CN117186337A - Low-dielectric thermosetting polymer and preparation method thereof - Google Patents
Low-dielectric thermosetting polymer and preparation method thereof Download PDFInfo
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- CN117186337A CN117186337A CN202311473451.2A CN202311473451A CN117186337A CN 117186337 A CN117186337 A CN 117186337A CN 202311473451 A CN202311473451 A CN 202311473451A CN 117186337 A CN117186337 A CN 117186337A
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 19
- 239000004634 thermosetting polymer Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 claims abstract description 19
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 16
- 150000004985 diamines Chemical class 0.000 claims abstract description 16
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 34
- 229920000642 polymer Polymers 0.000 abstract description 14
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract description 3
- 238000006683 Mannich reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000000178 monomer Substances 0.000 description 7
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a low dielectric thermosetting polymer and a preparation method thereof, wherein 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, 3, 4-dihydro coumarin and a solvent are mixed, dihydric phenol generated by the reaction of dihydro coumarin and dihydric primary amine, diamine and paraformaldehyde are used as raw materials, a main chain type benzoxazine polymer containing siloxane groups is generated by Mannich reaction, and the obtained polymer is further cured to obtain a material with lower dielectric constant. The invention has low cost of raw materials, simple preparation steps and synthesis process and easy mass production.
Description
Technical Field
The invention relates to the technical field of thermosetting resin and preparation thereof, in particular to a low-dielectric thermosetting polymer and a preparation method thereof.
Background
Benzoxazine is a substance formed by carrying out ring-opening polymerization reaction on a phenol source, an amine source and an aldehyde source through Mannich reaction under the action of heating and/or a catalyst, and is a novel heat-resistant polymer with the characteristics of high modulus, high strength, good heat resistance, low water absorption and the like.
With the development of aerospace and electronic technology, higher and higher requirements are being placed on the performance of thermosetting materials such as benzoxazines, and in particular, high-resistance polybenzoxazines with high glass transition temperatures are becoming a focus of attention.
The benzoxazine is used as a novel thermosetting resin derived under a phenolic system, the defect of the phenolic resin is avoided, the inherent excellent characteristics of autogenous are reserved, and the benzoxazine can be heated for ring opening under the condition of no catalyst due to the special N, O six-membered heterocyclic structure, so that the defect that the original phenolic resin forms a microporous structure in the condensation and crosslinking process is overcome, and the volume shrinkage rate is nearly zero. At the same time, the flame retardant has low dielectric property, low expansion coefficient, good mechanical property and excellent flame retardant property. With the advent of sustainable development, polymers synthesized based on natural renewable raw materials have become an ongoing research area to develop bio-sustainable development materials with excellent performance. In view of this, biobased polybenzoxazines have the potential to reach the mature stage of structural application.
The amine end group silane of the series of main chain benzoxazine polymers synthesized by the invention is functionalized, so that not only can excellent thermal performance be obtained, but also the dielectric constant can be effectively reduced.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a thermosetting polymer with good heat resistance and dielectric property and a preparation method thereof, which are simple and low in cost, and the low dielectric thermosetting polymer is prepared by reacting 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, 3, 4-dihydrocoumarin and paraformaldehyde.
The technical scheme of the invention is as follows:
a low dielectric thermosetting polymer characterized by the following structure:
wherein R is 1 Is any one of the following structures:
a method for preparing a low dielectric thermosetting polymer, comprising the steps of:
s1, adding 3, 4-dihydrocoumarin and 1, 3-bis (3-aminopropyl) tetramethyl disiloxane into a solvent, and reacting for 24 hours at room temperature to enable the 3, 4-dihydrocoumarin to react with primary diamine in a ring opening way to generate dihydric phenol;
s2, adding diamine and paraformaldehyde into the reaction of the S1, heating to 90-130 ℃ and reacting for 10-14 hours;
and S3, performing rotary evaporation on the solution after the reaction in the step S2, and drying to obtain a product, namely the low-dielectric thermosetting polymer.
Further, the diamine has one of the following structural formulas:
further, the molar ratio of the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, the 3, 4-dihydro coumarin, the diamine and the paraformaldehyde is 1:2:1:4 to 5.
Further, the molar ratio of the 1, 3-bis (3-aminopropyl) tetramethyl disiloxane, the 3, 4-dihydro coumarin, the diamine and the paraformaldehyde is 1:2:1:4.4.
further, in the step S1, the solvent is toluene: the volume ratio of the ethanol is 2: 1.
By means of the scheme, the invention has at least the following advantages:
the invention uses dihydric phenol obtained by ring-opening reaction of 3, 4-dihydrocoumarin and 1, 3-bis (3-aminopropyl) tetramethyl disiloxane as a phenol source, uses diamine as an amine source, and reacts with paraformaldehyde to generate main chain benzoxazine resin, wherein the resin structure has siloxane groups. Compared with the common benzoxazine resin, the main chain benzoxazine has better heat resistance and excellent hydrophobic property, has a dielectric constant of 2.5-3.0 at 1MHz, has simple synthesis process, high yield and lower equipment requirement, and is suitable for large-scale production.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is an infrared spectrum of a benzoxazine resin obtained in example 1;
FIG. 2 is a DSC chart of the benzoxazine resin obtained in example 1;
fig. 3 is a TGA spectrum of the cured material of the benzoxazine resin obtained in example 1.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Specific embodiments of a main chain type benzoxazine resin synthesized by 1, 3-bis (3-aminopropyl) tetramethyl disiloxane and 3, 4-dihydro coumarin and a preparation method thereof are provided below. It is necessary to point out that: the following examples are provided only to illustrate the present invention in more detail and are not intended to limit the scope of the invention. Modifications and adaptations of this invention, which do not depart from its spirit, are intended to be within the scope of the invention as claimed.
Example 13, 4-Dihydrocoumarin (1.482 g,0.010 mol), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol) was charged to ethanol (25 ml) in a 150ml flask with a toluene (50 ml) volume ratio of 1:2, and after stirring with a magnetic stirrer at room temperature for 24 hours, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol) and paraformaldehyde (0.66 g, 0.022 mol) were added to the flask, followed by a condenser, and stirred at 110℃and reacted for 12 h. After stopping the reaction, the solvent was removed by rotary evaporation and dried in a vacuum oven at 50 ℃ for one day to give 3.625. 3.625 g benzoxazine monomer in 83% yield.
In this example, the structure of the benzoxazine product obtained was:
FIG. 1 is an infrared absorption spectrum of 925 and 925 cm -1 And 1223 cm -1 Is the characteristic absorption peak of the benzoxazine ring. Fig. 2 is a DSC profile with a benzoxazine monomer cure exotherm peak temperature of 241.6 ℃. FIG. 3 is a TGA graph showing that the temperature of the cured resin material is as high as 361℃at 10% thermal weight loss.
The specific polymer is cured for 1 hour at 200 ℃ to form a film, a film layer with the thickness of 1.2mm is obtained, and the dielectric constant of the film layer is 2.6 under the condition of 1MHz at room temperature by using a broadband dielectric constant meter.
Example 2: the procedure of example 1 was followed except that ethylenediamine was used as a diamine to synthesize a benzoxazine resin.
Wherein the specific chemical structural formula of the ethylenediamine is as follows:
the amount of reactants was changed to: 3, 4-Dihydrocoumarin (1.482 g,0.010 mol), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol), ethylenediamine (0.300 g, 0.005 mol), paraformaldehyde (0.66 g, 0.022 mol) were weighed out.
The reaction conditions were changed to stirring at 90 ℃ and reacted 14h. After stopping the reaction, the solvent was removed by rotary evaporation, and the reaction mixture was dried in a vacuum oven at 50℃for one day to give 3.117g of benzoxazine monomer in 91% yield.
In this example, the structure of the benzoxazine product obtained was:
the specific polymer is cured for 1 hour at 200 ℃ to form a film, a film layer with the thickness of 1.2mm is obtained, and the dielectric constant of the film layer is 2.89 under the condition of 1MHz at room temperature by using a broadband dielectric constant meter.
EXAMPLE 3 Synthesis of benzoxazine resin Using 1, 3-propanediamine as diamine the procedure was followed in example 1.
Wherein the specific chemical structural formula of the 1, 3-propylene diamine is as follows:
the amount of reactants was changed to: 3, 4-Dihydrocoumarin (1.482 g,0.010 mol), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol), 1, 3-propanediamine (0.371 g, 0.005 mol), paraformaldehyde (0.66 g, 0.022 mol) were weighed out.
The reaction conditions were changed to stir and react for 11h at 110 ℃. After stopping the reaction, the reaction mixture was distilled off to remove the solvent and dried in a vacuum oven at 50℃for one day to give 3.041. 3.041 g of benzoxazine monomer in 87% yield.
In this example, the structure of the benzoxazine product obtained was:
the specific polymer is cured for 1 hour at 200 ℃ to form a film, a film layer with the thickness of 1.2mm is obtained, and the dielectric constant of the specific polymer is 2.79 under the condition of 1MHz at room temperature by using a broadband dielectric constant meter.
Example 4: the benzoxazine resin was synthesized using 1, 5-diaminopentane as diamine, and the other steps were the same as in example 1.
Wherein the specific chemical structural formula of the 1, 5-diaminopentane is as follows:
the amount of reactants was changed to: 3, 4-Dihydrocoumarin (1.482 g,0.010 mol), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol), 1, 5-diaminopentane (0.511 g, 0.005 mol), paraformaldehyde (0.66 g, 0.022 mol) were weighed out.
The reaction conditions were changed to stir and react for 10h at 130 ℃. After stopping the reaction, the solvent was removed by rotary evaporation, and the reaction mixture was dried in a vacuum oven at 50℃for one day to give 3.236g of benzoxazine monomer in 89% yield.
In this example, the structure of the benzoxazine product obtained was:
the specific polymer is cured for 1 hour at 200 ℃ to form a film, a film layer with the thickness of 1.2mm is obtained, and the dielectric constant of the specific polymer is 2.75 under the condition of 1MHz at room temperature by using a broadband dielectric constant meter.
Example 5: the procedure of example 1 was followed except that 1, 8-octanediamine was used as diamine for the synthesis of the benzoxazine resin.
Wherein the specific chemical structural formula of the 1, 8-octanediamine is as follows:
the amount of reactants was changed to: 3, 4-Dihydrocoumarin (1.482 g,0.010 mol), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol), 1, 8-octanediamine (0.721 g, 0.005 mol), paraformaldehyde (0.60 g, 0.020 mol) were weighed out.
The reaction conditions were changed to stir and react for 10h at 120 ℃. After stopping the reaction, the reaction mixture was distilled off to remove the solvent and dried in a vacuum oven at 50℃for one day to give 3.308. 3.308 g of benzoxazine monomer in 86% yield.
In this example, the structure of the benzoxazine product obtained was:
the specific polymer is cured for 1 hour at 200 ℃ to form a film, a film layer with the thickness of 1.2mm is obtained, and the dielectric constant of the film layer is 2.5 under the condition of 1MHz at room temperature by using a broadband dielectric constant meter.
Example 6: the procedure of example 1 was followed except that p-phenylenediamine was used as a diamine for the synthesis of benzoxazine resin.
Wherein the specific chemical structural formula of the p-phenylenediamine is as follows:
the amount of reactants was changed to: 3, 4-Dihydrocoumarin (1.482 g,0.010 mol), 1, 3-bis (3-aminopropyl) tetramethyldisiloxane (1.243 g, 0.005 mol), p-phenylenediamine (0.541 g, 0.005 mol), paraformaldehyde (0.75 g, 0.025 mol) were weighed out.
The reaction conditions were changed to stir and react for 14h at 120 ℃. After stopping the reaction, the solvent was removed by rotary evaporation, and the reaction mixture was dried in a vacuum oven at 50 ℃ for one day to give 3.116 g benzoxazine monomer in 85% yield.
In this example, the structure of the benzoxazine product obtained was:
the specific polymer is cured for 1 hour at 200 ℃ to form a film, a film layer with the thickness of 1.2mm is obtained, and the dielectric constant of the specific polymer is 3.0 under the condition of 1MHz at room temperature by using a broadband dielectric constant meter.
The invention has at least the following advantages:
the invention uses dihydric phenol obtained by ring-opening reaction of 3, 4-dihydrocoumarin and 1, 3-bis (3-aminopropyl) tetramethyl disiloxane as a phenol source, uses diamine as an amine source, and reacts with paraformaldehyde to generate main chain benzoxazine resin, wherein the resin structure has siloxane groups. Compared with the common benzoxazine resin, the main chain benzoxazine has better heat resistance and excellent hydrophobic property, has a dielectric constant of 2.5-3.0 at 1MHz, has simple synthesis process, high yield and lower equipment requirement, and is suitable for large-scale production.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and it should be noted that it is possible for those skilled in the art to make several improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims (6)
1. A low dielectric thermosetting polymer characterized by the following structure:
，
wherein R is 1 Is any one of the following structures
。
2. A method for preparing a low dielectric thermosetting polymer, comprising the steps of:
s1, adding 3, 4-dihydrocoumarin and 1, 3-bis (3-aminopropyl) tetramethyl disiloxane into a solvent, and reacting for 24 hours at room temperature to enable the 3, 4-dihydrocoumarin to react with primary diamine in a ring opening way to generate dihydric phenol;
s2, adding diamine and paraformaldehyde in the reaction of the step S1, heating to 90-130 ℃ and reacting for 10-14 hours;
and S3, performing rotary evaporation on the solution after the reaction in the step S2, and drying to obtain a product, namely the low-dielectric thermosetting polymer.
3. The method of preparing a low dielectric thermosetting polymer according to claim 2, wherein the diamine has one of the following structures:
。
4. the method for preparing a low dielectric thermosetting polymer according to claim 2, wherein the molar ratio of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 3, 4-dihydrocoumarin, diamine, paraformaldehyde is 1:2:1:4 to 5.
5. The method for preparing a low dielectric thermosetting polymer according to claim 4, wherein the molar ratio of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 3, 4-dihydrocoumarin, diamine, paraformaldehyde is 1:2:1:4.4.
6. the method for preparing a low dielectric thermosetting polymer according to claim 2, wherein the solvent in the step S1 is toluene: the volume ratio of the ethanol is 2: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585917A (en) * | 2009-06-19 | 2009-11-25 | 南京大学 | Polybenzoxazine precursor and preparing method thereof |
| CN116023612A (en) * | 2021-10-26 | 2023-04-28 | 华东理工大学 | Preparation method and application of silicon-containing low-dielectric polybenzoxazine resin |
| CN116288819A (en) * | 2023-04-12 | 2023-06-23 | 新创碳谷集团有限公司 | Bisphenol A main chain type benzoxazine polyether block modified carbon fiber oiling agent and preparation thereof |
| CN117004180A (en) * | 2023-09-27 | 2023-11-07 | 常州宏巨电子科技有限公司 | Main chain type benzoxazine foam material and preparation method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585917A (en) * | 2009-06-19 | 2009-11-25 | 南京大学 | Polybenzoxazine precursor and preparing method thereof |
| CN116023612A (en) * | 2021-10-26 | 2023-04-28 | 华东理工大学 | Preparation method and application of silicon-containing low-dielectric polybenzoxazine resin |
| CN116288819A (en) * | 2023-04-12 | 2023-06-23 | 新创碳谷集团有限公司 | Bisphenol A main chain type benzoxazine polyether block modified carbon fiber oiling agent and preparation thereof |
| CN117004180A (en) * | 2023-09-27 | 2023-11-07 | 常州宏巨电子科技有限公司 | Main chain type benzoxazine foam material and preparation method and application thereof |
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