CN113603848A - Low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segment and imine ring and preparation method thereof - Google Patents
Low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segment and imine ring and preparation method thereof Download PDFInfo
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- CN113603848A CN113603848A CN202110822374.1A CN202110822374A CN113603848A CN 113603848 A CN113603848 A CN 113603848A CN 202110822374 A CN202110822374 A CN 202110822374A CN 113603848 A CN113603848 A CN 113603848A
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- benzoxazine resin
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- dielectric
- imine ring
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- 229920005989 resin Polymers 0.000 title claims abstract description 152
- 239000011347 resin Substances 0.000 title claims abstract description 152
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 125000001183 hydrocarbyl group Chemical group 0.000 title 1
- 125000000879 imine group Chemical group 0.000 title 1
- 150000002466 imines Chemical group 0.000 claims abstract description 66
- 150000002430 hydrocarbons Chemical group 0.000 claims abstract description 53
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 24
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013032 Hydrocarbon resin Substances 0.000 claims abstract description 19
- 229920006270 hydrocarbon resin Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- -1 methacryloyl Chemical group 0.000 claims description 26
- 238000012644 addition polymerization Methods 0.000 claims description 21
- 125000005605 benzo group Chemical group 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 20
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 16
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 15
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 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 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002174 Styrene-butadiene Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical group 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012966 redox initiator Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical compound C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000805 composite resin Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 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
- 238000004132 cross linking Methods 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a low dielectric and high heat-resistant benzoxazine resin containing hydrocarbon chain segment and imine ring, which is shown in formula (I), and the preparation method of the compound comprises the following steps: adding benzoxazine resin containing double bonds, maleimide resin, a solvent and an initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 80-140 ℃, carrying out prepolymerization for 30-300 min, cooling to 80-120 ℃, adding hydrocarbon resin and the initiator, reacting at the temperature for 30-300 min, and cooling to obtain the benzoxazine resin/maleimide resin composite material. The low-dielectric and high-heat-resistant benzoxazine resin containing the hydrocarbon chain segment and the imine ring has the characteristics of low dielectric constant, low dielectric loss, high heat resistance and the like, and is particularly suitable for being used as a raw material for a high-frequency and high-speed copper-clad plate.
Description
Technical Field
The invention belongs to benzoxazine resin for a copper-clad plate and a preparation method thereof, and relates to low-dielectric and high-heat-resistance benzoxazine resin containing a hydrocarbon chain segment and an imine ring and a preparation method thereof. The low-dielectric and high-heat-resistant benzoxazine resin containing the hydrocarbon chain segment and the imine ring is particularly suitable for being used as a raw material for a high-frequency and high-speed copper-clad plate, and can also be used in the fields of laminated plates, integrated circuit packaging, high-density internet and the like.
Background
5G is becoming one of the most influential technological changes. Due to the requirements of data transmission rate, high reliability and the like of 5G communication, very high requirements on the aspects of dielectric constant, dielectric loss factor, heat resistance and the like of used laminated plates and copper-clad plates are provided. The electronic resin used as an important component of the laminated board and the copper-clad board has the key points of research on reducing the dielectric constant and the dielectric loss factor and improving the heat resistance of the electronic resin.
The benzoxazine resin is a six-membered heterocyclic compound containing C, N, O and prepared by condensing phenol, primary amine and formaldehyde, and the benzoxazine resin is subjected to ring-opening polymerization under the action of heating or a catalyst to generate a nitrogen-containing network structure similar to phenolic resin, and a cured product has the characteristics of low dielectric constant, low dielectric loss, low water absorption, high heat resistance, processing dimensional stability, good flame retardance and the like, and is one of suitable raw materials for preparing the copper-clad plate. However, the conventional benzoxazine resins such as bisphenol a type and bisphenol F type resins have slightly high dielectric constant and dielectric loss, are only suitable for pressing of common copper clad laminates, and cannot be applied to high-frequency and high-speed copper clad laminates, and therefore, people try to further develop and synthesize benzoxazine with low dielectric property.
In recent years, it has been attempted to introduce a long chain segment of carbon chain into a benzoxazine structure, and it is desired to achieve the effect of reducing dielectric constant, dielectric loss, and the like by increasing the free volume of molecules, and there have been, for example: the preparation of dodecylphenol benzoxazine resin (thermosetting resin, No. 2013), cardanol benzoxazine resin (high polymer material science and engineering, No. 2011, volume 27), nonylphenol modified benzoxazine resin (chemical and adhesion, No. 2018, volume 40) and other documents report, but the carbon chain carbon atom number introduced into the structure is 6-12, and the increase of the molecular free volume of the benzoxazine is not obvious, so that the dielectric property of the resin after curing is not good, the heat resistance of the product is reduced along with the increase of the carbon chain, the Tg is less than or equal to 140 ℃, and the application of the product in the field of high-frequency high-speed copper clad plates is limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a low-dielectric and high-heat-resistance benzoxazine resin containing a hydrocarbon chain segment and an imine ring and a preparation method thereof. The invention adds a certain amount of maleimide resin, hydrocarbon resin and initiator into benzoxazine resin, and then the reaction is carried out at a certain temperature to obtain the low dielectric and high heat-resistant benzoxazine resin containing hydrocarbon chain segments and imine rings, thereby providing the benzoxazine resin containing hydrocarbon chain segments and imine rings and having the characteristics of low dielectric constant, low dielectric loss, high heat resistance and the like, and the preparation method thereof.
The content of the invention is as follows: a low dielectric and high heat-resistant benzoxazine resin containing hydrocarbon chain segment and imine ring, which contains reactive double bond, imine ring and hydrocarbon chain segment besides oxazine ring in the structure, is characterized in that: the compound has a chemical structural general formula shown in a formula (I):
in the formula (I), n is 1-10, R1Is H, vinyl, allyl, or "-CH2-、-C(CH3)2-、-SO2A bisphenol with a bridging group of O-, -CO-, "an addition polymerization structure of double bonds on a benzo structure and double bonds in a formula (II)," an addition polymerization structure of double bonds on a benzo structure and double bonds on an imine ring in a formula (III), and the like;
R2is phenyl, nitrobenzene, vinyl, allyl, methacryloyl, or "-CH2-、-SO2-Diamine which is a bridging group, an addition polymerization structure of double bonds on a benzo structure and double bonds in a formula (II), an addition polymerization structure of double bonds on the benzo structure and double bonds on an imine ring in a formula (III) and the like;
R3h, a structure obtained by addition polymerization of a phenolic hydroxyl group on the "benzo structure and a double bond on the imine ring in the formula (III), and the like.
R4H, allyl, an addition polymerization structure of a double bond on a benzo structure and a double bond in a formula (II), an addition polymerization structure of a double bond on a benzo structure and a double bond on an imine ring in a formula (III), and the like;
in the formulas (II) and (III): x and y are 0-10, z is 5-20, n is 1-10, R5H, methyl, vinyl, etc.; r6is-CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、- (CH2)8-、-(CH2)10-，-(CH2)12-，
R7Is H, -CH3、-C2H5-、-C3H7-、-COOH、-NO2、-CH＝CH2、-CH2-CH＝CH2C ≡ CH, tert-butyl, phenyl, methacryloyl.
Another aspect of the invention is: a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings is characterized by comprising the following steps: adding 100g of double-bond-containing benzoxazine resin, 10-40 g of maleimide resin, 50-80 g of solvent and 0.001-0.05 g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 80-140 ℃, pre-polymerizing for 30-300 min, cooling to 80-120 ℃, adding 10-40 g of hydrocarbon resin and 0.001-0.05 g of initiator, reacting for 30-300 min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring;
the double-bond-containing benzoxazine resin is one or a mixture of more than two compounds with a chemical structural formula shown as a formula (IV) or a formula (VIII):
in the formulae (IV) to (VIII), R8、R14、R19Is- (CH)2) -n (n ═ 0, 1), -C ═ O, and the like; r9、R15、R20Is H, -CH3Etc.; r10Is H, C1～C6Alkyl, phenyl, epoxy, amino, nitro, naphthyl or cyclohexyl of (a); r11Phenyl, nitrobenzene, methacryloyl and the like; r12、R16、R24Methoxy, etc.; r13、R17、R23Is- (CH)2) -n (n ═ 0, 1), and the like; r18is-CH2-、-C(CH3)2-、-SO2O-, -CO-, etc.; r21Is allyl; r22is-CH2-、-SO2-, -O-, etc.
The maleimide resin is a compound having a chemical structural formula shown in the above formula (III);
the hydrocarbon resin is a compound having a chemical structural formula shown in the formula (II);
the initiator is peroxide, azo compound or redox initiator.
In another aspect of the invention: the maleimide resin can be MDA type bismaleimide resin, mono-maleimide resin or polymaleimide resin, and specifically can be provided for product production with enterprises and brands as follows: one or a mixture of more than two of BMI-1000, BMI-1100 and BMI-3000 of DAIWA in Japan, BMI-70 of KI in Japan, N-PMI of Tosoh chemical in North Hu China.
In another aspect of the invention: the initiator can be one or a mixture of more than two of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.
In another aspect of the invention: the solvent is one or a mixture of more than two of butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone.
In another aspect of the invention: the double bond-containing benzoxazine resin may be one of p-vinylphenol/aniline type benzoxazine resin (self-made), bisphenol F/vinylphenylamine type benzoxazine resin (self-made), MDA (short for diaminodiphenylmethane)/p-vinylphenol type benzoxazine resin (self-made), and bisphenol S/allylamine type benzoxazine resin (self-made).
The preparation method of the benzoxazine containing double bonds comprises the steps of adding 37% of formaldehyde solution into a three-necked bottle provided with a stirrer, a thermometer and a condenser, adjusting the pH value by using 1mol/L of NaOH solution, adding ethanol, and uniformly stirring, wherein the adding amount of the ethanol is 4 times of that of the formaldehyde solution. Then adding primary amine compound in batches, controlling the molar ratio of the amino group to the formaldehyde at 1:2.1, and controlling the reaction temperature to be not more than 30 ℃. After the reaction is finished in batches, the reaction is maintained for 10min, and then the phenolic compound is added, wherein the molar ratio of the phenolic hydroxyl group to the amino group is 1: 1. The reaction mixture was heated to reflux temperature, and the reaction was maintained for 4 hours, and the heating was stopped. And taking the resin layer, and removing the solvent by using a rotary evaporator to obtain the benzoxazine resin containing double bonds.
In another aspect of the invention: the hydrocarbon resin is a poly (styrene-butadiene) resin.
In another aspect of the invention: the hydrocarbon resin can be specifically a product production providing enterprise (the product production providing enterprise and the brand can be one or a mixture of more than two of Craiwili Ricon 100, Ricon 184, Ricon181 and the like.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
(1) by adopting the preparation method, the benzoxazine resin containing double bonds is adopted in the preparation of the low-dielectric and high-heat-resistance benzoxazine resin containing the hydrocarbon chain segment and the imine ring, the double bonds in the molecular structure can be used as reactive active points to introduce other high-performance resins containing double bonds, and the crosslinking points can be increased in the resin curing process, so that the resin crosslinking density is improved, and the heat resistance of the product is further improved;
(2) by adopting the invention, in the low-dielectric and high-heat-resistant benzoxazine resin containing the hydrocarbon chain segment and the imine ring, the double bond in the benzoxazine structure reacts with the double bond of the imine ring, so that the imine ring with high heat resistance is introduced into the benzoxazine resin structure, the heat resistance of the benzoxazine resin is improved, meanwhile, the dielectric property of the maleimide resin is better, particularly the dielectric loss is very excellent, and after the maleimide resin is introduced into the benzoxazine resin structure, the dielectric constant and the dielectric loss of the benzoxazine resin are further reduced;
(3) in the low-dielectric and high-heat-resistance benzoxazine resin containing the hydrocarbon chain segment and the imine ring, phenolic hydroxyl in a benzoxazine structure reacts with double bonds of the imine ring, so that the open phenolic hydroxyl is eliminated, and the dielectric constant and the dielectric loss of the benzoxazine resin are further reduced;
(4) by adopting the invention, the hydrocarbon resin is introduced into the low-dielectric and high-heat-resistant benzoxazine resin containing the hydrocarbon chain segment and the imine ring, more hydrocarbon chain segments are added in the whole structure, the dielectric constant and the dielectric loss of the product are lower, and the benzoxazine resin has better heat resistance by selecting the hydrocarbon containing a large number of benzene ring structures;
(5) the product of the invention has simple preparation process and easy operation, and the prepared low dielectric and high heat-resistant benzoxazine resin containing hydrocarbon chain segments and imine rings has the following properties: the dielectric constant is less than or equal to 2.80(10 GHz); the dielectric loss is less than or equal to 0.007 (10 GHz); the heat resistance Td5 percent is more than or equal to 380 ℃, and the Tg is more than or equal to 220 ℃; the resin has the characteristics of low dielectric constant, low dielectric loss and high glass transition temperature, has excellent comprehensive performance, can be used as resin for a high-performance copper-clad plate, and has good product performance and strong practicability.
Detailed Description
The following examples are intended to further illustrate the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims appended hereto.
Example 1:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: 100g of p-vinylphenol/aniline benzoxazine resin, 20g of MDA (diamino diphenyl methane, abbreviated as the same hereinafter) bismaleimide resin (BMI-1000 of DAIWA in Japan), 80g of cyclohexanone and 0.02g of dicumyl peroxide are added into a reactor provided with a stirrer, a thermometer and a condenser, the temperature is increased to 100 ℃, prepolymerization is carried out for 30min, the temperature is slightly reduced to 80 ℃,20 g of poly (styrene-butadiene resin) (Ricon 100) and 0.02g of dicumyl peroxide are added, reaction is carried out for 150min at the temperature, and the temperature is reduced, so that the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring is prepared, the benzoxazine resin is red brown transparent liquid, the solid content is 64%, and the chemical structure is as shown in the following formula (9):
in the formula (9), x, y, n are 1-10, z is 5-20
Example 2:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of bisphenol F/vinyl aniline benzoxazine resin, 30g of mono-maleimide resin (N-PMI in northern east Cao of lake), 50g of solvent and 0.01g of azobisisobutyronitrile into a reactor provided with a stirrer, a thermometer and a condenser, heating to 120 ℃, prepolymerizing for 60min, slightly cooling to 90 ℃, adding 30g of poly (styrene-butadiene) resin (Ricon 100) and 0.01g of dicumyl peroxide, reacting for 120min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring, wherein the benzoxazine resin is a red-brown transparent liquid, the solid content is 76.2%, and the chemical structure is as follows (10):
in the formula (10), x, y, n are 1-10, and z is 5-20.
Example 3:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of MDA/p-vinylphenol benzoxazine resin, 40g of MDA bismaleimide resin (BMI-1100 of DAIWA in Japan), 60g of butanone and 0.02g of azobisisobutyronitrile into a reactor provided with a stirrer, a thermometer and a condenser, heating to 100 ℃, pre-polymerizing for 3min, slightly cooling to 90 ℃, adding 10g of butylbenzene poly (Ricon 181) and 0.005g of tert-butyl peroxybenzoate, reacting for 200min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring, wherein the benzoxazine resin is a red-brown transparent liquid, the solid accounts for 71.4%, and the chemical structure is as follows (11):
in the formula (11), x, y, n are 1-10, and z is 5-20.
Example 4:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of bisphenol S/allylamine type benzoxazine resin, 20g of MDA type maleimide resin (BMI-1000 of DAIWA in Japan), 70g of toluene and 0.01g of tert-butyl peroxybenzoate into a reactor provided with a stirrer, a thermometer and a condenser, heating to 120 ℃, pre-polymerizing for 60min, slightly cooling to 90 ℃, adding 20g of butylbenzene poly (Ricon 100) and 0.02g of tert-butyl peroxybenzoate, reacting for 150min at the temperature, and cooling to obtain the low dielectric and high heat resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring, wherein the benzoxazine resin is a red brown transparent liquid, the solid content is 78.3%, and the chemical structure is as shown in the following formula (12):
in the formula (12), x, y, n are 1-10, and z is 5-20.
Some technical properties of the low dielectric and high heat resistant benzoxazine resin containing hydrocarbon chain segment and imine ring prepared in the above example are shown in table 1 below:
table 1: examples 1-4 resin Performance results Table:
the low dielectric and high heat-resistant benzoxazine resin containing hydrocarbon chain segments and imine rings prepared in the embodiment of the invention and the benzoxazine resin of the comparative example are cured according to the procedures of 140 ℃ for 1h, 160 ℃ for 1h, 180 ℃ for 1h and 200 ℃ for 2h to prepare a casting body of 50mm multiplied by 0.8mm, and part of the technical performance comparison conditions of the test casting body are shown in the following table 2:
table 2: examples 1-4 cast body performance results are shown in the table:
comparative examples 1 and 2 are data of performance tests of outsourced long chain benzoxazine resin castings.
The technical performance test methods in table 2 are as follows:
(1) dielectric constant
The dielectric constant at 10GHz was measured according to IPC-TM-650 using a network analyzer 2.5.5.9.
(2) Dielectric loss tangent
The dielectric loss tangent at 10GHz was measured using a network analyzer according to IPC-TM-650, 2.5.5.9.
(3) Glass transition temperature (Tg)
According to differential scanning calorimetry, the measurement was carried out according to the DSC method defined by 2.4.25 in IPC-TM-650.
(4) Thermal decomposition temperature (Td)
The measurement was carried out according to the method defined in IPC-TM-650, 2.4.26.
As can be seen from table 2, the low dielectric benzoxazine resin having a hydrocarbon segment and an imine ring obtained by applying the example of the present invention has excellent heat resistance, a low dielectric constant and a low dielectric loss tangent. The resin can be used in the fields of laminated boards, integrated circuit packaging, high-frequency high-speed copper-clad plates, high-density internet and the like, and has wide application prospect.
Example 5:
a low dielectric and high heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring, wherein the structure of the benzoxazine resin contains an oxazine ring, a reactive double bond, an imine ring and a hydrocarbon chain segment, and the compound has a chemical structural general formula shown in a formula (I):
in the formula (I), n is 1-10, R1Is H, vinyl, allyl, or "-CH2-、-C(CH3)2-、-SO2A bisphenol with a bridging group of O-, -CO-, "an addition polymerization structure of double bonds on a benzo structure and double bonds in a formula (II)," an addition polymerization structure of double bonds on a benzo structure and double bonds on an imine ring in a formula (III), and the like;
R2is phenyl, nitrobenzene, vinyl, allyl, methacryloyl, or "-CH2-、-SO2-Diamine which is a bridging group, an addition polymerization structure of double bonds on a benzo structure and double bonds in a formula (II), an addition polymerization structure of double bonds on the benzo structure and double bonds on an imine ring in a formula (III) and the like;
R3h, a structure obtained by addition polymerization of a phenolic hydroxyl group on the "benzo structure and a double bond on the imine ring in the formula (III), and the like.
R4Is H, allyl, the addition polymerization structure of double bond on the benzo structure and double bond in the formula (II), the double bond on the benzo structure anddouble bond addition polymerization structure on the imine ring in the formula (III), etc.;
in the formulas (II) and (III): x and y are 0-10, z is 5-20, n is 1-10, R5H, methyl, vinyl, etc.; r6is-CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、- (CH2)8-、-(CH2)10-，-(CH2)12-，
R7Is H, -CH3、-C2H5-、-C3H7-、-COOH、-NO2、-CH＝CH2、-CH2-CH＝CH2C ≡ CH, tert-butyl, phenyl, methacryloyl.
Example 6:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of double bond-containing benzoxazine resin, 25g of maleimide resin, 65g of solvent and 0.025g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 110 ℃, prepolymerizing for 160min, cooling to 100 ℃, adding 25g of hydrocarbon resin and 0.025g of initiator, reacting for 120min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring.
Example 7:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of double bond-containing benzoxazine resin, 40g of maleimide resin, 80g of solvent and 0.05g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 140 ℃, prepolymerizing for 300min, cooling to 120 ℃, adding 40g of hydrocarbon resin and 0.05g of initiator, reacting for 300min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring.
Example 8:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of double bond-containing benzoxazine resin, 10g of maleimide resin, 50g of solvent and 0.001g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 80 ℃, carrying out prepolymerization for 30min, cooling to 80 ℃, adding 10g of hydrocarbon resin and 0.001g of initiator, reacting for 30min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring.
Example 9:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of double bond-containing benzoxazine resin, 18g of maleimide resin, 58g of solvent and 0.017g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 100 ℃, prepolymerizing for 100min, cooling to 93 ℃, adding 16g of hydrocarbon resin and 0.015g of initiator, reacting for 100min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring.
Example 10:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of double bond-containing benzoxazine resin, 32g of maleimide resin, 70g of solvent and 0.04g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 130 ℃, carrying out prepolymerization for 200min, cooling to 110 ℃, adding 33g of hydrocarbon resin and 0.04g of initiator, reacting for 200min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring.
Example 11:
a preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings comprises the following steps: adding 100g of double-bond-containing benzoxazine resin, 35g of maleimide resin, 70g of solvent and 0.035g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 140 ℃, carrying out prepolymerization for 30min, cooling to 120 ℃, adding 30g of hydrocarbon resin and 0.035g of initiator, reacting for 60min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring.
Examples 6 to 11 above:
the double-bond-containing benzoxazine resin is one or a mixture of more than two compounds with a chemical structural formula shown as a formula (IV) or a formula (VIII):
in the formulae (IV) to (VIII), R8、R14、R19Is- (CH)2) -n (n ═ 0, 1), -C ═ O, and the like; r9、R15、R20Is H, -CH3Etc.; r10Is H, C1～C6Alkyl, phenyl, epoxy, amino, nitro, naphthyl or cyclohexyl of (a); r11Phenyl, nitrobenzene, methacryloyl and the like; r12、R16、R24Methoxy, etc.; r13、R17、R23Is- (CH)2) -n (n ═ 0, 1), and the like; r18is-CH2-、-C(CH3)2-、-SO2O-, -CO-, etc.; r21Is allyl; r15is-CH2-、-SO2And the like.
The maleimide resin is a compound having a chemical structural formula shown in the above formula (III);
the hydrocarbon resin is a compound having a chemical structural formula shown in the formula (II);
the initiator is peroxide, azo compound or redox initiator.
Examples 6 to 11 above:
the maleimide resin can be provided for product production enterprises and has the following grades: one or more of BMI-1000, BMI-1100 and BMI-3000 of DAIWA in Japan, BMI-70 of KI in Japan, N-PMI of Tosoh chemical in North Hu, etc.;
the initiator can be one or a mixture of more than two of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile;
the solvent is one or a mixture of more than two of butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone;
the hydrocarbon resin can be a poly styrene-butadiene resin, and particularly can be a mixture of one or more than two of production providing enterprises and brands of Clevix Ricon 100, Ricon 184, Ricon181 and the like.
Examples 6 to 11 above:
the double bond-containing benzoxazine resin may be one of p-vinylphenol/aniline type benzoxazine resin (self-made), bisphenol F/vinylphenol amine type benzoxazine resin (self-made), MDA/p-vinylphenol type benzoxazine resin (self-made), and bisphenol S/allylamine type benzoxazine resin (self-made).
The preparation method of the benzoxazine containing double bonds comprises the steps of adding 37% of formaldehyde solution into a three-necked bottle provided with a stirrer, a thermometer and a condenser, adjusting the pH value by using 1mol/L of NaOH solution, adding ethanol, and uniformly stirring, wherein the adding amount of the ethanol is 4 times of that of the formaldehyde solution. Then adding primary amine compound in batches, controlling the molar ratio of the amino group to the formaldehyde at 1:2.1, and controlling the reaction temperature to be not more than 30 ℃. After the reaction is finished in batches, the reaction is maintained for 10min, and then the phenolic compound is added, wherein the molar ratio of the phenolic hydroxyl group to the amino group is 1: 1. The reaction mixture was heated to reflux temperature, and the reaction was maintained for 4 hours, and the heating was stopped. And taking the resin layer, and removing the solvent by using a rotary evaporator to obtain the benzoxazine resin containing double bonds.
In the above embodiment: the definition of the amount of solids is: the percentage of solid neat resin in solution to the total solution (resin plus solvent) is, for example: the 64% solids level described in example 1 means that the percentage of pure resin of formula (9) in the total solution is 64%.
In the above embodiment: the process parameters (temperature, time, etc.) and the numerical values of the components in each step are in the range, and any point can be applicable.
The present invention and the technical contents not specifically described in the above examples are the same as those of the prior art, and the raw materials are all commercially available products.
The present invention is not limited to the above-described embodiments, and the present invention can be implemented with the above-described advantageous effects.
Claims (8)
1. A low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings is characterized in that: the compound has a chemical structural general formula shown in a formula (I):
in the formula (I), n is 1-10, R1Is H, vinyl, allyl, or "-CH2-、-C(CH3)2-、-SO2A bisphenol with bridging groups of O and CO-, "an addition polymerization structure of double bonds on a benzo structure and double bonds in a formula (II) and an addition polymerization structure of double bonds on a benzo structure and double bonds on an imine ring in a formula (III);
R2is phenyl, nitrobenzene, vinyl, allyl, methacryloyl, or "-CH2-、-SO2-"diamine which is bridging group," addition polymerization structure of double bond on benzo structure and double bond in formula (II), "addition polymerization structure of double bond on benzo structure and double bond on imine ring in formula (III)";
R3is H, a structure obtained by addition polymerization of a phenolic hydroxyl group on the "benzo structure and a double bond on the imine ring in the formula (III)".
R4Is H, allyl, an addition polymerization structure of double bonds on a benzo structure and double bonds in a formula (II) and an addition polymerization structure of double bonds on a benzo structure and double bonds on an imine ring in a formula (III);
in the formulas (II) and (III): x and y are 0-10, z is 5-20, n is 1-10, R5H, methyl, vinyl; r6is-CH2-、-SO2、-O-、-CO-、-S2-、-(CH2)2-、-(CH2)4-、-(CH2)6-、-(CH2) 8-、-(CH2)10-，-(CH2)12-，
R7Is H, -CH3、-C2H5-、-C3H7-、-COOH、-NO2、-CH＝CH2、-CH2-CH＝CH2、
Tert-butyl, phenyl, methacryloyl.
2. A preparation method of low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segments and imine rings is characterized by comprising the following steps: adding 100g of double-bond-containing benzoxazine resin, 10-40 g of maleimide resin, 50-80 g of solvent and 0.001-0.05 g of initiator into a reactor provided with a stirrer, a thermometer and a condenser, heating to 80-140 ℃, pre-polymerizing for 30-300 min, cooling to 80-120 ℃, adding 10-40 g of hydrocarbon resin and 0.001-0.05 g of initiator, reacting for 30-300 min at the temperature, and cooling to obtain the low-dielectric and high-heat-resistant benzoxazine resin containing a hydrocarbon chain segment and an imine ring;
the double-bond-containing benzoxazine resin is one or a mixture of more than two compounds with a chemical structural formula shown as a formula (IV) or a formula (VIII):
in the formulae (IV) to (VIII), R8、R14、R19Is- (CH)2)-n(n＝0、1)、-C＝O；R9、R15、R20Is H, -CH3；R10Is H, C1～C6Alkyl, phenyl, epoxy, amino, nitro, naphthyl or cyclohexyl of (a); r11Is phenyl, nitrobenzene, methacryloyl; r12、R16、R24Is methoxy; r13、R17、R23Is- (CH)2)-n(n＝0、1)；R18is-CH2-、-C(CH3)2-、-SO2、-O-、-CO-；R21Is allyl; r22is-CH2-、-SO2-、-O-。
The maleimide resin is a compound having a chemical structural formula shown in the above formula (III);
the hydrocarbon resin is a compound having a chemical structural formula shown in the formula (II);
the initiator is peroxide, azo compound or redox initiator.
3. A method for preparing a low dielectric, highly heat resistant benzoxazine resin containing hydrocarbon segment and imine ring according to claim 2, wherein: the maleimide resin provides enterprises for product production and has the following grades: one or more of BMI-1000, BMI-1100 and BMI-3000 of DAIWA in Japan, BMI-70 of KI in Japan, and N-PMI of Tosoh chemical in North of Hu.
4. A method for preparing a low dielectric, highly heat resistant benzoxazine resin containing hydrocarbon segment and imine ring according to claim 2, wherein: the initiator is one or a mixture of more than two of dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.
5. A method for preparing a low dielectric, highly heat resistant benzoxazine resin containing hydrocarbon segment and imine ring according to claim 2, wherein: the solvent is one or a mixture of more than two of butanone, toluene, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N-dimethylformamide, N-dimethylacetamide and methyl isobutyl ketone.
6. A method for preparing a low dielectric, highly heat resistant benzoxazine resin containing hydrocarbon segment and imine ring according to claim 2, wherein: the double-bond-containing benzoxazine resin is specifically one of p-vinylphenol/aniline type benzoxazine resin, bisphenol F/vinylaniline type benzoxazine resin, MDA/p-vinylphenol type benzoxazine resin and bisphenol S/allylamine type benzoxazine resin.
7. A method for preparing a low dielectric, highly heat resistant benzoxazine resin containing hydrocarbon segment and imine ring according to claim 2, wherein: the hydrocarbon resin is a poly (styrene-butadiene) resin.
8. A process for preparing a low dielectric, highly heat resistant benzoxazine resin containing hydrocarbon segment and imine ring as claimed in claim 7, wherein: the hydrocarbon resin is a mixture of one or more than two of the trademarks of Clevix Ricon 100, Ricon 184 and Ricon181 and provided for product production enterprises.
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| CN104845363A (en) * | 2014-02-14 | 2015-08-19 | 广东生益科技股份有限公司 | Halogen-free resin composite and use thereof |
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| CN111117154A (en) * | 2019-12-31 | 2020-05-08 | 广东生益科技股份有限公司 | Flame-retardant thermosetting resin composition, and prepreg, laminated board and printed circuit board manufactured from same |
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