETI) the serial performed polymer more than 100 kinds, wherein PETI-5 has good mechanical property and processibility is the representational kind of most, but after it is crosslinked, second-order transition temperature is relatively low only has 270 DEG C, melt viscosity is comparatively large simultaneously, and minimum melt viscosity is 60000Pas (371 DEG C).In the meantime, researcher have employed introduce lower molecular weight thinner, structure isomerization and control the methods such as the polymerization degree to improve PETI performance.Afterwards, the people such as Japan Yokota have employed 2,3,3', 4'-bibenzene tetracarboxylic dianhydride, 4,4'-diaminodiphenyl oxide and phenylacetylene benzoic anhydride have prepared asymmetrical polyimide (Tri-PI), and after its solidification, second-order transition temperature reaches 343 DEG C, and the minimum melt viscosity of performed polymer is 1000Pas (320 DEG C).
For many years, a lot of researcher is devoted to research Thermocurable polyimide material always can have low melt temperature, low melt viscosity and good solubility before curing, and after solidification, there is higher second-order transition temperature, thermostability and good toughness, there have been many significant contributions for this reason.
Summary of the invention
Technical problem to be solved by this invention is to provide polyimide prepolymer of a kind of high workability and wide process window and preparation method thereof, the present invention uses the diamines 3 of unsymmetric structure, 4'-diaminodiphenyl oxide, the middle diether linkage structure of introducing of dianhydride becomes 2 simultaneously, 3, 3', 4'-diphenyl ether tetraformic dianhydride, the asymmetry of polyimide molecule chain is reduced further with this, the kindliness of further raising polyimide molecule chain, thus further increase its solvability in organic solvent, reduce further the melt viscosity of performed polymer, widen process window when it uses.
The polyimide prepolymer of a kind of high workability of the present invention and wide process window, the structural formula of described polyimide prepolymer is as follows:
; Wherein n=1 ~ 20, and be integer.
The preparation method of the polyimide prepolymer of a kind of high workability of the present invention and wide process window, comprising:
Under nitrogen protection, by 3, 4'-diaminodiphenyl oxide 3, 4'-ODA is dissolved in organic solvent, until completely dissolved, add 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride a-ODPA, add residue organic solvent makes the solid content of solution be 10% ~ 40% simultaneously, react under room temperature after 1 ~ 4 hour and add end-capping reagent, continue reaction 2-8 hour, obtain polyamic acid solution, then dropwise dewatering agent is added, wherein dewatering agent and 3, the mol ratio of 4'-ODA is 1 ~ 6:1, 4-10 hour is reacted under room temperature, washing, dry, pulverize, obtain the polyimide prepolymer of high workability and wide process window, wherein the mol ratio of the consumption of 3,4'-diaminodiphenyl oxides, 2,3,3', 4'-diphenyl ether tetraformic dianhydrides, end-capping reagent is n+1:n:2, and wherein n is the integer of 1 ~ 20.
Described organic solvent is the one in N,N-dimethylacetamide DMAc, N-Methyl pyrrolidone NMP, DMF DMF.
Described 3,4'-diaminodiphenyl oxides 3,4'-ODA are dissolved in the organic solvent of 1/5 ~ 1/2 volume.
Described end-capping reagent is phenylacetylene benzoic anhydride PEPA.
Described dewatering agent is one or more in Acetyl Chloride 98Min., diacetyl oxide, pyridine, triethylamine.
Described washing is distilled water wash 1-5 time, and the pH value to filtration water outlet is 7.
Described oven dry for dry in 80 ~ 150 DEG C of vacuum drying ovens.
Polyimide prepolymer building-up reactions equation in the present invention is:
beneficial effect
1, the present invention adopt diamines and dianhydride be respectively 3,4'-diaminodiphenyl oxide and 2,3,3', 4'-diphenyl ether tetraformic dianhydride, flexible group ehter bond is all introduced in molecular structure, effectively can reduce the second-order transition temperature of performed polymer, widen its process window, its solvability in organic solvent can be improved simultaneously, can find out that its second-order transition temperature is only 123 DEG C from the polyimide prepolymer powder DSC curve prepared, start crosslinking temperature then up to 350 DEG C;
2, the diamines that adopts of the present invention and dianhydride all easily obtains and price is cheaper, their structure is all unsymmetric structure, Resin crystallization degree and Intermolecular Forces are declined, melt viscosity reduces, its minimum melt viscosity is only 0.089Pas and melt viscosity is 223 ~ 335 DEG C in the temperature range of 0.08Pas ~ 1.0Pas, there is the process window of low-down melt viscosity and non-constant width, reduce tonnage, be conducive to producing and reducing production cost;
3, the present invention adopts benzyne base as end-capping reagent, can curing cross-linking reaction be there is under the high temperature conditions in it, without small molecules release, and after solidification, the high-performance polyimide that obtains has good thermostability, its in a nitrogen atmosphere mass loss 5% time temperatures as high 533 DEG C;
4, the present invention adopts dewatering agent to carry out the chemical imidization of polyamic acid to prepare polyimide, and this reaction at room temperature just can be carried out;
5, the performed polymer that the present invention prepares has extraordinary fluidity of molten, its melt viscosity just starts sharply and continuous decrease at 120 DEG C, until 316 DEG C time be minimum melt viscosity 0.089Pas, melt viscosity starts to increase along with temperature raises afterwards, but until 336 DEG C of its melt viscosities just start to be greater than 1.0Pas, therefore this performed polymer has the process window of non-constant width equally, and this performed polymer not only can adopt compression molding, and is applicable to resin transfer molding process well.This performed polymer has potential using value preparing in high performance composite and high-temperature Resistance Adhesives etc.
Accompanying drawing explanation
It is the infrared spectrogram of the polyimide prepolymer that embodiment 2 prepares shown in Fig. 1;
The DSC single pass figure of the polyimide prepolymer that embodiment 2 prepares shown in Fig. 2;
It is the rheometer test curve of the polyimide prepolymer that embodiment 2 prepares shown in Fig. 3;
It is the thermogravimetric curve after polyimide prepolymer that embodiment 2 prepares is cross-linked in nitrogen shown in Fig. 4.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, N-N,N-DIMETHYLACETAMIDE (DMAc, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.02mol, 6.2g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.04mol, 9.92g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 22.51g of gray powdery, productive rate is 99.3%, the polymerization degree of polymkeric substance is 1.In this example, diamines: dianhydride: end-capping reagent mol ratio=2:1:2.
Embodiment 2
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, N-N,N-DIMETHYLACETAMIDE (DMAc, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.027mol, 8.27g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.02mol, 6.61g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 20.18g of gray powdery, productive rate is 95.1%, the polymerization degree of polymkeric substance is 2.In this example, diamines: dianhydride: end-capping reagent mol ratio=2:3:2.
Fig. 1 is the infrared spectrogram of the polyimide prepolymer prepared, and can find out, 1779cm
-1and 1722cm
-1for carbonyl absorption peak, 1378cm
-1, 1110cm
-1and 740cm
-1for the absorption peak of imide ring, and 2215cm
-1for the charateristic avsorption band of phenylacetylene base;
The DSC single pass figure of the polyimide prepolymer prepared by Fig. 2, can find out, its second-order transition temperature is about 123 DEG C, and 224 ~ 260 DEG C is the melting peak of performed polymer, and 350 ~ 470 DEG C is the crosslinked exothermic peak of alkynyl.
It is the rheometer test curve of the polyimide prepolymer that embodiment 2 prepares shown in Fig. 3;
It is the thermogravimetric curve after polyimide prepolymer that embodiment 2 prepares is cross-linked in nitrogen shown in Fig. 4, as seen from the figure, resin after crosslinked in a nitrogen atmosphere mass loss 5% time temperatures as high 533 DEG C, temperatures as high 558 DEG C during mass loss 10%, therefore this resin has higher thermostability.
Embodiment 3
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, N-N,N-DIMETHYLACETAMIDE (DMAc, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.032mol, 9.2g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.016mol, 3.968g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 18.67g of gray powdery, productive rate is 96.6%, the polymerization degree of polymkeric substance is 4.In this example, diamines: dianhydride: end-capping reagent mol ratio=5:4:2.
Embodiment 4
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, N-N,N-DIMETHYLACETAMIDE (DMAc, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.035mol, 10.85g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.01mol, 2.48g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 18.98g of gray powdery, productive rate is 95.4%, the polymerization degree of polymkeric substance is 7.In this example, diamines: dianhydride: end-capping reagent mol ratio=8:7:2.
Embodiment 5
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, N-N,N-DIMETHYLACETAMIDE (DMAc, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.036mol, 11.16g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.008mol, 1.984g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 19.09g of gray powdery, productive rate is 96.9%, the polymerization degree of polymkeric substance is 9.In this example, diamines: dianhydride: end-capping reagent mol ratio=10:9:2.
Embodiment 6
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, N-N,N-DIMETHYLACETAMIDE (DMAc, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.035mol, 10.85g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.01mol, 2.48g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with pyridine (0.12mol, 9.492g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 18.86g of gray powdery, productive rate is 95.8%, the polymerization degree of polymkeric substance is 7.In this example, diamines: dianhydride: end-capping reagent mol ratio=8:7:2.
Embodiment 7
Under nitrogen protection, N-Methyl pyrrolidone (the NMP after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.035mol, 10.85g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.01mol, 2.48g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 18.9g of gray powdery, productive rate is 95.0%, the polymerization degree of polymkeric substance is 7.In this example, diamines: dianhydride: end-capping reagent mol ratio=8:7:2.
Embodiment 8
Under nitrogen protection, the N after underpressure distillation is added in churned mechanically three mouthfuls of round-bottomed flasks, dinethylformamide (DMF, 20g), then 3 are added, 4'-diaminodiphenyl oxide (3, 4'-ODA, 0.04mol, 8g), after it dissolves completely, precise 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride (a-ODPA, 0.035mol, 10.85g), add DMAc again, control reaction density (diamines and dianhydride and be solute) 30%, temperature of reaction is at room temperature reacted after 4 hours and is added end-capping reagent phenylacetylene benzoic anhydride (PEPA, 0.01mol, 2.48g), continue reaction 2 hours, then in the polyamic acid solution generated, triethylamine (0.08mol is dropwise added, 8.08g) with diacetyl oxide (0.12mol, 12.24g), react 5 hours under room temperature, finally the distilled water of the solution 1000mL obtained is cleaned 2 times until the pH value filtering water outlet approximates 7, the product obtained is placed in 120 DEG C of vacuum drying ovens fully dry and pulverize simultaneously, finally obtain the polyimide prepolymer 18.93g of gray powdery, productive rate is 95.2%, the polymerization degree of polymkeric substance is 7.In this example, diamines: dianhydride: end-capping reagent mol ratio=8:7:2.
Claims (7)
1. a polyimide prepolymer for high workability and wide process window, is characterized in that: the structural formula of described polyimide prepolymer is as follows:
Wherein n=1 ~ 20, and be integer.
2. a preparation method for the polyimide prepolymer of high workability as claimed in claim 1 and wide process window, comprising:
Under nitrogen protection, by 3, 4'-diaminodiphenyl oxide 3, 4'-ODA is dissolved in organic solvent, until completely dissolved, add 2, 3, 3', 4'-diphenyl ether tetraformic dianhydride a-ODPA, add organic solvent makes the solid content of solution be 10% ~ 40% simultaneously, react under room temperature after 1 ~ 4 hour and add end-capping reagent, continue reaction 2-8 hour, obtain polyamic acid solution, then dropwise dewatering agent is added, wherein dewatering agent and 3, the mol ratio of 4'-ODA is 1 ~ 6:1, 4-10 hour is reacted under room temperature, washing, dry, pulverize, obtain the polyimide prepolymer of high workability and wide process window, wherein the mol ratio of 3,4'-diaminodiphenyl oxides, 2,3,3', 4'-diphenyl ether tetraformic dianhydrides, end-capping reagent consumption is n+1:n:2, and wherein n is the integer of 1 ~ 20.
3. the preparation method of the polyimide prepolymer of a kind of high workability according to claim 2 and wide process window, it is characterized in that: described organic solvent is N, one in N-N,N-DIMETHYLACETAMIDE DMAc, N-Methyl pyrrolidone NMP, DMF DMF.
4. the preparation method of the polyimide prepolymer of a kind of high workability according to claim 2 and wide process window, is characterized in that: described end-capping reagent is phenylacetylene benzoic anhydride PEPA.
5. the preparation method of the polyimide prepolymer of a kind of high workability according to claim 2 and wide process window, is characterized in that: described dewatering agent is one or more in Acetyl Chloride 98Min., diacetyl oxide, pyridine, triethylamine.
6. the preparation method of the polyimide prepolymer of a kind of high workability according to claim 2 and wide process window, is characterized in that: described washing is distilled water wash 1-5 time, and the pH value to filtration water outlet is 7.
7. the preparation method of the polyimide prepolymer of a kind of high workability according to claim 2 and wide process window, is characterized in that: described oven dry for dry in 80 ~ 150 DEG C of vacuum drying ovens.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410853090.9A CN104530429B (en) | 2014-12-31 | 2014-12-31 | High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410853090.9A CN104530429B (en) | 2014-12-31 | 2014-12-31 | High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104530429A true CN104530429A (en) | 2015-04-22 |
CN104530429B CN104530429B (en) | 2017-02-01 |
Family
ID=52846081
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410853090.9A Active CN104530429B (en) | 2014-12-31 | 2014-12-31 | High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104530429B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105504282A (en) * | 2016-01-11 | 2016-04-20 | 东华大学 | Fluorenyl Cardo type polymide diluting agent and preparing method and application thereof |
CN106188551A (en) * | 2016-07-21 | 2016-12-07 | 株洲时代新材料科技股份有限公司 | A kind of semi-aromatic polyimide modified nylon dragon and preparation method thereof and the preparation method of semi-aromatic polyimides |
CN106279688A (en) * | 2016-08-11 | 2017-01-04 | 中国科学院宁波材料技术与工程研究所 | Thermoset polyimide resin and its preparation method and application |
CN108395534A (en) * | 2018-01-16 | 2018-08-14 | 常州杰铭新材料科技有限公司 | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance |
CN111234222A (en) * | 2020-01-15 | 2020-06-05 | 神马实业股份有限公司 | Preparation method of copolymerization modified thermosetting polyimide material |
WO2022133722A1 (en) * | 2020-12-22 | 2022-06-30 | 宁波长阳科技股份有限公司 | Polyimide material and preparation method therefor and application thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
WO1999062989A1 (en) * | 1998-05-29 | 1999-12-09 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Films, preimpregnated tapes and composites made from polyimide 'salt-like' solutions |
WO2000069948A1 (en) * | 1999-05-18 | 2000-11-23 | The Government Of The United States As Represented By The Administrator Of The National Aeronautics And Space Administration | Composition of and method for making high performance resins for infusion and transfer molding processes |
US7015304B1 (en) * | 2004-07-23 | 2006-03-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Solvent free low-melt viscosity imide oligomers and thermosetting polyimide composites |
CN101089030A (en) * | 2007-06-18 | 2007-12-19 | 南京工业大学 | Prepn process of polyimide microsphere |
US7425650B1 (en) * | 2004-07-23 | 2008-09-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides |
JP4282750B1 (en) * | 2008-02-07 | 2009-06-24 | 大和製罐株式会社 | Imide oligomer and polyimide resin obtained by heat curing this |
CN102206346A (en) * | 2011-05-10 | 2011-10-05 | 中国科学院长春应用化学研究所 | Polyimide resin and preparation method thereof |
CN102492141A (en) * | 2010-12-30 | 2012-06-13 | 上海市合成树脂研究所 | Soluble polyimide molded plastic and preparation method thereof |
-
2014
- 2014-12-31 CN CN201410853090.9A patent/CN104530429B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5567800A (en) * | 1994-10-28 | 1996-10-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom |
WO1999062989A1 (en) * | 1998-05-29 | 1999-12-09 | The Government Of The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) | Films, preimpregnated tapes and composites made from polyimide 'salt-like' solutions |
WO2000069948A1 (en) * | 1999-05-18 | 2000-11-23 | The Government Of The United States As Represented By The Administrator Of The National Aeronautics And Space Administration | Composition of and method for making high performance resins for infusion and transfer molding processes |
US7015304B1 (en) * | 2004-07-23 | 2006-03-21 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Solvent free low-melt viscosity imide oligomers and thermosetting polyimide composites |
US7425650B1 (en) * | 2004-07-23 | 2008-09-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Synthesis of asymmetric tetracarboxylic acids and corresponding dianhydrides |
CN101089030A (en) * | 2007-06-18 | 2007-12-19 | 南京工业大学 | Prepn process of polyimide microsphere |
JP4282750B1 (en) * | 2008-02-07 | 2009-06-24 | 大和製罐株式会社 | Imide oligomer and polyimide resin obtained by heat curing this |
CN102492141A (en) * | 2010-12-30 | 2012-06-13 | 上海市合成树脂研究所 | Soluble polyimide molded plastic and preparation method thereof |
CN102206346A (en) * | 2011-05-10 | 2011-10-05 | 中国科学院长春应用化学研究所 | Polyimide resin and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
KATHY C. CHUANG ET AL: "Polyimide Composites Based on Asymmetric Dianhydrides (a-ODPA vs a-BPDA)", 《54TH INTERNATIONAL SAMPE SYMPOSIUM》 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105504282A (en) * | 2016-01-11 | 2016-04-20 | 东华大学 | Fluorenyl Cardo type polymide diluting agent and preparing method and application thereof |
CN106188551A (en) * | 2016-07-21 | 2016-12-07 | 株洲时代新材料科技股份有限公司 | A kind of semi-aromatic polyimide modified nylon dragon and preparation method thereof and the preparation method of semi-aromatic polyimides |
CN106188551B (en) * | 2016-07-21 | 2019-05-03 | 株洲时代新材料科技股份有限公司 | A kind of preparation method of semi-aromatic polyimide modified nylon dragon and preparation method thereof and semi-aromatic polyimides |
CN106279688A (en) * | 2016-08-11 | 2017-01-04 | 中国科学院宁波材料技术与工程研究所 | Thermoset polyimide resin and its preparation method and application |
CN108395534A (en) * | 2018-01-16 | 2018-08-14 | 常州杰铭新材料科技有限公司 | A kind of solubility height and the good bismaleimide performed polymer and its preparation method and application of temperature tolerance |
CN111234222A (en) * | 2020-01-15 | 2020-06-05 | 神马实业股份有限公司 | Preparation method of copolymerization modified thermosetting polyimide material |
WO2022133722A1 (en) * | 2020-12-22 | 2022-06-30 | 宁波长阳科技股份有限公司 | Polyimide material and preparation method therefor and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN104530429B (en) | 2017-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104530429A (en) | High-fluidity wide-processing-widow polyimide pre-polymer and preparation method thereof | |
CN108219133B (en) | Polyimide resin containing furan ring and preparation method thereof | |
CN105504282B (en) | A kind of fluorenyl Cardo types polyimides diluent and its preparation method and application | |
CN105461922B (en) | A kind of low viscosity thermoset polyimide resin and its preparation method and application | |
CN102492141B (en) | Soluble polyimide molded plastic and preparation method thereof | |
CN103788650A (en) | Colorless and transparent polyimide film and preparation method thereof | |
CN108641082B (en) | Thermosetting polyimide prepolymer and preparation method and application thereof | |
CN107501551B (en) | Polyimide resin, transparent polyimide film and preparation method thereof | |
CN102604091B (en) | Polyimide containing benzimidazole unit and preparation method thereof | |
CN107722314A (en) | A kind of preparation method of thermoplastic polyimide composite material | |
CN107793566B (en) | Thermoplastic polybenzimidazole imide and preparation method thereof | |
CN105017533A (en) | Preparation method for polyamide imide coating | |
CN105440283A (en) | Modified cyanate ester resin and preparation method of modified cyanate ester resin | |
CN107892745B (en) | Thermoplastic polybenzoxazole imide and preparation method thereof | |
CN108752928A (en) | A kind of crosslinked polyimide resin and preparation method thereof containing furan nucleus | |
CN105175721A (en) | Method for preparing polyimide moulding powder with uniform molecular weight distribution | |
CN101225169B (en) | Sulfur fluoro self-crosslinkable polyimide material and preparation method thereof | |
CN103547568B (en) | Employ the terminal-modified imide oligopolymer of 2-phenyl-4,4 '-diamino-diphenyl ethers, its mixture, varnish and cured resin | |
CN109735917A (en) | A kind of ternary copolymerization polyimide spinning solution and preparation method | |
CN104710789A (en) | Preparation method of polyimide molding powder | |
CN101684182B (en) | Preparation method of polyimide film | |
CN105968355B (en) | A kind of synthetic method of polyimides | |
CN101602856A (en) | Polyimide resin of a kind of terminated with phenylacetylene anhydride naphthalene groups and preparation method thereof and purposes | |
CN104371102A (en) | Negative photo-sensitive polyimide and method for preparing same | |
Yin et al. | Synthesis and characterization of soluble polyimides based on trifluoromethylated aromatic dianhydride and substitutional diaminetriphenylmethanes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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 |