CN110092909A - A kind of powder thermoplastic polyimides of lower glass transition temperatures and preparation method thereof - Google Patents
A kind of powder thermoplastic polyimides of lower glass transition temperatures and preparation method thereof Download PDFInfo
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- CN110092909A CN110092909A CN201910484858.2A CN201910484858A CN110092909A CN 110092909 A CN110092909 A CN 110092909A CN 201910484858 A CN201910484858 A CN 201910484858A CN 110092909 A CN110092909 A CN 110092909A
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- thermoplastic polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
Abstract
The present invention relates to powder thermoplastic polyimides of a kind of lower glass transition temperatures and preparation method thereof, the glass transition temperature of thermoplastic polyimide of the invention is 220-250 DEG C, 5-20 μm of average grain diameter.The present invention by introducing specific siloxane group in the molecular structure, polyimide molecule chain slightly cross-linked phenomenon at high temperature can be reduced, thermal stability and excellent in mechanical performance after molding, and then polyimides glass transition temperature can be reduced, therefore processing temperature can be reduced and improve production efficiency reduction production cost, and the safety index in production process can be improved.
Description
Technical field
The present invention relates to polyimides polymeric material fields, and in particular to a kind of powdery heat of lower glass transition temperatures
Plastic polyimide and preparation method thereof.
Background technique
Polyimides (PI) is the high molecular polymer containing cyclic imide group in molecule chain.Polyimides because
It is excellent high temperature resistant, low temperature resistant, high-intensitive, high creep resistant, high dimensionally stable, high electric insulation, low-k and low-loss, resistance to
The advantages that corrosion and be concerned, be known as one of " 21 century most promising engineering plastics ".In view of its excellent performance, again
It is considered as " expert solved the problems, such as ".It, can not be in heating however because polyimides cannot be dissolved in common organic solvent
In the case of melt-processed, and limited extensive use.
In this regard, researchers have researched and developed thermoplastic polyimide, specifically such as by introducing in backbone molecule
Flexible group (such as-O- ,-S- ,-CH2- etc.), reduces molecule chain rigidity, reduces intermolecular active force, or on main chain
Big side group, longer branch or dissymmetrical structure are introduced, intermolecular distance is increased, intermolecular force etc. is reduced, to mention
The thermoplasticity and dissolubility of high polyimides.However, the introducing of flexible group will destroy the thermal stability and machinery of polyimides
Performance, the monomer synthesis with big side group or dissymmetrical structure is relatively difficult, can not large-scale application.In addition to this, traditional
The thermoplastic polyimide of type is there is also assistant officer's problem to be solved, such as glass transition temperature are higher, processing thermoplastic polyamides
Imines needs higher reaction temperature, and temperature range is generally at 300~425 DEG C.Processing thermoplastic polyimides at this temperature,
Other than needing to expend biggish production cost, operator is often exposed under the occasion of potential danger in production process, peace
Full hidden danger is more.The most key is that slight crosslinking has occurred in polyimide molecule chain in this section, so also being claimed
For the polyimides of " pseudo-heat plasticity ".Therefore, pass through MOLECULE DESIGN, the appropriate glass transition temperature for reducing polyimides
(Tg), i.e., processing temperature is extremely important to cost, the safety of its processing procedure.
Summary of the invention
In view of the above shortcomings, the present invention provides a kind of powdered thermoplastic polyimide, glass transition temperature
Low, more conducively machine-shaping is spent, the phenomenon slightly cross-linked at high temperature of polyimide molecule chain, thermostabilization after molding can be reduced
Property and excellent in mechanical performance.
According to technical solution provided by the invention, the powder thermoplastic polyamides for providing a kind of lower glass transition temperatures is sub-
Amine, glass transition temperature are 220-250 DEG C, 5-20 μm of average grain diameter.
Wherein, the powder thermoplastic polyimides by aromatic series tetracid dianhydride and the not aromatic diamine of phenolic hydroxy group,
It is made containing siloxane diamine, contains following structural units:
Wherein, R1、R2For from the quadrivalent organic radical group of aromatic series tetracid dianhydride；G1For the virtue from not phenolic hydroxy group
The bivalent organic group of fragrant race's diamines；G2For from the bivalent organic group containing siloxane diamine；M and n is the whole of 1-500
Number, and n:m is 0.005-0.25:1.
In addition, the aromatic series tetracid dianhydride be the aromatic series tetracid dianhydride be 4,4'- biphenyl ether dianhydride (ODPA) or
One of bisphenol A-type dianhydride (BPADA).Wherein, 4, the 4'- biphenyl ether dianhydride (ODPA) or bisphenol A-type dianhydride (BPADA)
Structural formula it is as follows.
In addition, the aromatic diamine of the not phenolic hydroxy group can be 4,4 '-diamino-diphenyl ethers (ODA), 4,4 '-two
Aminodiphenyl base isophthalic diether (RsDA), 4,4 '-diamino-diphenyl Biphenyl Ethers (BAPB), 4,4 '-diamino-diphenyl bisphenol-As
One of type ether (BPODA), 4,4 '-diamino-diphenyl, four fluoro phenyl ether (BAT).
In addition, described contain siloxane diamine are as follows:
Wherein, the integer of n=0~100, R1With R2It is identical or different, it can be one of methyl, ethyl and phenyl.
It containing siloxane diamine is the double siloxanes of tetramethyl diamines propyl, the double silicon oxygen of tetraethyl diamines propyl in addition, described
One of double siloxanes of alkane, tetraphenyl diamines propyl.On the not diamines of phenolic hydroxy group structure specifically:
It is that will be free of phenol hydroxyl the present invention also provides a kind of preparation method of powder thermoplastic polyimides as described above
It the aromatic diamine of base and is added in reaction kettle containing siloxane diamine, adds solvent, open stirring, clarification to be dissolved
Afterwards, it is slowly added to aromatic series tetracid dianhydride, controls 0-80 DEG C of reaction temperature, reacts 2-6h, polyamide thermoplastic acid resin is made
Then solution is added acetic anhydride and methanol sloughs solvent, obtains the powder thermoplastic polyimides of lower glass transition temperatures.
In addition, the aromatic series tetracid dianhydride and the not aromatic diamine of phenolic hydroxy group and the summation containing siloxane diamine
Molar ratio be 1:1~1.1；Wherein, with molar percent, the aromatic diamine of not phenolic hydroxy group is accounted for containing siloxane diamine
With the 0.1-20mol% of the summation containing siloxane diamine, preferably 0.5-10%.
In addition, the solid content of the polyamide thermoplastic acid resin solution is 5-40wt%, viscosity profile 10000-
250000cps(20℃)。
In addition, the solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone, two
One or more of methyl sulfoxide, sulfolane, 1,4- dioxane, tetrahydrofuran, metacresol.
In the present invention, inventors believe that, it includes flexible on strand for influencing the internal cause of molecular glass transition temperature
Number, space geometry configuration and the molecule of group and intermolecular interaction force size etc..Siloxy group is introduced on main chain,
So that the conformation of strand increases, the resistance of motion of segment is smaller, and energy needed for sub-chain motion is lower, glass transition temperature
Also lower, the active force between segment reduces, and glass transition temperature reduces.
Beneficial effects of the present invention: the present invention provides a kind of powdered powder thermoplastic polyimides, and vitrifying turns
Temperature is low, is more conducive to machine-shaping, can reduce the phenomenon slightly cross-linked at high temperature of polyimide molecule chain, hot after molding
Stability and excellent in mechanical performance.The present invention can reduce the processing temperature raising production efficiency drop that polyimides manufactures process
Low production cost, and the safety index in production process can be improved.
Specific embodiment
It enumerates embodiment more specifically to illustrate the present invention, but the present invention is not by any limit of these embodiments
System, in the technical concept of the present invention, those skilled in the art can carry out various deformation.
In the present invention, described to carry out imidization with acid anhydrides, the acid anhydrides can be trifluoroacetic anhydride, acetic anhydride, propionic acid
One or more of acid anhydride, aromatic monocarboxylate's acid anhydrides, chloroacetic chloride, the dosage of acid anhydrides can be the aromatic series tetracid of 1-4 equivalent
Dianhydride, reaction temperature is at 150-200 DEG C.In addition, the progress that promotor promotes imidization can also be added while reaction, promote
The dosage of agent can be the aromatic series tetracid dianhydride of 1-2 equivalent, and the promotor can be selected from pyridine, β-pyrrolin, diformazan
Yl pyridines, trimethylpyridine, quinoline, isoquinolin, triethylamine, N, one or more of N- dimethylethanolamine.In addition, chemical
Solvent, washing, filtering, drying can be sloughed after imidization, is dried between 100-250 DEG C, and lower glass transition temperatures are obtained
Powder thermoplastic polyimide powder.The solvent of sloughing can choose addition alcohols, washing filtering, and the additional amount of alcohols does not have
Especially limitation, sloughs solvent and cleans pure.
In the present invention, the solid content of the polyamide thermoplastic acid resin is 5-40wt%, more preferable in order to obtain performance
Resin, the preferred 15-30wt% of solid content, the viscosity profile of the polyamide thermoplastic acid resin is 10000-250000cps (20
℃).In addition, accounting for the not aromatic diamine of phenolic hydroxy group with molar percent containing siloxane diamine and containing siloxanes two
The 0.1-20mol% of the summation of amine, from powder thermoplastic polyimides thermal bonding, resistance to ag(e)ing and the stability in use obtained
From the aspect of more preferably, preferably 0.5-10%.
In addition, the application about powder thermoplastic polyimides of the invention, it can be by powdered powder produced by the present invention
Shape thermoplastic polyimide dissolves in a solvent, is coated on substrate, substrate or metal foil material are then covered on coating,
Heat pressure adhesive under high temperature.The coating method does not limit, and can be spin-coating method, spraying coating method, screen printing, dipping
The well-known methods such as method, curtain coating, dip coating, die coating method.
Wherein, the metal foil material can be copper foil, aluminium foil, silver foil etc., and copper foil can be such as rolled copper foil, electrolysis
Copper foil etc..The thickness of the metal foil is not particularly limited, and from obtaining, flexibility is more excellent and the angle of operational stability is examined
Consider, the thickness of metal foil is preferably 50 μm or less.
In the present invention, part material code name used in each embodiment is as follows, is commercially available product.
ODA:4,4'- diamino-diphenyl ether ODPA:4,4'- biphenyl ether dianhydride
RsDA:4,4'- diamino-diphenyl isophthalic diether BAPB:4,4'- diamino-diphenyl Biphenyl Ether
BPODA:4,4'- diamino-diphenyl bisphenol A-type ether DMF:N, dinethylformamide
Four fluoro phenyl ether BPADA of BAT:4,4'- diamino-diphenyl: bisphenol A-type dianhydride
DMAC:N, N- dimethyl acetamide
Embodiment
The aromatic diamine of not phenolic hydroxy group and silicone-containing diamines are added in reaction kettle, solvent is added, is opened
After clarification to be dissolved, aromatic series tetracid dianhydride is added in stirring, is controlled reaction temperature at 50 DEG C, is reacted 3h.The polyimides of preparation
Acid solution contains 20.0% admittedly, and viscosity control is at 100000-250000cps (20 DEG C), and at 20 DEG C, using viscosimeter, (rich strangle flies viscosity
Viscosimeter Brookfield LVT115) measurement.
Acid anhydrides is added, is warming up to 180 DEG C, reacts 4h, methanol is added, filters to obtain powdery product.
Table 1. prepares thermoplastic polyimide
The powdered polyimides performance parameter of table 2.
| The products weight (g) of acquisition | Yield (%) | Appearance | Partial size (μm) | |
| Embodiment 1 | 306.15 | 60% | Pale yellow powder | 5 |
| Embodiment 2 | 331.66 | 65% | Pale yellow powder | 5 |
| Embodiment 3 | 350.37 | 68% | Pale yellow powder | 12 |
| Embodiment 4 | 329.21 | 62% | Pale yellow powder | 12 |
| Embodiment 5 | 385.69 | 63% | Pale yellow powder | 10 |
| Embodiment 6 | 581.36 | 65% | Pale yellow powder | 18 |
| Embodiment 7 | 599.23 | 65% | Pale yellow powder | 20 |
| Embodiment 8 | 417.33 | 66% | Pale yellow powder | 15 |
| Embodiment 9 | 388.74 | 63% | Pale yellow powder | 10 |
| Comparative example 1 | 421.40 | 70% | Yellow powder has bulky grain | Bulky grain |
| Comparative example 2 | 326.70 | 65% | Yellow powder has particle | Little particle |
<test of glass transition temperature Tg>
It is measured by differential scanning calorimetry DSC, test condition: the sample of 10-15mg is placed in crucible, showing difference
Test, test condition are put on scanning amount instrument are as follows: nitrogen atmosphere, heating rate are 10 DEG C/min, and temperature test range is room temperature-
450℃。
<water absorption rate test>
It by the powdex that drying to constant weight (Wd), is placed 48 hours at 80 DEG C, rapidly weighs (Ws) on balance.
Water absorption rate S can calculate S=(Ws-Wd)/Wd*100 (%) by formula.
The performance test of 3. thermoplastic polyimide of table
| Glass transition temperature Tg (DEG C) | Water absorption rate (%) | |
| Embodiment 1 | 220 | 0.32 |
| Embodiment 2 | 238 | 0.30 |
| Embodiment 3 | 230 | 0.26 |
| Embodiment 4 | 241 | 0.36 |
| Embodiment 5 | 248 | 0.28 |
| Embodiment 6 | 253 | 0.31 |
| Embodiment 7 | 250 | 0.30 |
| Embodiment 8 | 249 | 0.35 |
| Embodiment 9 | 245 | 0.29 |
| Comparative example 1 | 286 | 0.42 |
| Comparative example 2 | 326 | 0.45 |
With suitable thermoplastic polyimide powder, under hot pressing temperature, hot-forming under the pressure of 5MPa is 20 micro-
Rice thin slice, obtains thermoplastic polyimide sheet coupon, and test performance is as shown in the table.
<thermal expansion coefficient>
Using thermomechanical analyzer (TMA), the polyimides sample to test is warming up to 350 DEG C in TMA, in the temperature
Degree is lower to be kept after ten minutes, with the rate of temperature fall of 5 DEG C/min, finding out the thermal expansion coefficient between 350 DEG C to 100 DEG C.
The hot-forming polyimides performance of table 4.
Powder thermoplastic polyimides produced by the present invention, glass transition temperature is lower, is more conducive to machine-shaping.This
Invention reduces the light at high temperature of polyimide molecule chain because specific siloxane group is added in the molecular structure
Micro- crosslinking phenomena, thermal stability and excellent in mechanical performance after molding, and then the processing that polyimides manufactures process can be reduced
Temperature, therefore production efficiency reduction production cost can be improved, and the safety index in production process can be improved.
Claims (10)
1. a kind of powder thermoplastic polyimides of lower glass transition temperatures, which is characterized in that its glass transition temperature is
220-250 DEG C, 5-20 μm of average grain diameter.
2. powder thermoplastic polyimides according to claim 1, which is characterized in that the powder thermoplastic polyimides
It is made by aromatic series tetracid dianhydride with the aromatic diamine of not phenolic hydroxy group, containing siloxane diamine, contains following structure lists
Member:
Wherein, R1、R2For from the quadrivalent organic radical group of aromatic series tetracid dianhydride；G1For the aromatic series from not phenolic hydroxy group
The bivalent organic group of diamines；G2For from the bivalent organic group containing siloxane diamine；M and n is the integer of 1-500,
And n:m is 0.005-0.25:1.
3. powder thermoplastic polyimides according to claim 2, which is characterized in that the aromatic series tetracid dianhydride is 4,
One of 4'- biphenyl ether dianhydride (ODPA) or bisphenol A-type dianhydride (BPADA).
4. powder thermoplastic polyimides according to claim 2, which is characterized in that the aromatic series of the not phenolic hydroxy group
Diamines can be 4,4 '-diamino-diphenyl ethers (ODA), 4,4 '-diamino-diphenyl isophthalic diether (RsDA), 4,4 '-diaminos
Base diphenyl Biphenyl Ether (BAPB), 4,4 '-diamino-diphenyl bisphenol A-type ethers (BPADA), 4,4 '-diamino-diphenyl tetrafluoros
For one of phenyl ether (BAT).
5. powder thermoplastic polyimides according to claim 2, which is characterized in that described to contain siloxane diamine are as follows:
Wherein, the integer of n=0~100, R1With R2It is identical or different, it can be one of methyl, ethyl and phenyl.
6. powder thermoplastic polyimides according to claim 5, which is characterized in that it is described containing siloxane diamine be four
One of the double siloxanes of methanediamine propyl, the double siloxanes of tetraethyl diamines propyl, the double siloxanes of tetraphenyl diamines propyl.
7. a kind of preparation method of the powder thermoplastic polyimides as described in any one of claim 1-6, feature exist
In being added in reaction kettle by the aromatic diamine of not phenolic hydroxy group and containing siloxane diamine, add solvent, unlatching is stirred
It mixes, after clarification to be dissolved, is slowly added to aromatic series tetracid dianhydride, controls 0-80 DEG C of reaction temperature, react 2-6h, thermoplasticity is made
Polyamic acid resin solution sloughs solvent after further carrying out imidization with acid anhydrides, obtains powdered lower glass transition temperatures
Powder thermoplastic polyimides.
8. powder thermoplastic polyimides according to claim 7, which is characterized in that the aromatic series tetracid dianhydride with not
The molar ratio of the aromatic diamine of phenolic hydroxy group and the summation containing siloxane diamine is 1:1~1.1；Wherein, with Mole percent
Than meter, the 0.1- of the not aromatic diamine of phenolic hydroxy group and the summation containing siloxane diamine is accounted for containing siloxane diamine
20mol%, preferably 0.5-10%.
9. preparation method according to claim 7, which is characterized in that the consolidating for polyamide thermoplastic acid resin solution contains
Amount is 5-40wt%, viscosity profile is 10000-250000cps (20 DEG C).
10. preparation method according to claim 7, spy are, the solvent is n,N-Dimethylformamide, N, N- bis-
Methylacetamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran, in metacresol
One or more.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332779A (en) * | 1998-12-28 | 2002-01-23 | 西洋化学公司 | Polyamideimidesiloxane hot melt adhesive |
| JP2008081534A (en) * | 2006-09-26 | 2008-04-10 | Toray Ind Inc | Heat-resistant resin precursor composition |
| JP2009096028A (en) * | 2007-10-16 | 2009-05-07 | Toray Ind Inc | Laminated resin film, laminated film with metal layer using the same, and flexible circuit board |
| CN101506270A (en) * | 2006-06-22 | 2009-08-12 | 沙伯基础创新塑料知识产权有限公司 | Polysiloxane/polyimide copolymers and blends thereof |
| CN101506271A (en) * | 2006-06-22 | 2009-08-12 | 沙伯基础创新塑料知识产权有限公司 | Process for making polysiloxane/polyimide copolymer blends |
| CN103524768A (en) * | 2013-10-30 | 2014-01-22 | 宏威高新材料有限公司 | Novel electronic-grade polyimide film with low linear expansion coefficient and production method thereof |
-
2019
- 2019-06-05 CN CN201910484858.2A patent/CN110092909A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332779A (en) * | 1998-12-28 | 2002-01-23 | 西洋化学公司 | Polyamideimidesiloxane hot melt adhesive |
| CN101506270A (en) * | 2006-06-22 | 2009-08-12 | 沙伯基础创新塑料知识产权有限公司 | Polysiloxane/polyimide copolymers and blends thereof |
| CN101506271A (en) * | 2006-06-22 | 2009-08-12 | 沙伯基础创新塑料知识产权有限公司 | Process for making polysiloxane/polyimide copolymer blends |
| JP2008081534A (en) * | 2006-09-26 | 2008-04-10 | Toray Ind Inc | Heat-resistant resin precursor composition |
| JP2009096028A (en) * | 2007-10-16 | 2009-05-07 | Toray Ind Inc | Laminated resin film, laminated film with metal layer using the same, and flexible circuit board |
| CN103524768A (en) * | 2013-10-30 | 2014-01-22 | 宏威高新材料有限公司 | Novel electronic-grade polyimide film with low linear expansion coefficient and production method thereof |
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Application publication date: 20190806 |