CN104530429B - 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
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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 thermosetting performed polymer material and its preparation field, particularly to a kind of high fluidity and wide process window
Polyimide prepolymer of mouth and preparation method thereof.
Background technology
In past more than 30 year, polyimides are due to having very high thermo-oxidative stability, excellent chemical and brilliance
Mechanical performance etc. so that it serves very important effect at the aspect such as new material and high-tech area, be produced
Various products are become, including thin film, fiber, adhesive, engineering plastics, coating and advanced composite material etc..
The processing difficult problem such as the dissolubility in order to solve high-performance polymer is low, melt viscosity is high, meets Aero-Space simultaneously
And the demand to new material for the microelectronic, the research and development of the polyimide prepolymer containing reactive group cause scientists
Widely pay close attention to.This kind of material is by hot property good to processing characteristics excellent for thermoplastic and thermosets and mechanicalness
Can organically unite, during the low molecule performed polymer made, there is good processability, become the resistance to height of high-performance after cross-linking
The thermosets of temperature, its composite material combination property is excellent, can in the environment of very severe life-time service.
The eighties in 20th century, the research institution with U.S. nasa as representative develops phenylacetylene-capped more than 100 kinds
Polyimides (peti) series performed polymer, it is most representational that wherein peti-5 has good mechanical performance and processability
Kind, but relatively low only 270 DEG C of glass transition temperature after its crosslinking, melt viscosity is larger simultaneously, and minimum melt sticks
Spend for 60000pa s (371 DEG C).In the meantime, researcher employs introducing low molecular weight diluent, the isomery of structure
Change and control the methods such as the degree of polymerization to improve peti performance.Later, Japanese yokota et al. employed 2,3,3', 4'- biphenyl four
Formic acid dianhydride, 4,4'- diaminodiphenyl ether and phenylacetylene benzoic anhydride are prepared for asymmetrical polyimides (tri-pi), after its solidification
Glass transition temperature reaches 343 DEG C, and the minimum melt viscosity of performed polymer is 1000pa s (320 DEG C).
For many years, a lot of researchers always be devoted to study Thermocurable polyimide material can have before curing
Low melt temperature, low melt viscosity and good dissolubility, and it is steady to have higher glass transition temperature, heat after solidifying
Qualitative and good toughness, has had many significant contributions for this.
Content of the invention
The technical problem to be solved is to provide the polyimides pre-polymerization of a kind of high fluidity and wide process window
Body and preparation method thereof, the present invention uses the diamidogen 3 of unsymmetric structure, 4'- diaminodiphenyl ether, the middle introducing of dianhydride simultaneously
Diether linkage structure is changed into 2,3,3', 4'- diphenyl ether tetraformic dianhydride, to reduce the asymmetric of polyimide molecule chain further with this
Property, improving the compliance of polyimide molecule chain further, thus further increasing its dissolubility in organic solvent, entering
One step reduces the melt viscosity of performed polymer, has widened process window during its use.
A kind of high fluidity of the present invention and the polyimide prepolymer of wide process window, described polyimide prepolymer
Structural formula is as follows:
；
Wherein n=1～20, and be integer.
A kind of preparation method of the polyimide prepolymer of the high fluidity of the present invention and wide process window, comprising:
Under nitrogen protection, by 3,4'- diaminodiphenyl ether 3,4'-oda is dissolved in organic solvent, until completely dissolved,
Add 2,3,3', 4'- diphenyl ether tetraformic dianhydride a-odpa, be simultaneously introduced remaining organic solvent so that the solid content of solution is
10%～40%, add end-capping reagent after reacting 1～4 hour under room temperature, continue 2-8 hour of reaction, obtain polyamic acid molten
Liquid, the mol ratio being then added dropwise over dehydrant, wherein dehydrant and 3,4'-oda is 1～6:1, reaction 4-10 at room temperature
Hour, washing, dry, pulverize, obtain final product high fluidity and the polyimide prepolymer of wide process window；Wherein 3,4'- diaminourea
Diphenyl ether, 2,3,3', 4'- diphenyl ether tetraformic dianhydride, the mol ratio of the consumption of end-capping reagent are n+1:n:2, and wherein n is 1～20
Integer.
Described organic solvent is n, n- dimethyl acetylamide dmac, n- methyl pyrrolidone nmp, n, n- dimethyl formyl
One of amine dmf.
Described 3,4'- diaminodiphenyl ether 3,4'-oda is dissolved in the organic solvent of 1/5～1/2 volume.
Described end-capping reagent is phenylacetylene benzoic anhydride pepa.
Described dehydrant is one or more of chloroacetic chloride, acetic anhydride, pyridine, triethylamine.
Described wash as distilled water wash 1-5 time, be 7 to filtering the ph value of water outlet.
Described drying is to dry in 80～150 DEG C of vacuum drying ovens.
Polyimide prepolymer synthetic reaction equation in the present invention is:
Beneficial effect
1st, the diamidogen that the present invention adopts and dianhydride are respectively 3,4'- diaminodiphenyl ether and 2,3,3', 4'- diphenyl ether tetramethyl
Acid dianhydride, all introduces flexible group ehter bond, can be effectively reduced the glass transition temperature of performed polymer, open up in molecular structure
Its process window wide, can improve its dissolubility in organic solvent, from the polyimide prepolymer powder prepared simultaneously
Dsc curve can be seen that its glass transition temperature is only 123 DEG C, starts then up to 350 DEG C of crosslinking temperature；
2nd, the present invention adopt diamidogen and dianhydride is all readily available and price is less expensive, their structure is all unsymmetrical knot
So that Resin crystallization degree and intermolecular force decline, melt viscosity reduces structure, and its minimum melt viscosity is only 0.089pa s
And melt viscosity 0.08pa s～1.0pa s temperature range be 223～335 DEG C, have low-down melt viscosity and
The process window of non-constant width, reduces tonnage, is conducive to producing and reduces production cost；
3rd, the present invention adopts benzyne base as end-capping reagent, and it can occur curing cross-linking reaction under the high temperature conditions, no little
Molecule discharges, and the high-performance polyimide that obtains has good heat stability after solidifying, its in a nitrogen atmosphere quality damage
Lose up to 533 DEG C of temperature when 5%；
4th, the present invention to prepare polyimides using the chemical imidization that dehydrant carries out polyamic acid, and this reaction is at room temperature
Just can carry out；
5th, the performed polymer that the present invention prepares has extraordinary fluidity of molten, and its melt viscosity is just opened at 120 DEG C
Begin drastically and continuous decrease, until being minimum melt viscosity 0.089pa s when 316 DEG C, melt viscosity raises with temperature afterwards
Start to increase, but until 336 DEG C of its melt viscosities just start more than 1.0pa s, therefore this performed polymer equally has non-constant width
Process window, this performed polymer not only can adopt compression molding, and is perfectly suitable for resin transfer molding process.Should
Performed polymer has potential using value preparing the aspects such as high-performance composite materials and high-temperature Resistance Adhesives.
Brief description
It is the infrared spectrogram of the polyimide prepolymer that embodiment 2 prepares shown in Fig. 1；
It is 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 thermogravimetric curve in nitrogen after the polyimide prepolymer crosslinking that embodiment 2 prepares shown in Fig. 4.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Yl acetamide (dmac, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely molten
Xie Hou, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.02mol, 6.2g), add dmac, control
30%, reaction temperature adds end-capping reagent after reacting 4 hours at room temperature to reaction density (diamidogen and dianhydride and be solute)
Phenylacetylene benzoic anhydride (pepa, 0.04mol, 9.92g), continues reaction 2 hours, then dropwise adds in the polyamic acid solution generating
Enter triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react 5 hours at room temperature, finally will obtain
Solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 22.51g of gray powdery, yield
For 99.3%, the degree of polymerization of polymer is 1.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=2:1:2.
Embodiment 2
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Yl acetamide (dmac, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely molten
Xie Hou, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.027mol, 8.27g), add dmac, control
30%, reaction temperature adds end-blocking after reacting 4 hours at room temperature to reaction density processed (diamidogen and dianhydride and be solute)
Agent phenylacetylene benzoic anhydride (pepa, 0.02mol, 6.61g), continues reaction 2 hours, then in the polyamic acid solution generating dropwise
Add triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react at room temperature 5 hours, finally incite somebody to action
To solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 20.18g of gray powdery, yield
For 95.1%, the degree of polymerization of polymer is 2.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=2:3:2.
Fig. 1 is the infrared spectrogram of the polyimide prepolymer preparing it can be seen that 1779cm-1And 1722cm-1
For carbonyl absorption peak, 1378cm-1、1110cm-1And 740cm-1For the absworption peak of imide ring, and 2215cm-1Spy for phenylacetylene base
Levy absworption peak；
The dsc single pass figure of the polyimide prepolymer being prepared by Fig. 2 is it can be seen that its glass transition temperature
Degree 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 thermogravimetric curve in nitrogen after the polyimide prepolymer crosslinking that embodiment 2 prepares shown in Fig. 4, by
Figure as can be seen that resin after crosslinking in a nitrogen atmosphere mass loss 5% when up to 533 DEG C of temperature, during mass loss 10%
Up to 558 DEG C of temperature, therefore this resin has higher heat stability.
Embodiment 3
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Yl acetamide (dmac, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely molten
Xie Hou, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.032mol, 9.2g), add dmac, control
30%, reaction temperature adds end-capping reagent after reacting 4 hours at room temperature to reaction density (diamidogen and dianhydride and be solute)
Phenylacetylene benzoic anhydride (pepa, 0.016mol, 3.968g), continues reaction 2 hours, then in the polyamic acid solution generating dropwise
Add triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react at room temperature 5 hours, finally incite somebody to action
To solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 18.67g of gray powdery, yield
For 96.6%, the degree of polymerization of polymer is 4.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=5:4:2.
Embodiment 4
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Yl acetamide (dmac, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely molten
Xie Hou, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.035mol, 10.85g), add dmac, control
30%, reaction temperature adds end-blocking after reacting 4 hours at room temperature to reaction density processed (diamidogen and dianhydride and be solute)
Agent phenylacetylene benzoic anhydride (pepa, 0.01mol, 2.48g), continues reaction 2 hours, then in the polyamic acid solution generating dropwise
Add triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react at room temperature 5 hours, finally incite somebody to action
To solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 18.98g of gray powdery, yield
For 95.4%, the degree of polymerization of polymer is 7.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=8:7:2.
Embodiment 5
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Yl acetamide (dmac, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely molten
Xie Hou, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.036mol, 11.16g), add dmac, control
30%, reaction temperature adds end-blocking after reacting 4 hours at room temperature to reaction density processed (diamidogen and dianhydride and be solute)
Agent phenylacetylene benzoic anhydride (pepa, 0.008mol, 1.984g), continue reaction 2 hours, then generate polyamic acid solution in by
It is added dropwise to triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react at room temperature 5 hours, finally will
The solution the obtaining distilled water of 1000ml cleans 2 times until the ph value filtering water outlet approximates 7, the product obtaining is put simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 19.09g of gray powdery, produce
Rate is 96.9%, and the degree of polymerization of polymer is 9.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=10:9:2.
Embodiment 6
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Yl acetamide (dmac, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely molten
Xie Hou, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.035mol, 10.85g), add dmac, control
30%, reaction temperature adds end-blocking after reacting 4 hours at room temperature to reaction density processed (diamidogen and dianhydride and be solute)
Agent phenylacetylene benzoic anhydride (pepa, 0.01mol, 2.48g), continues reaction 2 hours, then in the polyamic acid solution generating dropwise
Add triethylamine (0.08mol, 8.08g) and pyridine (0.12mol, 9.492g), react 5 hours at room temperature, finally will obtain
Solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 18.86g of gray powdery, yield
For 95.8%, the degree of polymerization of polymer is 7.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=8:7:2.
Embodiment 7
Under nitrogen protection, add the n- methyl pyrrole after vacuum distillation in churned mechanically three neck round bottom flask
Pyrrolidone (nmp, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely dissolved
Afterwards, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.035mol, 10.85g), add dmac, control
30%, reaction temperature adds end-capping reagent after reacting 4 hours at room temperature to reaction density (diamidogen and dianhydride and be solute)
Phenylacetylene benzoic anhydride (pepa, 0.01mol, 2.48g), continues reaction 2 hours, then dropwise adds in the polyamic acid solution generating
Enter triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react 5 hours at room temperature, finally will obtain
Solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 18.9g of gray powdery, yield
For 95.0%, the degree of polymerization of polymer is 7.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=8:7:2.
Embodiment 8
Under nitrogen protection, add the n after vacuum distillation, n- diformazan in churned mechanically three neck round bottom flask
Base Methanamide (dmf, 20g), is subsequently adding 3,4'- diaminodiphenyl ether (3,4'-oda, 0.04mol, 8g), treats that it is completely dissolved
Afterwards, precise 2,3,3', 4'- diphenyl ether tetraformic dianhydride (a-odpa, 0.035mol, 10.85g), add dmac, control
30%, reaction temperature adds end-capping reagent after reacting 4 hours at room temperature to reaction density (diamidogen and dianhydride and be solute)
Phenylacetylene benzoic anhydride (pepa, 0.01mol, 2.48g), continues reaction 2 hours, then dropwise adds in the polyamic acid solution generating
Enter triethylamine (0.08mol, 8.08g) and acetic anhydride (0.12mol, 12.24g), react 5 hours at room temperature, finally will obtain
Solution cleaned with the distilled water of 1000ml 2 times until filter water outlet ph values approximate 7, the product obtaining is placed in simultaneously
Fully dry in 120 DEG C of vacuum drying ovens and pulverize, finally give the polyimide prepolymer 18.93g of gray powdery, yield
For 95.2%, the degree of polymerization of polymer is 7.In this example, diamidogen: dianhydride: end-capping reagent mol ratio=8:7:2.
Claims (7)
1. a kind of high fluidity and wide process window polyimide prepolymer it is characterised in that: described polyimide prepolymer
Structural formula as follows:
；
Wherein n=1～20, and be integer, polyimide prepolymer melt viscosity is in the temperature range of 0.08pa s ~ 1.0pa s
For 223 ~ 335 DEG C.
2. the preparation method of the polyimide prepolymer of a kind of high fluidity as claimed in claim 1 and wide process window, bag
Include:
Under nitrogen protection, by 3,4'- diaminodiphenyl ether 3,4'-oda is dissolved in organic solvent, until completely dissolved, adds
2,3,3', 4'- diphenyl ether tetraformic dianhydride a-odpa, being simultaneously introduced organic solvent and making the solid content of solution is 10%～40%,
Add end-capping reagent after reacting 1～4 hour under room temperature, continue 2-8 hour of reaction, obtain polyamic acid solution, then dropwise
Add dehydrant, the wherein mol ratio of dehydrant and 3,4'-oda is 1～6:1, reacts 4-10 hour, washing at room temperature, dries
Dry, pulverizing, obtains final product high fluidity and the polyimide prepolymer of wide process window；Wherein 3,4'- diaminodiphenyl ether, 2,3,
3', 4'- diphenyl ether tetraformic dianhydride, the mol ratio of end-capping reagent consumption are n+1:n:2, and wherein n is 1～20 integer.
3. the preparation method of the polyimide prepolymer of a kind of high fluidity according to claim 2 and wide process window,
It is characterized in that: described organic solvent is n, n- dimethyl acetylamide dmac, n- methyl pyrrolidone nmp, n, n- dimethyl
One of Methanamide dmf.
4. the preparation method of the polyimide prepolymer of a kind of high fluidity according to claim 2 and wide process window,
It 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 fluidity according to claim 2 and wide process window,
It is characterized in that: described dehydrant is one or more of chloroacetic chloride, acetic anhydride, pyridine, triethylamine.
6. the preparation method of the polyimide prepolymer of a kind of high fluidity according to claim 2 and wide process window,
It is characterized in that: described wash as distilled water wash 1-5 time, be 7 to filtering the ph value of water outlet.
7. the preparation method of the polyimide prepolymer of a kind of high fluidity according to claim 2 and wide process window,
It is characterized in that: described drying is to dry in 80～150 DEG C of vacuum drying ovens.
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| CN105504282B (en) * | 2016-01-11 | 2018-01-02 | 东华大学 | A kind of fluorenyl Cardo types polyimides diluent and its preparation method and application |
| 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 |
| CN106279688B (en) * | 2016-08-11 | 2019-01-11 | 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 |
| CN114018425A (en) * | 2021-11-04 | 2022-02-08 | 辽宁佳宇电子产品有限公司 | Flexible thin film platinum resistance sensor and preparation method thereof |
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| 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 |
| US6222007B1 (en) * | 1998-05-29 | 2001-04-24 | The United States Of America As Represented By The National Aeronautics And Space Administration | Films, preimpregnated tapes and composites made from polyimide “Salt-like” Solutions |
| ATE340208T1 (en) * | 1999-05-18 | 2006-10-15 | Nasa | COMPOSITION AND METHOD FOR PRODUCING HIGH-PERFORMANCE RESINS FOR INFUSION AND TRANSFER SPRAY PROCESSES |
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| 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 |
| CN100506886C (en) * | 2007-06-18 | 2009-07-01 | 南京工业大学 | Preparation method of polyimide microspheres |
| 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 |
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| CN102206346B (en) * | 2011-05-10 | 2013-04-10 | 中国科学院长春应用化学研究所 | Polyimide resin and preparation method thereof |
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