CN102618206B - Polyimide adhesive - Google Patents
Polyimide adhesive Download PDFInfo
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- CN102618206B CN102618206B CN2012100856516A CN201210085651A CN102618206B CN 102618206 B CN102618206 B CN 102618206B CN 2012100856516 A CN2012100856516 A CN 2012100856516A CN 201210085651 A CN201210085651 A CN 201210085651A CN 102618206 B CN102618206 B CN 102618206B
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Abstract
A polyimide adhesive relates to an adhesive and aims at solving problems that the existing polyimide structural adhesive is poor in toughness and decreasing in viscosity and strength is apt to occur in the storing process. The polyimide adhesive is composed of polyimide carrier membranes and polyamide acid primers which are independently packaged. The polyimide adhesive has the advantages that shearing strength at room temperature is 18MPa-22MPa, shearing strength at temperature of 320 DEG C is 10MPa-16MPa, peeling strength at temperature of 90 DEG C is 2kN/m-4kN/m, glass-transition temperature is larger than 300 DEG C, and 5% thermo-gravimetric temperature is larger than 520 DEG C; and bonding strength change is smaller than 5% after thermal ageing at temperature of 300 DEG C after 160 hours, and the polyimide adhesive is suitable for being used as a high temperature structural adhesive. The polyimide adhesive is mainly used for polyimide adhesive preparing.
Description
Technical field
The present invention relates to a kind of tackiness agent.
Background technology
Since polyesteramide model plastic in 1964 comes out, the polyimide heatproof oxidation performance energy excellent with it, mechanical property, dielectric properties, good solvent resistance, high glass-transition temperature etc., develop into gradually covering extensive fields, goods are various, a widely used class high temperature material, all have application in fields such as moulding resin/part, insulated wire, film, fiber, preimpregnation material/matrix material, coating, tackiness agent and foams.
At adhesive area, as the important material connected for material, can partly replace traditional welding, riveted joint or bolt and connect, especially, in the connection of the members such as matrix material that at all can't use welding or riveted joint, have a extensive future.Polyimide is used and is subject to great restriction as tackiness agent, mainly that polyimide main chain section rigidity is high, poor toughness, due to conventional toughner and the polyimide compatibility poor, and reduce the high-temperature behavior of polyimide, therefore the improvement of polyimide toughness generally all realizes by the design change of main chain segment structure, but the decline that the raising of same main chain section flexibility also brings high thermal resistance.In addition, polyimide solution type tackiness agent polyimide main chain section in depositing process degrades, causes tackiness agent viscosity, bonding strength to descend gradually.
Summary of the invention
Purpose of the present invention will solve existing polyimide structures tackiness agent poor toughness, and there will be the problem of reduced viscosity, strength degradation in storage process, and a kind of polyimides adhesive and preparation method thereof is provided.
A kind of polyimides adhesive is comprised of polyimide support film and the polyamic acid primer of independent packing.
Advantage of the present invention: one, polyimides adhesive normal temperature down cut intensity of the present invention is that 18MPa～22MPa, 320 ℃ of down cut intensity are that 10MPa～16MPa, 90 ° of stripping strength 2kN/m～4kN/m, second-order transition temperatures are greater than 300 ℃, 5% thermal weight loss temperature and are greater than 520 ℃; Two, polyimides adhesive of the present invention is very little through the bonding strength variation in 160 hours of 300 ℃ of thermal ageings, has excellent thermotolerance, is suitable as high-temperature-resistant structure bonding.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: to be a kind of polyimides adhesive be comprised of polyimide support film and the polyamic acid primer of independent packing present embodiment.
The using method of present embodiment polyimides adhesive is as follows: the docking side that at first the polyamic acid primer is spread upon to thing A to be pasted and thing B to be pasted, then the polyimide support film is sticked on to thing A joint to be pasted or thing B joint to be pasted, finally docking extruding is bonding, completes taping process.
Present embodiment polyimides adhesive normal temperature down cut intensity is that 18MPa～22MPa, 320 ℃ of down cut intensity are that 10MPa～16MPa, 90 ° of stripping strength 2kN/m～4kN/m, second-order transition temperatures are greater than 300 ℃, 5% thermal weight loss temperature and are greater than 520 ℃.
The present embodiment polyimides adhesive reduces and is less than 5% through 160 hours bonding strengths of 300 ℃ of thermal ageings, changes very littlely, has excellent thermotolerance, is suitable as high-temperature-resistant structure bonding; And the present embodiment polyimides adhesive is comprised of polyimide support film and the polyamic acid primer of independent packing, therefore in storage process, not there will be the situation of reduced viscosity, strength decreased.
Embodiment two: the difference of present embodiment and embodiment one is: the carrier film that described polyimide support film is polyimide content 40%～60%; The polyamide thermoplastic acid solution that described polyamic acid primer is mass concentration 5%～10%.
Embodiment three: the difference of present embodiment and embodiment two is: described polyimide support film is preparation according to the following steps specifically: one, prepare thermosetting polyamide acid: at first by 4, 4 '-diaminodiphenyl oxide adds in non-proton type solvent, be stirred to fully and dissolve, obtain clear solution I, clear solution I is cooled to 5 ℃～10 ℃ under condition of ice bath, then low whipping speed is to add 3 under 50 turn/min～200 turn/min, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, and low whipping speed is to continue stirring reaction 3h～5h under 50 turn/min～200 turn/min, obtain initial reaction liquid, then low whipping speed is under 50 turn/min～200 turn/min, 4-phenylacetylene base phthalic anhydride to be joined in initial reaction liquid, and low whipping speed is to continue stirring reaction 5h～7h under 50 turn/min～200 turn/min, the thermosetting polyamide acid solution that to obtain mass concentration be 30%～50%, described in step 13,3 ', 4,4 '-mol ratio of benzophenone tetracarboxylic dianhydride and 4-phenylacetylene base phthalic anhydride is (2～3): 2, the mol ratio of the 4，4′-diaminodipohenyl ether described in step 1 and 4-phenylacetylene base phthalic anhydride is (3～4): 2, the amount of substance of 4，4′-diaminodipohenyl ether described in step 1 is m
1, 3,3 ', 4,4 '-amount of substance of benzophenone tetracarboxylic dianhydride is m
2, m
1with m
2meet m
1-m
2=1mol, two, prepare polyamide thermoplastic acid: by 1, two (4-amino-benzene oxygen) benzene of 3-adds in non-proton type solvent, be stirred to fully and dissolve, obtain clear solution II, clear solution II is cooled to 5 ℃～10 ℃ under condition of ice bath, then low whipping speed is to add 3 under 50 turn/min～200 turn/min, 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 5h～10h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 30%～50%, described in step 21, two (4-amino-benzene oxygen) benzene and 3,3 of 3-', 4,4 '-mol ratio that oxygen supports adjacent pyromellitic dianhydride is 1: 1, three, blend: thermosetting polyamide acid and polyamide thermoplastic acid that mass concentration is identical are 10 in mass ratio: (3～7) mix, and obtain blend, four, moulding: the blend that step 3 is obtained is coated on carrier, then under 110 ℃～130 ℃, dries 40min～80min, finally, at 180 ℃～220 ℃ lower thermal treatment 40min～80min, obtains the carrier film that polyimide content is 40～60%.
Present embodiment is used polyamide thermoplastic acid toughened thermosetting polyimide, has improved the toughness of polyimide, has improved the bonding strength of tackiness agent; Also improved the film-forming properties of tackiness agent simultaneously, be prepared into after carrier film and solved polyimide solution type tackiness agent and deposit the problem that degraded in process, viscosity, bonding strength descend.
Embodiment four: the difference of present embodiment and embodiment three is: the non-proton type solvent described in step 1 is N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide or N-Methyl pyrrolidone.
Embodiment five: present embodiment and one of embodiment three or four difference are: described carrier is that specification is 100g/m
2～180g/m
2Woven fiber glass or specification be 100g/m
2～180g/m
2Quartz fabric.
Embodiment six: the difference of present embodiment and embodiment two is: described polyamic acid primer is preparation according to the following steps specifically: by 1, two (4-amino-benzene oxygen) benzene of 3-adds in non-proton type solvent, be stirred to fully and dissolve, obtain clear solution, clear solution is cooled to 5 ℃～10 ℃ under condition of ice bath, then low whipping speed is to add 3 under 50 turn/min～200 turn/min, 3 ', 4, 4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 5h～10h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 30%～50%, add non-proton type solvent to be diluted, the mass concentration that is diluted to polyamide thermoplastic acid is till 5%～10%, obtain the polyamic acid primer, described 1, two (4-amino-benzene oxygen) benzene and 3,3 of 3-', 4,4 '-mol ratio that oxygen supports adjacent pyromellitic dianhydride is 1: 1.
Embodiment seven: the difference of present embodiment and embodiment six is: described non-proton type solvent is N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide or N-Methyl pyrrolidone.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of polyimides adhesive comprises polyimide support film and polyamic acid primer two portions of independent packing, and concrete preparation process is as follows:
One, preparation polyimide support film: 1. prepare thermosetting polyamide acid: at first by 4 of 3mol, 4 '-diaminodiphenyl oxide adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution I, under condition of ice bath, clear solution I is cooled to 7 ℃, then low whipping speed is to add 3 of 2mol under 50 turn/min～200 turn/min, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, and low whipping speed is to continue stirring reaction 4h under 50 turn/min～200 turn/min, obtain initial reaction liquid, then low whipping speed is under 50 turn/min～200 turn/min, the 4-phenylacetylene base phthalic anhydride of 2mol to be joined in initial reaction liquid, and low whipping speed is to continue stirring reaction 6h under 50 turn/min～200 turn/min, the thermosetting polyamide acid solution that to obtain mass concentration be 42.8%, 2., prepare polyamide thermoplastic acid: by 1 of 1mol, two (4-amino-benzene oxygen) benzene of 3-adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution II, under condition of ice bath, clear solution II is cooled to 7 ℃, then low whipping speed is to add 3 of 1mol under 50 turn/min～200 turn/min, 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 7h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 42.8%, 3. blend: polyamide thermoplastic acid 2. prepared by thermosetting polyamide acid 1. prepared by the 100g step and 40g step mixes, and obtains blend, 4. moulding: the blend that 3. step is obtained is coated on carrier, then under 120 ℃, dries 60min, finally, at 200 ℃ of lower thermal treatment 60min, obtains polyimide content and is about 45% carrier film, is the polyimide support film,
Two, prepare the polyamic acid primer: by 1 of 1mol, two (4-amino-benzene oxygen) benzene of 3-adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution, clear solution is cooled to 7 ℃ under condition of ice bath, then low whipping speed is to add 3 of 1mol under 50 turn/min～200 turn/min, 3 ', 4, 4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 7h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 42.8%, add N-Methyl pyrrolidone to be diluted, the mass concentration that is diluted to polyamide thermoplastic acid is about till 7%, obtain the polyamic acid primer.
Adopt the bonding carbon steel test specimen of polyimides adhesive of this test preparation, normal temperature down cut intensity be 19.9MPa, 320 ℃ of down cut intensity be 11.6MPa, 300 ℃ of thermal ageings after 160 hours normal temperature down cut intensity be 20.7MPa.
Adopt 90 ° of stripping strength 3.5kN/m of the bonding aluminium alloy test specimen of polyimides adhesive of this test preparation; Second-order transition temperature surpasses 548 ℃ of 327 ℃, 5% thermal weight loss temperature.
Test two: a kind of polyimides adhesive comprises polyimide support film and polyamic acid primer two portions of independent packing, and concrete preparation process is as follows:
One, preparation polyimide support film: 1. prepare thermosetting polyamide acid: at first by 4 of 3mol, 4 '-diaminodiphenyl oxide adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution I, under condition of ice bath, clear solution I is cooled to 7 ℃, then low whipping speed is to add 3 of 2mol under 50 turn/min～200 turn/min, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, and low whipping speed is to continue stirring reaction 4h under 50 turn/min～200 turn/min, obtain initial reaction liquid, then low whipping speed is under 50 turn/min～200 turn/min, the 4-phenylacetylene base phthalic anhydride of 2mol to be joined in initial reaction liquid, and low whipping speed is to continue stirring reaction 6h under 50 turn/min～200 turn/min, the thermosetting polyamide acid solution that to obtain mass concentration be 42.8%, 2., prepare polyamide thermoplastic acid: by 1 of 1mol, two (4-amino-benzene oxygen) benzene of 3-adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution II, under condition of ice bath, clear solution II is cooled to 7 ℃, then low whipping speed is to add 3 of 1mol under 50 turn/min～200 turn/min, 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 7h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 42.8%, 3. blend: polyamide thermoplastic acid 2. prepared by thermosetting polyamide acid 1. prepared by the 100g step and 50g step mixes, and obtains blend, 4. moulding: the blend that 3. step is obtained is coated on carrier, then under 120 ℃, dries 60min, finally, at 200 ℃ of lower thermal treatment 60min, obtains polyimide content and is about 45% carrier film, is the polyimide support film,
Two, prepare the polyamic acid primer: by 1 of 1mol, two (4-amino-benzene oxygen) benzene of 3-adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution, clear solution is cooled to 7 ℃ under condition of ice bath, then low whipping speed is to add 3 of 1mol under 50 turn/min～200 turn/min, 3 ', 4, 4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 7h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 42.8%, add N-Methyl pyrrolidone to be diluted, the mass concentration that is diluted to polyamide thermoplastic acid is about till 7%, obtain the polyamic acid primer.
Adopt the bonding carbon steel test specimen of polyimides adhesive of this test preparation, the normal temperature shearing resistance is that 20.5MPa, 320 ℃ of shearing resistances are 17.1MPa; Adopt 90 ° of stripping strength 3.1kN/m of the bonding aluminium alloy test specimen of polyimides adhesive of this test preparation.
Test three: a kind of polyimides adhesive comprises polyimide support film and polyamic acid primer two portions of independent packing, and concrete preparation process is as follows:
One, preparation polyimide support film: 1. prepare thermosetting polyamide acid: at first by 4 of 4mol, 4 '-diaminodiphenyl oxide adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution I, under condition of ice bath, clear solution I is cooled to 7 ℃, then low whipping speed is to add 3 of 3mol under 50 turn/min～200 turn/min, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, and low whipping speed is to continue stirring reaction 4h under 50 turn/min～200 turn/min, obtain initial reaction liquid, then low whipping speed is under 50 turn/min～200 turn/min, the 4-phenylacetylene base phthalic anhydride of 2mol to be joined in initial reaction liquid, and low whipping speed is to continue stirring reaction 6h under 50 turn/min～200 turn/min, the thermosetting polyamide acid solution that to obtain mass concentration be 42.8%, 2., prepare polyamide thermoplastic acid: by 1 of 1mol, two (4-amino-benzene oxygen) benzene of 3-adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution II, under condition of ice bath, clear solution II is cooled to 7 ℃, then low whipping speed is to add 3 of 1mol under 50 turn/min～200 turn/min, 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 7h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 42.8%, 3. blend: polyamide thermoplastic acid 2. prepared by thermosetting polyamide acid 1. prepared by the 100g step and 50g step mixes, and obtains blend, 4. moulding: the blend that 3. step is obtained is coated on carrier, then under 120 ℃, dries 60min, finally, at 200 ℃ of lower thermal treatment 60min, obtains polyimide content and is about 45% carrier film, is the polyimide support film,
Two, prepare the polyamic acid primer: by 1 of 1mol, two (4-amino-benzene oxygen) benzene of 3-adds in N-Methyl pyrrolidone, be stirred to fully and dissolve, obtain clear solution, clear solution is cooled to 7 ℃ under condition of ice bath, then low whipping speed is to add 3 of 1mol under 50 turn/min～200 turn/min, 3 ', 4, 4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 7h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 42.8%, add N-Methyl pyrrolidone to be diluted, the mass concentration that is diluted to polyamide thermoplastic acid is about till 7%, obtain the polyamic acid primer.
Adopt the bonding carbon steel test specimen of polyimides adhesive of this test preparation, the normal temperature shearing resistance is that 18.1MPa, 320 ℃ of shearing resistances are 13.4MPa; Adopt 90 ° of stripping strength 2.8kN/m of the bonding aluminium alloy test specimen of polyimides adhesive of this test preparation.
Claims (4)
1. a polyimides adhesive, is characterized in that polyimides adhesive is comprised of polyimide support film and the polyamic acid primer of independent packing;
The carrier film that described polyimide support film is polyimide content 40%～60%; The polyamide thermoplastic acid solution that described polyamic acid primer is mass concentration 5%～10%;
Specifically prepared by described polyimide support film: one according to the following steps, prepare thermosetting polyamide acid: at first by 4, 4 '-diaminodiphenyl oxide adds in non-proton type solvent, be stirred to fully and dissolve, obtain clear solution I, clear solution I is cooled to 5 ℃～10 ℃ under condition of ice bath, then low whipping speed is to add 3 under 50 turn/min～200 turn/min, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, and low whipping speed is to continue stirring reaction 3h～5h under 50 turn/min～200 turn/min, obtain initial reaction liquid, then low whipping speed is under 50 turn/min～200 turn/min, 4-phenylacetylene base phthalic anhydride to be joined in initial reaction liquid, and low whipping speed is to continue stirring reaction 5h～7h under 50 turn/min～200 turn/min, the thermosetting polyamide acid solution that to obtain mass concentration be 30%～50%, described in step 13,3 ', 4,4 '-mol ratio of benzophenone tetracarboxylic dianhydride and 4-phenylacetylene base phthalic anhydride is (2～3): 2, the mol ratio of the 4，4′-diaminodipohenyl ether described in step 1 and 4-phenylacetylene base phthalic anhydride is (3～4): 2, the amount of substance of 4，4′-diaminodipohenyl ether described in step 1 is m
1, 3,3 ', 4,4 '-amount of substance of benzophenone tetracarboxylic dianhydride is m
2, m
1with m
2meet m
1-m
2=1mol, two, prepare polyamide thermoplastic acid: by 1, two (4-amino-benzene oxygen) benzene of 3-adds in non-proton type solvent, be stirred to fully and dissolve, obtain clear solution II, clear solution II is cooled to 5 ℃～10 ℃ under condition of ice bath, then low whipping speed is to add 3 under 50 turn/min～200 turn/min, 3 ', 4,4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 5h～10h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 30%～50%, described in step 21, two (4-amino-benzene oxygen) benzene and 3,3 of 3-', 4,4 '-mol ratio that oxygen supports adjacent pyromellitic dianhydride is 1:1, three, blend: thermosetting polyamide acid and polyamide thermoplastic acid that mass concentration is identical are 10:(3～7 in mass ratio) mix, obtain blend, four, moulding: the blend that step 3 is obtained is coated on carrier, then under 110 ℃～130 ℃, dries 40min～80min, finally, at 180 ℃～220 ℃ lower thermal treatment 40min～80min, obtains the carrier film that polyimide content is 40～60%,
Carrier described in step 4 is that specification is 100g/m
2～180g/m
2Woven fiber glass or specification be 100g/m
2～180g/m
2Quartz fabric.
2. a kind of polyimides adhesive according to claim 1, is characterized in that described non-proton type solvent is N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide or N-Methyl pyrrolidone.
3. a kind of polyimides adhesive according to claim 1, it is characterized in that specifically prepared according to the following steps by described polyamic acid primer: by 1, two (4-amino-benzene oxygen) benzene of 3-adds in non-proton type solvent, be stirred to fully and dissolve, obtain clear solution, clear solution is cooled to 5 ℃～10 ℃ under condition of ice bath, then low whipping speed is to add 3 under 50 turn/min～200 turn/min, 3 ', 4, 4 '-after oxygen supports adjacent pyromellitic dianhydride, and low whipping speed is to continue stirring reaction 5h～10h under 50 turn/min～200 turn/min, the polyamide thermoplastic acid solution that to obtain mass concentration be 30%～50%, add non-proton type solvent to be diluted, the mass concentration that is diluted to polyamide thermoplastic acid is till 5%～10%, obtain the polyamic acid primer, described 1, two (4-amino-benzene oxygen) benzene and 3,3 of 3-', 4,4 '-mol ratio that oxygen supports adjacent pyromellitic dianhydride is 1:1.
4. a kind of polyimides adhesive according to claim 3, is characterized in that described non-proton type solvent is N, N '-N,N-DIMETHYLACETAMIDE, N, N '-dimethyl formamide or N-Methyl pyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100856516A CN102618206B (en) | 2012-03-28 | 2012-03-28 | Polyimide adhesive |
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|---|---|---|---|
| CN2012100856516A CN102618206B (en) | 2012-03-28 | 2012-03-28 | Polyimide adhesive |
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| CN102618206B true CN102618206B (en) | 2013-12-04 |
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| CN103965824B (en) * | 2014-05-16 | 2015-06-17 | 黑龙江省科学院石油化学研究院 | Acetenyl polyimide modified cyanate ester adhesive and preparation method thereof |
| CN105398136B (en) * | 2015-12-29 | 2018-03-09 | 广东生益科技股份有限公司 | A kind of two layers of method double side flexible copper coated board |
| CN107474535A (en) * | 2017-07-28 | 2017-12-15 | 北京玻钢院复合材料有限公司 | The preparation method of electromagnetic wave transparent material |
| CN110499137B (en) * | 2019-09-02 | 2021-05-28 | 黑龙江省科学院石油化学研究院 | High-temperature-resistant polyimide carrier type adhesive and preparation method thereof |
| CN114686157B (en) * | 2022-03-09 | 2023-08-18 | 江苏环峰电工材料有限公司 | Three-dimensional reticular polymer for adhesive and preparation method thereof |
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