CN115746300A - Preparation method and application of resin with low dielectric constant and high glass transition temperature - Google Patents
Preparation method and application of resin with low dielectric constant and high glass transition temperature Download PDFInfo
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- CN115746300A CN115746300A CN202211390202.2A CN202211390202A CN115746300A CN 115746300 A CN115746300 A CN 115746300A CN 202211390202 A CN202211390202 A CN 202211390202A CN 115746300 A CN115746300 A CN 115746300A
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- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 230000009477 glass transition Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 80
- 229920005575 poly(amic acid) Polymers 0.000 claims description 51
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 40
- 150000004985 diamines Chemical class 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000004643 cyanate ester Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 23
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 13
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 claims description 7
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001029 thermal curing Methods 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 2
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000003053 piperidines Chemical class 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 abstract description 16
- 239000011521 glass Substances 0.000 abstract description 16
- 229920001721 polyimide Polymers 0.000 abstract description 16
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000007704 transition Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 4
- 125000006159 dianhydride group Chemical group 0.000 description 4
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- -1 2-amino-4,4-diaminopiperidine Chemical compound 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- NUKYPUAOHBNCPY-UHFFFAOYSA-N 4-aminopyridine Chemical compound NC1=CC=NC=C1 NUKYPUAOHBNCPY-UHFFFAOYSA-N 0.000 description 1
- HKQPBNQSLPIIBZ-UHFFFAOYSA-N 5-nitropiperidin-2-amine Chemical compound NC1CCC([N+]([O-])=O)CN1 HKQPBNQSLPIIBZ-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229960004979 fampridine Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- ZHSQVYOLNBKTRH-UHFFFAOYSA-N piperidine-2,3-diamine Chemical compound NC1CCCNC1N ZHSQVYOLNBKTRH-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the technical field of high-performance high polymer materials, and discloses a preparation method and application of a low-dielectric high-glass transition temperature resin. The preparation method of the resin with low dielectric constant and high glass transition temperature provided by the invention has the characteristics of simple process and easy operation. The introduction of the triazine resin with polyimide with a special structure is more beneficial to maintaining the low loss of the material and improving the thermal performance, so that the prepared resin has low dielectric constant, low dielectric loss and high glass transition temperature.
Description
Technical Field
The invention relates to the technical field of packaging material preparation, in particular to a preparation method and application of a low-dielectric and high-glass transition temperature resin.
Background
With the development of modern information technology and electronic industry, various intelligent electronic devices have entered into the aspects of people's life, and great convenience is provided for our life. However, as electronic devices are becoming more miniaturized, portable, and multifunctional, higher demands are being made on packaging materials. Common packaging materials include epoxy resin, polyphenylene oxide resin, bismaleimide resin, cyanate ester resin, and the like. The bismaleimide-triazine resin (BT) can be applied to the aspects of high-performance copper clad laminates, IC chips, carrier plates for memory chips, high-frequency application copper clad laminates and the like by virtue of excellent dielectric property, heat resistance, good dimensional stability, heat shrinkability and the like.
Although BT resin has many excellent properties, it still cannot meet the requirements of the continuously developing electronic devices, and especially the dielectric properties and heat resistance of the existing BT resin substrate still cannot meet the requirements, and the BT resin needs to be optimized.
Therefore, the prior art for BT resin is still subject to further improvement and promotion.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a low-dielectric and high-glass transition temperature resin, a preparation method and application thereof, and aims to solve the problems of high dielectric constant and low glass transition temperature of the conventional encapsulating resin.
A preparation method of a resin with low dielectric constant and high glass transition temperature comprises the following steps:
preparing a polyamic acid precursor solution; the polyamic acid precursor solution is prepared from different diamine monomers and different dianhydride monomers;
dispersing the polyamic acid precursor solution into a bisphenol A cyanate ester solution to obtain a mixed solution;
and adding a catalyst into the mixed solution, and performing thermocuring and high-temperature imidization treatment to obtain the resin with low dielectric constant and high glass transition temperature.
Optionally, the method for preparing a low dielectric, high glass transition temperature resin, wherein the diamine monomer comprises 4,4 '-bis (3-aminophenoxy) diphenyl sulfone and 4,4' -diaminodiphenyl ether; the dianhydride monomers include 3,3'4,4' -benzophenone tetracarboxylic dianhydride and 1,2,4,5-pyromellitic dianhydride.
Alternatively, the method for preparing a low dielectric, high glass transition temperature resin, wherein the catalyst is selected from any one of, but not limited to, dibutyltin dilaurate, cobalt acetylacetonate, aluminum acetylacetonate, zinc acetylacetonate, nickel acetylacetonate, cadmium acetylacetonate, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2,3-diaminopiperidine, 2-amino-5-nitropiperidine, 2-amino-4,4-diaminopiperidine, 4-dimethylpyridine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine.
Optionally, the preparation method of the low dielectric and high glass transition temperature resin, wherein the preparation of the polyamic acid precursor solution includes the following steps:
dispersing two diamine monomers in dimethyl acetamide according to different proportions to obtain a diamine mixed solution;
dispersing two dianhydride monomers in dimethyl acetamide according to different proportions to obtain a dianhydride mixed solution;
and mixing the diamine mixed solution and the dianhydride mixed solution to obtain the polyamic acid precursor solution.
Optionally, in the preparation method of the low dielectric and high glass transition temperature resin, a solid content of the polyamic acid precursor solution is 0-40%.
Optionally, the preparation method of the low dielectric and high glass transition temperature resin comprises the step of mixing the diamine mixed solution and the dianhydride mixed solution, wherein the solute molar ratio of the diamine mixed solution to the dianhydride mixed solution is 1:1.
Optionally, the preparation method of the low-dielectric and high-glass transition temperature resin comprises the step of dispersing the polyamic acid precursor solution into a bisphenol a cyanate ester solution, wherein the solute ratio of the polyamic acid solution to the cyanate ester solution is 1 (1-4).
Optionally, the method for preparing a low dielectric and high glass transition temperature resin, wherein the thermal curing and high temperature imidization process comprises:
maintaining the mixed solution containing catalyst at 80-100 deg.C for 10-12h, maintaining at 120-150 deg.C for 1-2h, maintaining at 180-200 deg.C for 1-2h, maintaining at 220-240 deg.C for 1-2h, and maintaining at 300 deg.C for 0.5-1h.
The resin with low dielectric constant and high glass transition temperature is prepared by the preparation method.
The low-dielectric and high-glass transition temperature resin is applied as an encapsulating material.
Has the advantages that: compared with the prior art, the preparation method of the resin with low dielectric constant and high glass transition temperature has the characteristics of simple process, easy operation and the like. The introduction of the triazine resin with polyimide with a special structure is more beneficial to maintaining the low loss of the material and improving the heat resistance of the material, so that the prepared resin has low dielectric constant, low dielectric loss and high glass transition temperature.
Drawings
FIG. 1 is a flow chart of a method for preparing a low dielectric and high glass transition temperature resin according to an embodiment of the present invention.
Detailed Description
The invention provides a resin with low dielectric constant and high glass transition temperature, a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method for preparing a resin with low dielectric constant and high glass transition temperature comprises the following steps:
and S10, respectively filling the prepared two diamines into respective glass bottles, dissolving the two diamines into DMAc according to different proportions under an anhydrous condition to prepare diamine solutions, stirring at normal temperature, and filling into the glass bottles. Among the diamine species are: 4,4 '-bis (3-aminophenoxy) diphenyl sulfone (BAPS-m), 4,4' -diaminodiphenyl ether (ODA).
S20, the prepared two kinds of dianhydride are filled in a glass bottle, the two kinds of dianhydride are dissolved in DMAc according to different proportions under the anhydrous condition, and the dianhydride solution is prepared by stirring at normal temperature until the dianhydride is completely dissolved. The dianhydride types are as follows: 3'4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 1,2,4,5-pyromellitic dianhydride (PMDA).
S30, under the condition of nitrogen, mixing the prepared dianhydride solution with a diamine: dianhydride 1:1, dropwise adding the mixture into the prepared diamine solution, and stirring at normal temperature for more than 10 hours to finally prepare the polyamic acid precursor solution with the solid content of 0-40%.
S40, dissolving bisphenol A type cyanate in DMAc to prepare cyanate solution (the solid content is 80%), and uniformly stirring at normal temperature and then standing for later use.
And S50, adding the prepared polyamic acid into the cyanate ester solution according to different mass ratios, and stirring for 2 hours to obtain the cyanate ester/polyamic acid mixed solution.
And S60, adding a catalyst such as dibutyltin dilaurate (DBTDL), cobalt acetylacetonate, aluminum acetylacetonate and the like into the prepared cyanate/polyamic acid mixed solution, and uniformly stirring.
And S70, further drying and curing the cyanate/polyamic acid mixed solution added with the catalyst, and imidizing at high temperature to obtain the modified BT resin.
In the embodiment, the polyimide has excellent heat resistance and dielectric property, the polyimide with a special structure is introduced into a cyanate ester system, so that the polyimide is uniformly dispersed in a triazine network structure, and an interpenetrating network structure is realized by utilizing a high-temperature imidization process. Polyimide monomers with low polarity, low dielectric constant and high rigidity are adopted, and the obtained polyimide has low dielectric constant, low dielectric loss and high glass transition temperature; the interpenetrating network structure can inhibit the relaxation of chain segments, reduce the motion of molecular chain segments, further reduce the dielectric constant and dielectric loss and improve the glass transition temperature. Therefore, the triazine resin combined with the polyimide with a special structure is more beneficial to maintaining low loss and improved thermal performance of materials, and the BT resin prepared by the method has low dielectric constant, low dielectric loss and high glass transition temperature (Tg).
In this embodiment, the solid content of the prepared polyamic acid precursor is 0% to 20%, the solubility of the aromatic polyimide is not good, when the solid content is higher than 20%, the viscosity is too high, and the back-end dissolution sample preparation is not easy to occur, and meanwhile, the too high solid content is not beneficial to the uniform dispersion in the cyanate ester solution, which affects the modification effect.
In this embodiment, the polyamic acid precursor solution is added to a bisphenol a cyanate ester solution, wherein the solute ratio of the polyamic acid solution to the cyanate ester solution is 1 (1-4). By controlling the solute ratio of the polyamic acid solution and the cyanate ester solution, the polyimide structure is optimized, the concentration of the polyimide in the BT resin is changed, and the three-dimensional network structure and the composition of the final cured product are adjusted, so that the modified BT resin with the optimal performance is obtained. Because the dielectric and thermal properties of the polyamic acid and the cyanate ester resin are different, the content and structure of polyimide in the BT resin, which is finally cyclized from the polyamic acid, affect the performance of the prepared modified BT resin.
The preparation of the low dielectric, high glass transition temperature resin provided by the present invention is further illustrated by the following specific examples.
Example 1
Prepared two diamines 4,4 '-bis (3-aminophenoxy) diphenyl sulfone (BAPS-m) and 4,4' -diaminodiphenyl ether (ODA) were respectively contained in respective glass bottles, and the ratio was adjusted to 3:7 in DMAc, and stirring at normal temperature to prepare a diamine solution.
The prepared dianhydrides 3,3'4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 1,2,4,5-pyromellitic dianhydride (PMDA) were respectively put in respective glass bottles, and the ratio of the dianhydride to the dianhydride was adjusted to 3:7 is dissolved in DMAc, and the mixture is stirred at normal temperature to prepare dianhydride solution.
Under the condition of nitrogen, the prepared dianhydride solution is mixed with diamine: dianhydride 1:1 is added into the prepared diamine solution drop by drop under the condition of a molar ratio of 1, and is stirred for more than 10 hours at normal temperature, and finally, the polyamic acid precursor solution with the solid content of 10 percent is prepared.
Bisphenol A cyanate ester is dissolved in DMAc to prepare cyanate ester solution (solid content is 80%), and the cyanate ester solution is stirred uniformly at normal temperature and then is placed for standby.
Adding the prepared polyamic acid solution into a cyanate solution (the mass ratio of the polyamic acid to the cyanate solute is 2:8), stirring for more than 2 hours, and uniformly stirring to obtain the cyanate/polyamic acid mixed solution.
To the prepared cyanate ester/polyamic acid mixed solution was added 0.2% dibutyltin dilaurate (DBTDL) catalyst.
And further drying, curing and imidizing the cyanate/polyamic acid mixed solution added with the catalyst at high temperature to obtain the modified BT resin. The specific conditions of drying and heat treatment are that 12h is maintained at 80 ℃, 2h is maintained at 150 ℃, 1h is maintained at 200 ℃, 1h is maintained at 240 ℃ and 0.5h is maintained at 300 ℃.
Example 2
Prepared two diamines 4,4 '-bis (3-aminophenoxy) diphenyl sulfone (BAPS-m) and 4,4' -diaminodiphenyl ether (ODA) were respectively contained in respective glass bottles, and the ratio was adjusted to 5:5 is dissolved in DMAc, and the mixture is stirred at normal temperature to prepare a diamine solution.
The prepared dianhydrides 3,3'4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 1,2,4,5-pyromellitic dianhydride (PMDA) were respectively put in respective glass bottles, and the ratio of the dianhydride to the dianhydride was adjusted to 5:5 is dissolved in DMAc, and the mixture is stirred at normal temperature to prepare dianhydride solution.
Under the condition of nitrogen, the prepared dianhydride solution is mixed with diamine: dianhydride 1:1 is added into the prepared diamine solution drop by drop under the condition of a molar ratio of 1, and is stirred for more than 10 hours at normal temperature, and finally, the polyamic acid precursor solution with the solid content of 10 percent is prepared.
Bisphenol A cyanate ester is dissolved in DMAc to prepare cyanate ester solution (solid content is 80 percent), and the cyanate ester solution is evenly stirred at normal temperature and then is placed for standby.
Adding the prepared polyamic acid solution into a cyanate solution (the mass ratio of the polyamic acid to the cyanate solute is 3:7), stirring for more than 2 hours, and uniformly stirring to obtain the cyanate/polyimide mixed solution.
To the prepared cyanate ester/polyamic acid mixed solution was added 0.2% dibutyltin dilaurate (DBTDL) catalyst.
And further drying, curing and imidizing the cyanate/polyamic acid mixed solution added with the catalyst at high temperature to obtain the modified BT resin. The specific conditions of drying and heat treatment are that 12h is maintained at 80 ℃, 2h is maintained at 150 ℃, 1h is maintained at 200 ℃, 1h is maintained at 240 ℃ and 1h is maintained at 300 ℃.
Example 3
Prepared two diamines 4,4 '-bis (3-aminophenoxy) diphenyl sulfone (BAPS-m) and 4,4' -diaminodiphenyl ether (ODA) were respectively contained in respective glass bottles, and the ratio was adjusted to 7:3 is dissolved in DMAc, and the mixture is stirred at normal temperature to prepare diamine solution.
The prepared dianhydrides 3,3'4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 1,2,4,5-pyromellitic dianhydride (PMDA) were respectively put in respective glass bottles, and the ratio of the dianhydride to the dianhydride was adjusted to 7:3 is dissolved in DMAc, and is stirred at normal temperature to prepare dianhydride solution.
Under the condition of nitrogen, the prepared dianhydride solution is mixed with diamine: dianhydride is 1:1, dropwise adding the solution into the prepared diamine solution, and stirring at normal temperature for more than 10 hours to finally prepare the polyamic acid precursor solution with the solid content of 20%.
Bisphenol A cyanate ester is dissolved in DMAc to prepare cyanate ester solution (solid content is 80%), and the cyanate ester solution is stirred uniformly at normal temperature and then is placed for standby.
Adding the prepared polyamic acid into a cyanate solution (the mass ratio of the polyamic acid to the cyanate solute is 5:5), stirring for more than 2 hours, and uniformly stirring to obtain the cyanate/polyamic acid mixed solution.
And adding 0.2% of aluminum acetylacetonate catalyst into the prepared cyanate ester/polyamic acid mixed solution.
And further drying, curing and imidizing the cyanate/polyamic acid mixed solution added with the catalyst at high temperature to obtain the modified BT resin. The specific conditions of drying and heat treatment are that the temperature is maintained at 90 ℃ for 10h, the temperature is maintained at 120 ℃ for 2h, the temperature is maintained at 180 ℃ for 1h, the temperature is maintained at 220 ℃ for 1h, and the temperature is maintained at 300 ℃ for 1h.
Example 4
Prepared two diamines 4,4 '-bis (3-aminophenoxy) diphenyl sulfone (BAPS-m) and 4,4' -diaminodiphenyl ether (ODA) were respectively contained in respective glass bottles, and the ratio was adjusted to 2:8 in a molar ratio in DMAc, and stirring at normal temperature to prepare a diamine solution.
Two kinds of dianhydride 3,3 'and 4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 1,2,4,5-pyromellitic dianhydride (PMDA) were prepared, and filled in respective glass bottles, and the mixture was measured in a dry condition according to the following ratio of 2:8 is dissolved in DMAc, and the mixture is stirred at normal temperature to prepare dianhydride solution.
Under the condition of nitrogen, the prepared dianhydride solution is mixed with diamine: dianhydride 1:1, dropwise adding the solution into the prepared diamine solution, and stirring at normal temperature for more than 10 hours to finally prepare the polyamic acid precursor solution with the solid content of 20%.
Bisphenol A cyanate ester is dissolved in DMAc to prepare cyanate ester solution (solid content is 80%), and the cyanate ester solution is stirred uniformly at normal temperature and then is placed for standby.
Adding the prepared polyamic acid solution into a cyanate solution (the mass ratio of the polyamic acid to the cyanate solute is 1:3), stirring for more than 2 hours, and uniformly stirring to obtain the cyanate/polyimide mixed solution.
And adding 0.2% cobalt acetylacetonate catalyst into the prepared cyanate/polyamic acid mixed solution.
And further drying, curing and imidizing the cyanate/polyamic acid mixed solution added with the catalyst at high temperature to obtain the modified BT resin. The specific conditions of drying and heat treatment are that the temperature is maintained at 90 ℃ for 10h, the temperature is maintained at 120 ℃ for 2h, the temperature is maintained at 180 ℃ for 1h, the temperature is maintained at 220 ℃ for 1h, and the temperature is maintained at 300 ℃ for 0.5h.
Comparative example 1
Bisphenol A cyanate ester is dissolved in DMAc to prepare cyanate ester solution (solid content is 80 percent), and the cyanate ester solution is evenly stirred at normal temperature and then is placed for standby.
And adding 0.2% of aluminum acetylacetonate catalyst into the prepared cyanate ester solution.
And drying and curing the solution to obtain the BT resin which is not modified by the polyimide.
The specific conditions of drying and heat treatment are that 90 ℃ is maintained for 10h,120 ℃ is maintained for 2h,180 ℃ is maintained for 1h, and 220 ℃ is maintained for 1h.
The BT resin in the above examples and comparative examples was tested for glass transition temperature, dielectric constant, and dielectric loss, and the test results were as follows:
as can be seen from the test results, the modified BT resin prepared by the preparation method provided by the invention has higher glass transition temperature (278-303 ℃), lower dielectric constant and dielectric loss.
In summary, the invention provides a low dielectric and high glass transition temperature resin, a preparation method and an application thereof, the method comprises the steps of preparing a polyamic acid precursor solution by adopting two diamines and two dianhydrides, adding the polyamic acid precursor solution into a bisphenol A type cyanate ester solution according to a preset proportion, then adding a catalyst, and drying, thermocuring and carrying out high-temperature imidization to obtain the modified BT resin. The preparation method of the resin with low dielectric constant and high glass transition temperature provided by the invention has the characteristics of simple process and easy operation. The triazine resin with the polyimide with the special structure is more beneficial to maintaining the low loss of the material and improving the heat resistance of the material, so that the prepared resin has low dielectric constant, low dielectric loss and high glass transition temperature.
It is to be understood that the invention is not limited in its application to the details of the foregoing description, and that modifications and variations may be effected by those skilled in the art in light of the above teachings, all within the scope and range of equivalents of the appended claims.
Claims (10)
1. A preparation method of resin with low dielectric constant and high glass transition temperature is characterized by comprising the following steps:
preparing a polyamic acid precursor solution; the polyamic acid precursor solution is prepared from different diamine monomers and different dianhydride monomers;
adding the polyamic acid precursor solution into a bisphenol A cyanate solution to obtain a mixed solution;
and adding a catalyst into the mixed solution, and performing thermocuring and high-temperature imidization treatment to obtain the resin with low dielectric constant and high glass transition temperature.
2. The method of claim 1, wherein the diamine monomers include 4,4 '-bis (3-aminophenoxy) diphenyl sulfone and 4,4' -diaminodiphenyl ether; the dianhydride monomers include 3,3'4,4' -benzophenone tetracarboxylic dianhydride and 1,2,4,5-pyromellitic dianhydride.
3. The method of claim 1, wherein the catalyst is selected from any one of dibutyl tin dilaurate, acetylacetone metal salts, imidazoles, piperidines, and pyridines.
4. The method of claim 1, wherein the polyamic acid precursor solution is prepared by the steps of:
dissolving two diamine monomers in dimethyl acetamide according to different proportions to obtain a diamine mixed solution;
dissolving two dianhydride monomers in dimethyl acetamide according to different proportions to obtain a dianhydride mixed solution;
and mixing the diamine mixed solution and the dianhydride mixed solution to obtain the polyamic acid precursor solution.
5. The method of claim 4, wherein the polyamic acid precursor solution has a solid content of 0-40%.
6. The method of claim 1, wherein the diamine mixed solution and the dianhydride mixed solution are mixed, wherein the molar ratio of the diamine mixed solution to the dianhydride mixed solution is 1:1.
7. The method of claim 1, wherein the polyamic acid precursor solution is added to a bisphenol A cyanate ester solution, and the mass ratio of the polyamic acid solution to the cyanate ester solution is 1 (1-4).
8. The method of claim 1, wherein the thermal curing and high temperature imidization process comprises:
maintaining the mixed solution containing catalyst at 80-100 deg.C for 10-12h, maintaining at 120-150 deg.C for 1-2h, maintaining at 180-200 deg.C for 1-2h, maintaining at 220-240 deg.C for 1-2h, and maintaining at 300 deg.C for 0.5-1h.
9. A low dielectric, high glass transition temperature resin, wherein the low dielectric, high glass transition temperature resin is prepared by the method of any one of claims 1-8.
10. Use of the low dielectric, high glass transition temperature resin of claim 9 as an encapsulating material.
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|---|---|---|---|---|
| CN1480490A (en) * | 2003-07-21 | 2004-03-10 | 复旦大学 | Cyanate resin modified by polyether imide |
| CN105440283A (en) * | 2016-01-07 | 2016-03-30 | 中国科学院长春应用化学研究所 | Modified cyanate ester resin and preparation method of modified cyanate ester resin |
| CN106433122A (en) * | 2016-09-07 | 2017-02-22 | 深圳先进技术研究院 | Modified cyanate ester composite material, and preparation method and application thereof |
| CN111040450A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | Low-dielectric fluorine-containing polyimide composite film and preparation method thereof |
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| CN1480490A (en) * | 2003-07-21 | 2004-03-10 | 复旦大学 | Cyanate resin modified by polyether imide |
| CN105440283A (en) * | 2016-01-07 | 2016-03-30 | 中国科学院长春应用化学研究所 | Modified cyanate ester resin and preparation method of modified cyanate ester resin |
| CN106433122A (en) * | 2016-09-07 | 2017-02-22 | 深圳先进技术研究院 | Modified cyanate ester composite material, and preparation method and application thereof |
| CN111040450A (en) * | 2019-12-31 | 2020-04-21 | 山东华夏神舟新材料有限公司 | Low-dielectric fluorine-containing polyimide composite film and preparation method thereof |
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