CN111040377A - Organic silicon modified phenolic resin composition, composite material and preparation method thereof - Google Patents
Organic silicon modified phenolic resin composition, composite material and preparation method thereof Download PDFInfo
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- CN111040377A CN111040377A CN201911415490.0A CN201911415490A CN111040377A CN 111040377 A CN111040377 A CN 111040377A CN 201911415490 A CN201911415490 A CN 201911415490A CN 111040377 A CN111040377 A CN 111040377A
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- -1 silicon modified phenolic resin Chemical class 0.000 title claims abstract description 101
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 61
- 239000010703 silicon Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 claims abstract description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 59
- 239000002904 solvent Substances 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 43
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000011541 reaction mixture Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000010992 reflux Methods 0.000 claims description 28
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 27
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 27
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 26
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 25
- 229920002866 paraformaldehyde Polymers 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 239000012074 organic phase Substances 0.000 claims description 23
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 22
- 150000005130 benzoxazines Chemical class 0.000 claims description 19
- 229920002050 silicone resin Polymers 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 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 16
- 238000001914 filtration Methods 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 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 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 7
- 229930185605 Bisphenol Natural products 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 37
- 239000007788 liquid Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 238000003760 magnetic stirring Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 11
- 230000001681 protective effect Effects 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 8
- 229920001568 phenolic resin Polymers 0.000 description 7
- 239000012776 electronic material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 5
- 229910018540 Si C Inorganic materials 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
-
- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention relates to an organic silicon modified phenolic resin composition, a composite material and a preparation method thereof. The organic silicon modified phenolic resin composition comprises the following components in parts by weight: 100-120 parts of siloxane modified benzoxazine and 20-200 parts of hydroxyphenyl silicon resin; the content of the catalyst is 20-50 ppm. The polymer composite material cured by the organic silicon modified phenolic resin composition has low dielectric constant and low dielectric loss, and can be used for a miniature high-frequency printing plate.
Description
Technical Field
The invention relates to the field of electronic materials, in particular to an organic silicon modified phenolic resin composition with a low dielectric constant, a composite material and a preparation method thereof.
Background
Phenolic resin has good high temperature resistance, can maintain the structural integrity and dimensional stability even at very high temperature, is often applied to high temperature fields such as refractory materials, friction materials, adhesives, casting industries and the like, and is also a common traditional electronic material.
However, with the advent of the 5G high frequency era and the continuous miniaturization of the size of electronic components, low dielectric constant and low dielectric loss have become essential requirements for 5G application materials. The phenolic resin is used as a traditional electronic material and has a dielectric constant DkMore than 3.5, can not meet the requirements of 5G high-frequency times on materials, in particular to a miniature high-frequency printing plate which requires the dielectric constant D of the materialskIs less than 3.0. Therefore, it is of great significance to develop a new polymer material with low dielectric constant and low dielectric loss to meet the requirements of 5G high frequency era on electronic materials.
Disclosure of Invention
Accordingly, an object of the present invention is to provide a silicone-modified phenol resin composition which has a low dielectric constant and a low dielectric loss in a cured polymer composite material and can be used for a high-frequency micro-printed board.
In order to achieve the purpose, the invention provides the following technical scheme:
an organic silicon modified phenolic resin composition comprises the following components in parts by weight:
100-120 parts of siloxane modified benzoxazine
20-200 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
In some embodiments, the silicone modified phenolic resin composition comprises the following components in parts by weight:
siloxane modified benzoxazine 100 parts
20-100 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
In some embodiments, the silicone modified phenolic resin composition comprises the following components in parts by weight:
siloxane modified benzoxazine 100 parts
40-100 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
In some embodiments, the silicone modified phenolic resin composition comprises the following components in parts by weight:
siloxane modified benzoxazine 100 parts
40-60 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
In some embodiments, the silicone modified phenolic resin composition comprises the following components in parts by weight:
siloxane modified benzoxazine 100 parts
50 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
In some embodiments, the silicone modified phenolic resin composition comprises the following components in parts by weight:
siloxane modified benzoxazine 100 parts
100 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
In some of these embodiments, the catalyst is present in an amount of 25 to 35 ppm.
In some of these embodiments, the siloxane-modified benzoxazine is selected from at least one of the following compounds:
in some embodiments, the siloxane-modified benzoxazine is prepared from the following raw materials: a base, a solvent, paraformaldehyde, 3-aminopropyltrialkoxysilane, and phenol.
In some of these embodiments, the molar ratio of paraformaldehyde, 3-aminopropyltrialkoxysilane and phenolic hydroxyl groups is 2:1: 1.
In some of these embodiments, the phenol is selected from at least one of phenol, bisphenol a, hexafluorobisphenol a, naphthol, bisphenol fluorene, and bisphenol F.
In some of these embodiments, the solvent is selected from at least one of toluene, xylene, and chloroform.
In some of these embodiments, the base is selected from CaH2At least one of NaH and LiH.
In some of these embodiments, the method of making the siloxane-modified benzoxazine comprises the steps of:
and mixing and stirring the alkali and the solvent, then adding the paraformaldehyde and the 3-aminopropyl trialkoxysilane, reacting for 0.5-2 h at the temperature of 40-70 ℃, adding the phenol, performing reflux reaction for 2-10h, filtering, and evaporating the filtrate to remove the solvent to obtain the formaldehyde-free formaldehyde-based catalyst.
In some of these embodiments, the method of making the siloxane-modified benzoxazine comprises the steps of:
and mixing and stirring the alkali and the solvent, then adding the paraformaldehyde and the 3-aminopropyl trialkoxysilane, reacting for 0.8-1.5 h at 55-65 ℃, adding the phenol, performing reflux reaction for 5-7h, filtering, and evaporating the filtrate to remove the solvent to obtain the formaldehyde-containing aqueous solution.
In some of these embodiments, the hydroxyphenyl silicon resin is prepared from a mixture of, by mole, 1.0: 0.5-3.0 parts of phenylmethyldimethoxysilane and phenyltrimethoxysilane.
In some of these embodiments, the hydroxyphenyl silicon resin is prepared from a mixture of, by mole, 1.0: 1.0-2.0 parts of phenylmethyldimethoxysilane and phenyltrimethoxysilane.
In some embodiments, the method for preparing the hydroxyphenyl silicon resin comprises the following steps:
mixing the phenyl methyl dimethoxy silane, the phenyl trimethoxy silane and a solvent, heating to 50-60 ℃, and dropwise adding 100-150 g of 8-12% HCl solution for 1-2 h; after dripping, heating to 75-80 ℃, continuing to react for 1-2 h, and carrying out post-treatment on the obtained reaction mixture to obtain the catalyst.
In some of these embodiments, the post-treating the resulting reaction mixture comprises: separating the obtained reaction mixture, removing the upper layer aqueous solution, washing the organic phase to be neutral, drying, and removing the solvent to obtain the catalyst.
In some of these embodiments, the solvent removal conditions comprise: the temperature is 100 ℃ and 120 ℃, and the pressure is not more than 0.09 MPa.
In some of these embodiments, the solvent is toluene and ethanol.
In some of these embodiments, the solvent is toluene and ethanol in a volume ratio of 1-2: 1.
In some of these examples, the ratio of the total molar amount of phenylmethyldimethoxysilane and phenyltrimethoxysilane to the amount of solvent used is 1.0 mol: 50mL-110 mL.
In some of these examples, the ratio of the total molar amount of phenylmethyldimethoxysilane and phenyltrimethoxysilane to the amount of solvent used is 1.0 mol: 65mL-80 mL.
In some of these embodiments, the catalyst is selected from at least one of stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin diacetate.
The invention also provides an organic silicon modified phenolic resin composite material.
The specific technical scheme is as follows:
an organic silicon modified phenolic resin composite material is obtained by curing the organic silicon modified phenolic resin composition at the temperature of 130-180 ℃.
In some embodiments, the silicone-modified phenolic resin composite material is obtained by curing the silicone-modified phenolic resin composition at the temperature of 140-160 ℃.
The invention also provides a preparation method of the organic silicon modified phenolic resin composite material.
The specific technical scheme is as follows:
a preparation method of an organic silicon modified phenolic resin composite material comprises the following steps:
uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, and standing in a mold at room temperature for 0-4 h; then heating the mixture to 130-.
A preparation method of an organic silicon modified phenolic resin composite material comprises the following steps:
uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, and placing in a die at room temperature for 1.5-2.5 h; then heating the mixture to 140-.
Compared with the prior art, the invention has the following beneficial effects:
in order to meet the requirements of 5G high-frequency times on the dielectric property of electronic materials, the invention obtains an organic silicon modified phenolic resin composition consisting of hydroxyphenyl silicon resin, siloxane modified benzoxazine and a catalyst through a large amount of experimental research, and the composition can obtain a low dielectric composite material with a microscopic layered structure after being cured at high temperature. According to the invention, the problem of poor compatibility of the phenolic resin and the organic silicon material is effectively solved through the reaction of siloxane in the siloxane modified benzoxazine and silicon hydroxyl in the hydroxyphenyl silicon resin, and the silicon-rich phase and carbon-rich phase hybrid material with a microscopic layered structure is prepared, and the layered structure provides help for reducing the dielectric constant and the loss factor of the phenolic resin material. The combination of the above factors makes the dielectric constant D of the organosilicon modified phenolic resin composite material of the inventionkLess than 2.8, and loss factor tan delta less than or equal to 0.002, and meets the requirement of the micro high-frequency printing plate on the dielectric property of the material. Under the condition that the dielectric constant of the existing phenolic resin is larger than 3.5 and can not meet the requirements of 5G high-frequency times on electronic materials, the organic silicon modified phenolic resin composition and the composite material provide a new material choice for the development of the electronic industry.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. It is to be understood that the experimental procedures in the following examples, where specific conditions are not noted, are generally in accordance with conventional conditions, or with conditions recommended by the manufacturer. The various reagents used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention provides an organic silicon modified phenolic resin composition which comprises the following components in parts by weight:
100-120 parts of siloxane modified benzoxazine
20-200 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
The macromolecular composite material obtained after the organic silicon modified phenolic resin composition is cured has low dielectric constant and low dielectric loss.
Wherein, the siloxane modified benzoxazine and hydroxyphenyl silicon resin are further preferably prepared by the following steps:
siloxane modified benzoxazine 100 parts
20-100 parts of hydroxyphenyl silicone resin;
more preferably:
siloxane modified benzoxazine 100 parts
40-100 parts of hydroxyphenyl silicone resin;
more preferably:
siloxane modified benzoxazine 100 parts
40-60 parts of hydroxyphenyl silicone resin;
more preferably:
siloxane modified benzoxazine 100 parts
And 50 parts of hydroxyphenyl silicon resin.
In some embodiments, the catalyst content is further preferably from 25 to 35ppm, more preferably 30 ppm.
By further optimizing the raw material proportion, the dielectric constant and the dielectric loss of the material can be further reduced.
The siloxane modified benzoxazine can be prepared from the following raw materials: a base, a solvent, paraformaldehyde, 3-aminopropyltrialkoxysilane, and phenol. Paraformaldehyde and 3-aminopropyl trialkoxy silane are taken as raw materials, various phenolic compounds are matched, and the raw materials react in a solvent under the action of alkali to obtain a series of siloxane modified benzoxazine compounds, for example, at least one selected from the following compounds:
wherein the molar ratio of the paraformaldehyde to the 3-aminopropyltrialkoxysilane to the phenolic hydroxyl is 2:1: 1.
The phenol may be any of a variety of common phenolic compounds, preferably: phenol, bisphenol A, naphthol, bisphenol fluorene, hexafluorobisphenol A, bisphenol F. Wherein, the siloxane modified benzoxazine prepared by taking hexafluorobisphenol A and the composition of the hexafluorobisphenol A and other phenols as raw materials is prepared into the organic silicon modified phenolic resin composition, and the dielectric property of the cured organic silicon modified phenolic resin composition is best.
The solvent may be an oily organic solvent conventional in the art, and is preferably at least one of toluene, xylene, and chloroform.
The base is used for rapid removal of water from the reaction system and may be selected from CaH, for example2At least one of NaH and LiH.
The siloxane modified benzoxazine can be prepared from the following raw materials by a preparation method conventional in the field: a base, a solvent, paraformaldehyde, 3-aminopropyltrialkoxysilane, and phenol. Preferably, the preparation method of the siloxane modified benzoxazine comprises the following steps:
and mixing and stirring the alkali and the solvent, then adding the paraformaldehyde and the 3-aminopropyl trialkoxysilane, reacting for 0.5-2 h at the temperature of 40-70 ℃, adding the phenol, performing reflux reaction for 2-10h, filtering, and evaporating the filtrate to remove the solvent to obtain the formaldehyde-free formaldehyde-based catalyst.
Further preferably, the preparation method of the siloxane modified benzoxazine comprises the following steps:
and mixing and stirring the alkali and the solvent, then adding the paraformaldehyde and the 3-aminopropyl trialkoxysilane, reacting for 0.8-1.5 h at 55-65 ℃, adding the phenol, performing reflux reaction for 5-7h, filtering, and evaporating the filtrate to remove the solvent to obtain the formaldehyde-containing aqueous solution.
The hydroxyphenyl silicon resin is preferably prepared from phenyl methyl dimethoxy silane and phenyl trimethoxy silane, and more preferably prepared from phenyl methyl dimethoxy silane and phenyl trimethoxy silane in a molar ratio of 1.0: 0.5-3.0 parts of phenylmethyldimethoxysilane and phenyltrimethoxysilane, and the molar ratio is more preferably 1.0: 1.0-2.0 parts of phenylmethyldimethoxysilane and phenyltrimethoxysilane. The hydroxyphenyl silicone resin prepared from the phenyl methyl dimethoxy silane and the phenyl trimethoxy silane in the preferable proportioning range is viscous liquid at normal temperature, and is convenient for molding and processing.
The hydroxyphenyl silicone resin can be prepared by a preparation method which is conventional in the field, and preferably, the preparation method comprises the following steps:
mixing the phenyl methyl dimethoxy silane, the phenyl trimethoxy silane and a solvent, heating to 50-60 ℃, and dropwise adding 100-150 g of 8-12% HCl solution for 1-2 h; after dripping, heating to 75-80 ℃, continuing to react for 1-2 h, and carrying out post-treatment on the obtained reaction mixture to obtain the catalyst.
Wherein the post-treatment of the obtained reaction mixture comprises: separating the obtained reaction mixture, removing the upper layer aqueous solution, washing the organic phase to be neutral, drying, and removing the solvent to obtain the catalyst.
Wherein the solvent removal conditions are preferably: the temperature is 100 ℃ and 120 ℃, and the pressure is not more than 0.09 MPa.
The reaction solvent used to prepare the hydroxyphenyl silicone resin may be an organic solvent conventional in the art, preferably a combination of toluene and ethanol, preferably in a volume ratio of 0.5 to 5:1, more preferably 1 to 4: 1, more preferably 1-2: 1. The solvent is preferably the combination of toluene and ethanol, so that hydroxyphenyl liquid silicone resin with uniform structure can be obtained more easily, the product structure is more uniform under the preferable volume ratio, and the yield is higher. The amount of the solvent used is preferably: the ratio of the total molar amount of the phenyl methyl dimethoxy silane and the phenyl trimethoxy silane to the amount of the solvent is 1.0 mol: 50mL-110 mL; more preferably, the ratio of the total molar amount of the phenylmethyldimethoxysilane and the phenyltrimethoxysilane to the amount of the solvent is 1.0 mol: 65mL-80 mL.
The catalyst in the above-mentioned organosilicon-modified phenolic resin composition may be a conventional curing catalyst, and is preferably at least one of stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin diacetate.
The obtained organic silicon modified phenolic resin composition is reacted and cured at a certain temperature, so as to obtain the organic silicon modified phenolic resin composite material, wherein the certain temperature is preferably 130-180 ℃, more preferably 140-160 ℃, more preferably 145-155 ℃ and most preferably 150 ℃. The preparation method is preferably as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, and standing in a mold at room temperature for 0-4 h; then heating the mixture to 130-. More preferably: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, and placing in a die at room temperature for 1.5-2.5 h; then heating the mixture to 140-.
Wherein, the reaction of siloxane in the siloxane modified benzoxazine and silicon hydroxyl in the hydroxyphenyl silicon resin can effectively solve the problem of the reaction between phenolic resin and organic siliconThe material has poor compatibility, and the silicon-rich phase and carbon-rich phase hybrid material with a microscopic layered structure can be prepared, and the layered structure can reduce the dielectric constant and the loss factor of the phenolic resin material. The dielectric constant D of the organic silicon modified phenolic resin composite material is ensured by the cooperation of a plurality of factorskLess than 2.8, and loss factor tan delta less than or equal to 0.002, and meets the requirement of the micro high-frequency printing plate on the dielectric property of the material.
The present invention will be described in detail with reference to specific examples.
The room temperature of the invention is 20-30 ℃.
The preparation of siloxane modified benzoxazine in the following examples has the following raw material ratio: the molar ratio of paraformaldehyde, 3-aminopropyltrialkoxysilane and phenolic hydroxyl is 2:1: 1.
Example 1
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
the preparation method comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and chloroform (400ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (88.6g, 0.4mol) and paraformaldehyde (24.24g, 0.8mol), stirred at 60 ℃ for 1 hour, added with bisphenol A (45.6g, 0.2mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, the yield being 89 wt%.
Nuclear magnetic hydrogen spectrum of the obtained siloxane modified benzoxazine: two methylene groups Ar-C on oxazine ring structureH 2-N and O-CH 2The chemical shifts of the protons of N are 3.91 and 4.82ppm, respectively; O-CH 2–CH3Chemical shift of 3.77 ppm; N-CH 2–CH2Has a chemical shift of 2.71ppm, CH2–CH 2–CH2Has a chemical shift of 1.64ppm, C-CH 3Chemical shift of 1.55ppm, CH2–CH 3Has a chemical shift of 1.19ppm, Si-CH 2The chemical shift of (A) is 0.64ppm, and the chemical shift of proton hydrogen on the benzene ring is multiple peaks of 6.92-6.88, 6.79-6.76, and 6.64-6.60 ppm.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were added to a four-necked flask equipped with a heating device, a magnetic stirring device, a reflux device, a shielding gas inlet/outlet, and a temperature controller. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase.
Nuclear magnetic hydrogen spectrum of hydroxyphenyl silicon resin: the characteristic absorption peak of phenyl hydrogen is 7.05-8.00ppm, the chemical shift of methyl hydrogen is 0-0.82ppm, and the chemical shifts of hydrogen in silicon-hydroxyl and silicon-methoxyl are 2.41ppm and 3.41ppm respectively.
The curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 1.
Example 2
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and toluene (400ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (88.6g, 0.4mol) and paraformaldehyde (24.24g, 0.8mol), stirred at 60 ℃ for 1 hour, then added with bisphenol A (45.6g, 0.2mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid is obtained by filtration, and the yield is 97 wt%.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase.
The curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 2.
Example 3
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and xylene (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with phenol (18.8g, 0.2mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid is obtained by filtration, and the yield is 91 wt%.
Nuclear magnetic hydrogen spectrum of modified benzoxazine: two methylene groups Ar-C on oxazine ring structureH 2-N and O-CH 2The chemical shifts of the protons of N are 3.94 and 4.79ppm, respectively; O-CH 2–CH3A chemical shift of 3.73 ppm; N-CH 2–CH2Has a chemical shift of 2.68ppm, CH2–CH 2–CH2Chemical shift of 1.64ppm, CH2–CH 3Has a chemical shift of 1.23ppm, Si-CH 2The chemical shift of the compound is 0.64ppm, and the chemical shift of proton hydrogen on a benzene ring is a multiplet of 7.01-6.98, 6.91-6.87, 6.77-6.74 and 6.61-6.59 ppm.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase. Viscosity:
the curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 3.
Example 4
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
The preparation method of the phenol type siloxane modified benzoxazine comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and xylene (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with phenol (18.8g, 0.2mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
The preparation method of the bisphenol siloxane modified benzoxazine comprises the following steps:
with heating means, magnetic stirring means, return means, shielding gas inlet and outlet, and temperature controllerThe four-neck flask is added with CaH2(12.6g, 0.3mol) and toluene (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with bisphenol A (22.8g, 0.1mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase. Viscosity:
the curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 4.
Example 5
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
the preparation method comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and chloroform (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with naphthol (28.8g, 0.2mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
Nuclear magnetic hydrogen spectrum of the obtained siloxane modified benzoxazine: two methylene groups Ar-C on oxazine ring structureH 2-N and O-CH 2The chemical shifts of the protons of N are 4.31 and 4.92ppm, respectively; O-CH 2–CH3Has a chemical shift of 3.86 ppm; N-CH 2–CH2Has a chemical shift of 2.91ppm, CH2–CH 2–CH2Chemical shift of 1.77ppm, CH2–CH 3Has a chemical shift of 1.29ppm, Si-CH 2The chemical shift of (A) is 0.73ppm, the chemical shift of proton hydrogen on naphthalene ring is multiple peaks of 6.91-6.93, 7.31-7.33, 7.42-7.45, 7.48-7.49, 7.68-7.73, and 7.86-7.88 ppm.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were added to a four-necked flask equipped with a heating device, a magnetic stirring device, a reflux device, a shielding gas inlet/outlet, and a temperature controller. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase. Viscosity:
the curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 5.
Example 6
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
the preparation method comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and chloroform (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with hexafluorobisphenol A (33.6g, 0.1mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
Nuclear magnetic hydrogen spectrum of modified benzoxazine: two methylene groups Ar-C on oxazine ring structureH 2-N and O-CH 2The chemical shifts of the protons of N are 3.85 and 4.72ppm, respectively; O-CH 2–CH3A chemical shift of 3.78 ppm; is N-CH 2–CH2Has a chemical shift of 2.76ppm, CH2–CH 2–CH2Has a chemical shift of 1.87ppm, CH2–CH 3Has a chemical shift of 1.15ppm, Si-CH 2Chemical shift of 0.62ppm, chemistry of proton hydrogen on benzene ringThe shift is multiple peaks of 6.93-6.85, 6.79-6.76, 6.64-6.60 ppm.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase.
Viscosity of the oil
The curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 6.
Example 7
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
the preparation method comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and chloroform (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), and allowed to stand at 60 ℃After stirring the reaction mixture for 1 hour, bisphenol fluorene (35g, 0.1mol) was added thereto, and the mixture was heated to reflux temperature and then subjected to reaction under N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
Nuclear magnetic hydrogen spectrum of modified benzoxazine: proton Ar-C of two methylene groups on oxazine ring structureH 2-N and O-CH 2Chemical shifts of-N are 3.91 and 4.82ppm, respectively; O-CH 2–CH3Chemical shift of 3.77 ppm; is N-CH 2–CH2Has a chemical shift of 2.71ppm, CH2–CH 2–CH2Chemical shift of 1.64ppm, CH2–CH 3Has a chemical shift of 1.19ppm, Si-CH 2The chemical shift of the compound is 0.64ppm, and the chemical shift of proton hydrogen on a benzene ring is multiple peaks of 7.82-7.85,7.38-7.42, 6.92-6.88 and 6.64-6.60 ppm.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 1.00mole of phenyltrimethoxysilane, 90ml of toluene and 60ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase.
The curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 7.
Example 8
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
The preparation method of the phenol type siloxane modified benzoxazine comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and xylene (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with phenol (18.8g, 0.2mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
The preparation method of the bisphenol siloxane modified benzoxazine comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and toluene (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with bisphenol A (22.8g, 0.1mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 2.00mole of phenyltrimethoxysilane, 120ml of toluene and 80ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 150g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 2h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase.
The curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 8.
Example 9
The silicone-modified phenolic resin composition of this example consisted of 100 parts of siloxane-modified benzoxazine, 50 parts of hydroxyphenyl silicone, and 30ppm dibutyltin dilaurate.
Wherein the structural formula of the siloxane modified benzoxazine is as follows:
the preparation method comprises the following steps:
adding CaH into a four-neck flask with a heating device, a magnetic stirring device, a reflux device, a protective gas inlet and outlet and a temperature controller2(12.6g, 0.3mol) and chloroform (200ml), stirred at room temperature for 20 minutes, added with (3-aminopropyl) triethoxysilane (44.3g, 0.2mol) and paraformaldehyde (12.12g, 0.4mol), stirred at 60 ℃ for 1 hour, added with hexafluorobisphenol A (33.6g, 0.1mol), heated to reflux temperature, and added with N2The reaction was continued for 6 hours under protection of (1). After the reaction, a yellow-green viscous liquid was obtained by filtration, and the yield was 93 wt%.
The preparation method of the hydroxyphenyl silicon resin comprises the following steps:
1.0mole of phenylmethyldimethoxysilane, 2.00mole of phenyltrimethoxysilane, 120ml of toluene and 80ml of ethanol were taken in a reaction vessel. The temperature of the reaction mixture was heated to 55 ℃ and 100g of a 10% strength HCl solution were added dropwise over a period of about 1 h. After dripping, heating to 77 ℃, continuing to react for 1h, pouring the reaction mixture into a separating funnel for separating liquid, removing the upper-layer aqueous solution, washing the obtained organic phase to neutral pH with deionized water, drying with anhydrous magnesium sulfate, and removing the solvent at 120 ℃/0.09MPa to obtain the organic phase.
The curing of the organic silicon modified phenolic resin composition is carried out by two steps:
the first step is as follows: uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, pouring into a mold with the diameter of 5cm multiplied by 2mm, and standing for 2 hours at room temperature;
a second part: and heating the resin composition pretreated in the first step to 150 ℃ and baking for 2h to obtain a cured resin (namely, the organic silicon modified phenolic resin composite material) which is marked as BP 9.
Example 10
The BP1-BP9 products prepared in the examples were tested for overall performance by the following test methods:
glass transition temperature: the glass transition temperature of the cured resin sample is measured by a Diamond/Pyris DSC differential scanning calorimeter, the sample is added into a sample tank, the temperature is raised to 350 ℃, the sample is kept for 5min, then the temperature is reduced to room temperature, and then the temperature is measured at the rate of 20 ℃/min.
Dielectric constant at 23 ℃: the dielectric constant of the cured resin sample was measured with an HP-4291B dielectric analyzer at a frequency of 1 MHz.
Loss factor at 23 ℃: the loss factor of the cured resin sample was measured with an HP-4291B dielectric analyzer at a frequency of 1 MHz.
Water absorption test: the cured resin sample for testing was sized into a cylinder of 20mm diameter and 2mm thickness. Weight before boiling in water is recorded as M1Soaking in boiling water for 6 hr, taking out, wiping off water on the surface of the sample, weighing and recording as M2. The water absorption was calculated by the following formula: a.b (wt%) (M)2-M1)/M1×100％。
Hardness (25 ℃): the hardness of the cured resin sample was measured using a Shore D durometer model TH200, Shanghai Lorentz electromechanical instruments Ltd, and the measurement sample size was (60 cm. times.60 cm. times.10 cm).
The test results are shown in the following table: the dielectric constant D of the organosilicon modified phenolic resin composition iskLess than 2.8, and loss factor tan delta less than or equal to 0.002, and meets the requirement of the micro high-frequency printing plate on the dielectric property of the material. In particular, the dielectric constant D of BP9 prepared in example 9k2.28, tan delta of 0.0012 and excellent comprehensive performance.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (16)
1. The organic silicon modified phenolic resin composition is characterized by comprising the following components in parts by weight:
100-120 parts of siloxane modified benzoxazine
20-200 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
2. The organic silicon modified phenolic resin composition as claimed in claim 1, which comprises the following components and catalysts in parts by weight:
siloxane modified benzoxazine 100 parts
40-100 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm.
3. The organosilicon modified phenolic resin composition of claim 2, comprising the following components in parts by weight and a catalyst:
siloxane modified benzoxazine 100 parts
40-60 parts of hydroxyphenyl silicone resin;
the content of the catalyst is 20-50 ppm; preferably 25-35 ppm.
4. The silicone-modified phenolic resin composition of claim 1, wherein the siloxane-modified benzoxazine is selected from at least one of the following compounds:
5. the silicone-modified phenolic resin composition of claim 1, wherein the siloxane-modified benzoxazine is prepared from the following raw materials: a base, a solvent, paraformaldehyde, 3-aminopropyltrialkoxysilane, and phenol.
6. The silicone-modified phenolic resin composition of claim 5, wherein the molar ratio of the paraformaldehyde, the 3-aminopropyltrialkoxysilane, and the phenolic hydroxyl group is 2:1: 1; and/or the presence of a catalyst in the reaction mixture,
the phenol is selected from at least one of phenol, bisphenol A, hexafluorobisphenol A, naphthol, bisphenol fluorene and bisphenol F; and/or the presence of a catalyst in the reaction mixture,
the solvent is at least one selected from toluene, xylene and chloroform; and/or the presence of a catalyst in the reaction mixture,
the base is CaH2At least one of NaH and LiH.
7. The silicone-modified phenolic resin composition of claim 5, wherein the siloxane-modified benzoxazine is prepared by a process comprising the steps of:
and mixing and stirring the alkali and the solvent, then adding the paraformaldehyde and the 3-aminopropyl trialkoxysilane, reacting for 0.5-2 h at the temperature of 40-70 ℃, adding the phenol, performing reflux reaction for 2-10h, filtering, and evaporating the filtrate to remove the solvent to obtain the formaldehyde-free formaldehyde-based catalyst.
8. The silicone-modified phenolic resin composition of any of claims 1-7, wherein the hydroxyphenyl silicon resin is prepared from a molar ratio of 1.0: 0.5-3.0 parts of phenylmethyldimethoxysilane and phenyltrimethoxysilane; preferably, the hydroxyphenyl silicon resin is prepared by mixing the following components in a molar ratio of 1.0: 1.0-2.0 parts of phenylmethyldimethoxysilane and phenyltrimethoxysilane.
9. The silicone-modified phenolic resin composition of claim 8, wherein the method for preparing the hydroxyphenyl silicon resin comprises the following steps:
mixing the phenyl methyl dimethoxy silane, the phenyl trimethoxy silane and a solvent, heating to 50-60 ℃, and dropwise adding 100-150 g of 8-12% HCl solution for 1-2 h; after dripping, heating to 75-80 ℃, continuing to react for 1-2 h, and carrying out post-treatment on the obtained reaction mixture to obtain the catalyst.
10. The silicone-modified phenolic resin composition of claim 9, wherein said post-treating the resulting reaction mixture comprises: separating the obtained reaction mixture, removing the upper aqueous solution, washing the organic phase to be neutral, drying, and removing the solvent to obtain the compound; and/or the presence of a catalyst in the reaction mixture,
the solvent is toluene and ethanol; and/or the presence of a catalyst in the reaction mixture,
the ratio of the total molar amount of the phenyl methyl dimethoxy silane and the phenyl trimethoxy silane to the amount of the solvent is 1.0 mol: 50mL-110 mL.
11. The silicone-modified phenolic resin composition of claim 10, wherein said post-treating the resulting reaction mixture comprises: separating the obtained reaction mixture, removing the upper-layer aqueous solution, washing the organic phase to be neutral, drying, and removing the solvent under the conditions that the temperature is 100-120 ℃ and the pressure is not more than 0.09MPa to obtain the organic phase; and/or the presence of a catalyst in the reaction mixture,
the solvent is toluene and ethanol with the volume ratio of 1-2: 1; and/or the presence of a catalyst in the reaction mixture,
the ratio of the total molar amount of the phenyl methyl dimethoxy silane and the phenyl trimethoxy silane to the amount of the solvent is 1.0 mol: 65mL-80 mL.
12. The silicone-modified phenolic resin composition of any of claims 1-7, wherein the catalyst is selected from at least one of stannous octoate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin diacetate.
13. An organosilicon modified phenolic resin composite material, which is obtained by curing the organosilicon modified phenolic resin composition as described in any one of claims 1 to 12 at a temperature of 130-180 ℃.
14. The silicone-modified phenolic resin composite material of claim 13, wherein the silicone-modified phenolic resin composition is cured at a temperature of 140 ℃ and 160 ℃.
15. A method for preparing the silicone-modified phenolic resin composite material of claim 13 or 14, comprising the steps of:
uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, and standing in a mold at room temperature for 0-4 h; then heating the mixture to 130-.
16. The method of preparing the silicone-modified phenolic resin composite material of claim 15, comprising the steps of:
uniformly mixing the organic silicon modified phenolic resin composition, removing bubbles, and placing in a die at room temperature for 1.5-2.5 h; then heating the mixture to 140-.
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