CN114957154B - High heat-resistant low-dielectric benzoxazine prepolymer and copolymer resin containing polymerizable end groups and preparation method thereof - Google Patents
High heat-resistant low-dielectric benzoxazine prepolymer and copolymer resin containing polymerizable end groups and preparation method thereof Download PDFInfo
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- CN114957154B CN114957154B CN202111675027.7A CN202111675027A CN114957154B CN 114957154 B CN114957154 B CN 114957154B CN 202111675027 A CN202111675027 A CN 202111675027A CN 114957154 B CN114957154 B CN 114957154B
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229920006026 co-polymeric resin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 phenol compound Chemical class 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 14
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 238000005266 casting Methods 0.000 claims abstract description 8
- 238000004100 electronic packaging Methods 0.000 claims abstract description 7
- 239000005022 packaging material Substances 0.000 claims abstract description 7
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- 229920002866 paraformaldehyde Polymers 0.000 claims description 11
- 238000004891 communication Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- GOCRPOKWZIVUQG-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propan-1-amine Chemical compound CCOC(OCC)[SiH2]CCCN GOCRPOKWZIVUQG-UHFFFAOYSA-N 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- FNVCMFDUMKLCTC-UHFFFAOYSA-N 3-methylsilylpropan-1-amine Chemical group C[SiH2]CCCN FNVCMFDUMKLCTC-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 23
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 12
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 10
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 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 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 3
- KURPPWHPIYBYBS-UHFFFAOYSA-N 2-ethenylaniline Chemical compound NC1=CC=CC=C1C=C KURPPWHPIYBYBS-UHFFFAOYSA-N 0.000 description 3
- ALQPJHSFIXARGX-UHFFFAOYSA-N 2-ethynylaniline Chemical compound NC1=CC=CC=C1C#C ALQPJHSFIXARGX-UHFFFAOYSA-N 0.000 description 3
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 3
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical compound NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 3
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 3
- YBAZINRZQSAIAY-UHFFFAOYSA-N 4-aminobenzonitrile Chemical compound NC1=CC=C(C#N)C=C1 YBAZINRZQSAIAY-UHFFFAOYSA-N 0.000 description 3
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 3
- ZSDKRCVZMXLSPK-UHFFFAOYSA-N bicyclo[4.2.0]octa-1(6),2,4-trien-5-amine Chemical compound NC1=CC=CC2=C1CC2 ZSDKRCVZMXLSPK-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 description 2
- IJWIRZQYWANBMP-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-propan-2-ylphenyl)propan-2-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C(C)(C)C=2C=C(C(O)=CC=2)C(C)C)=C1 IJWIRZQYWANBMP-UHFFFAOYSA-N 0.000 description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 2
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- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
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- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
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- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- CJYCVQJRVSAFKB-UHFFFAOYSA-N octadecane-1,18-diamine Chemical compound NCCCCCCCCCCCCCCCCCCN CJYCVQJRVSAFKB-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a high heat-resistant low-dielectric benzoxazine prepolymer containing a polymerizable end group, a copolymer resin and a preparation method thereof, wherein the preparation method comprises the following steps: mixing a dihydric phenol compound, a diamine compound, a monoamine compound containing active functional groups, formaldehyde and a solvent, and reacting at 50-110 ℃ to prepare the benzoxazine prepolymer containing the polymerizable terminal groups. And dissolving the benzoxazine prepolymer in a solvent, forming a film by a casting method, and heating to enable oxazine ring to open and polymerize, enabling polymerizable end groups to self-polymerize or carrying out dealcoholization condensation reaction to obtain the benzoxazine copolymer resin with high heat resistance and low dielectric property. The synthesized benzoxazine copolymer resin has potential application value in the fields of high-frequency high-speed circuit substrate materials, composite material matrix resins, electronic packaging materials and the like.
Description
Technical Field
The invention relates to a high heat-resistant low-dielectric benzoxazine copolymer resin, in particular to a high heat-resistant low-dielectric benzoxazine prepolymer containing a polymerizable end group, a copolymer resin and a preparation method thereof, belonging to the technical field of functional high polymer materials.
Background
In the field of high frequency and high speed communications (e.g., 5G communications), resistance-capacitance (RC) delay has become one of the bottlenecks in the development of large-scale integrated circuits, even very large-scale integrated circuits. RC delay causes problems such as signal propagation delay, noise interference, and increase in power dissipation, so RC delay is disadvantageous for high-speed propagation and high-quality propagation of signals. Since the RC delay is proportional to the dielectric constant of the Printed Circuit Board (PCB) substrate material, lowering the dielectric constant of the substrate material can attenuate the RC delay. In addition, the propagation loss of the communication signal increases with the increase of the dielectric loss tangent, the dielectric constant and the signal transmission frequency of the substrate material, so that lowering the dielectric loss tangent and the dielectric constant can reduce the signal propagation loss. In summary, both for the resolution of the RC delay problem and for the resolution of the signal propagation loss problem, PCB substrate materials are required to have low dielectric constants and low dielectric losses.
Polybenzoxazines (PBZ) are a new class of phenolic resins with many excellent properties such as high thermal stability, low hygroscopicity, good flame retardant properties, etc. Accordingly, PBZ is particularly suitable for electronic materials (e.g., PCB substrate materials, electronic packaging materials, etc.). However, the dielectric properties of the common PBZ are poor (dk=3.5), and the use requirements of the PCB on the substrate material with low dielectric constant and low dielectric loss cannot be met. There is an urgent need to develop PBZ having excellent dielectric properties.
Currently, low dielectric modification methods of benzoxazine resins include the following: (1) introducing F atoms. Since the C-F bond has a smaller molecular polarizability than the C-H bond, the C-F bond can be used instead of the C-H bond to lower the dielectric constant of the material. (2) increasing the free volume of the molecule. The polar molecular density and the polar group density of the material are reduced by increasing the free volume of the molecules. The introduction of low-polarity and large-volume groups (such as dicyclopentadiene structures, tert-butyl structures and the like) into the polymer reduces the packing density of polymer molecular chains, thereby reducing the dielectric constant and dielectric loss of the material. (3) introducing a micro-nano hole structure. Since air having an extremely low dielectric constant (about 1) is introduced while the polarized molecular density and the polar group density of the polymer are reduced, excellent dielectric properties can be obtained. The introduction mode of the micro-nano holes comprises two modes: one is to form micro-nano pore structures by alkaline hydrolysis of labile polymers in benzoxazine copolymers; the other is to add micro-nano-pore-containing inorganic particles (graphene oxide, polyhedral oligomeric silsesquioxanes, mesoporous silica, etc.) to the polymer. (4) Synthesizing benzoxazine monomer containing low dielectric functional groups and copolymerizing benzoxazine resin with other low dielectric resin. The purpose of improving the dielectric properties of the benzoxazine resin can be achieved by introducing low dielectric functional groups (norbornene groups, benzoxazole rings, acetylene groups, vinyl groups, etc.) into the benzoxazine monomer or by copolymerizing the benzoxazine resin with other low dielectric resins (polydimethylsiloxane, bismaleimide resins, cyanate resins, etc.). (5) preparing a main chain benzoxazine copolymer oligomer. By utilizing the molecular design advantages of benzoxazine monomer synthesis, a low-polarity fatty chain structure, a large-volume low-polarity structure and a high-regularity structure are introduced into a main chain benzoxazine prepolymer, and the main chain benzoxazine resin with excellent high-frequency dielectric property is obtained after curing.
Since 5G communication is a high frequency and high speed communication, a substrate material of a PCB is required to have excellent high frequency dielectric properties, and thus a high frequency and low dielectric benzoxazine resin can be synthesized using the method (5). However, the benzoxazine resin prepared by the method has low heat resistance, for example, tg of the benzoxazine cured resin in the documents 1.Polym Chem 2018,9,2913 and 2.ACS Appl Polym Mater 2019,1,625 is lower than 205 ℃, and the requirement of the copper clad laminate for 5G communication on the high heat resistance of the substrate material cannot be met.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a benzoxazine prepolymer containing a polymerizable end group and having high heat resistance and low dielectric property, a copolymer resin and a preparation method thereof. The invention selects monoamine containing polymerizable groups or groups contained in end-capping groups and capable of reacting with a benzoxazine skeleton as an end-capping agent of the benzoxazine prepolymer, and improves the crosslinking density of a benzoxazine resin crosslinking network through polymerization reaction of the active groups or dealcoholization condensation reaction of siloxy groups contained in the end-capping groups and phenolic hydroxyl groups, so that the benzoxazine copolymer resin with high heat resistance and low dielectric property is obtained.
In order to solve the technical problems, the technical scheme of the invention is as follows:
1. a benzoxazine prepolymer, wherein the structure of the benzoxazine prepolymer is shown in a formula (I):
wherein the method comprises the steps of
R 1 Selected from the group consisting of
R 2 Selected from the group consisting of single bonds,
R 3 is a group capable of polymerizing to form a crosslinked structure having a double bond, a triple bond, a cyano group, benzocyclobutene, or an alkoxysilane.
2. The benzoxazine prepolymer according to item 1, wherein the R 3 Selected from the group consisting of
3. A method for preparing a benzoxazine prepolymer according to formula (I) as described in item 1 or 2, comprising the steps of:
a step of preparing a benzoxazine prepolymer represented by the formula (I) by reacting a dihydric phenol compound, a diamine compound, and a monoamine compound having an active functional group in the presence of an aldehyde compound and a solvent.
4. The production method as described in item 3, wherein the dihydric phenol compound has a structure represented by formula (II),
the structure of the diamine compound is shown as a formula (III),
H 2 N-R 1 -NH 2
(III)
the structure of the monoamine compound is shown as a formula (IV),
R 3 -NH 2
the R is 1 、R 2 And R is 3 R as set forth in item 1 1 、R 2 And R is 3 。
5. The production method according to item 3 or 4, wherein,
the dihydric phenol compound is bisphenol A, bisphenol F, 4 '-dihydroxydiphenyl ether, bisphenol S, dicyclopentadiene diphenol, bisphenol fluorene or 4,4' -dihydroxybiphenyl;
preferably, the diamine compound is 4,4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminobiphenyl or p-phenylenediamine;
preferably, the monoamine compound is allylamine, propargylamine, 4-cyanoaniline, 4-aminobenzocyclobutene, 4-vinylaniline, 3-vinylaniline, 2-vinylaniline, 4-ethynylaniline, 3-ethynylaniline, 2-ethynylaniline, diethoxymethyl aminopropyl silane or dimethoxy methyl aminopropyl silane;
preferably, the aldehyde compound is formaldehyde or paraformaldehyde, and more preferably, the aldehyde compound is formaldehyde aqueous solution or paraformaldehyde with the mass concentration of 37%;
preferably, the solvent is water, ethanol, tetrahydrofuran, acetone, N-dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, dioxane, chloroform or toluene.
6. The production process according to any one of the above 3 to 5, wherein, in parts by weight,
30-80 parts of dihydric phenol compound, 15-40 parts of diamine compound, 15-40 parts of monoamine compound, 20-50 parts of aldehyde compound and 40-100 parts of solvent;
preferably, the dihydric phenol compound is 40-80 parts, the diamine compound is 20-40 parts, the monoamine compound is 20-40 parts, the aldehyde compound is 30-50 parts, and the solvent is 70-95 parts.
7. The production process according to any one of items 3 to 6, wherein the reaction temperature is 50 to 110 ℃, preferably 75 to 100 ℃, further preferably 80 to 95 ℃;
the reaction time is preferably 1 to 24 hours, more preferably 3 to 20 hours, still more preferably 5 to 18 hours.
8. The production method according to any one of items 3 to 7, wherein the production method further comprises a step of washing the benzoxazine prepolymer by the following method,
the prepared benzoxazine prepolymer is washed by ethanol, methanol, petroleum ether or n-hexane.
9. The production method according to any one of the above 3 to 8, wherein the production method further comprises a step of vacuum-drying the benzoxazine prepolymer at a temperature of 50 to 90 ℃ for a time of 6 to 24 hours.
10. A benzoxazine copolymer resin, wherein it is self-crosslinked after opening by an oxazine ring of a benzoxazine prepolymer represented by formula (I) as described in item 1 or 2; and
R 3 double bonds, triple bonds, cyano groups or benzocyclobutene in the groups are polymerized to form a crosslinked structure; or (b)
R 3 The ethoxy or methoxy of the group reacts with phenolic hydroxyl generated after oxazine ring opening to form Si-O-Ph bond crosslinking structure;
solidifying to obtain the final product.
11. The benzoxazine-based copolymer resin according to item 10, wherein, when R 3 Is thatIn the process, the structural formula of the copolymer resin is shown as a formula (V),
wherein the method comprises the steps of
R 1 Selected from the group consisting of
R 2 Selected from the group consisting of single bonds,
12. the benzoxazine-based copolymer resin according to item 10, wherein, when R 3 Is thatWhen in use, the co-ordinatesThe structural formula of the polyresin is shown as a formula (VI),
wherein the method comprises the steps of
R 1 Selected from the group consisting of
R 2 Selected from the group consisting of single bonds,
13. a method of preparing the benzoxazine-based copolymer resin according to any one of claims 10 to 12, comprising the steps of:
the benzoxazine prepolymer shown in the formula (I) in the item 1 or 2 is dissolved in a solvent, and is formed into a film by a casting method and thermally cured to obtain the benzoxazine copolymer resin.
14. The production method according to item 13, wherein the solvent is toluene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, methylene chloride, chloroform, dioxane or tetrahydrofuran.
15. The use of a benzoxazine copolymer resin according to any one of claims 10 to 12 in the fields of high frequency high speed circuit substrate materials, microwave and millimeter wave communications, vehicle radar and other composite matrix resins and electronic packaging materials.
Effects of the invention
The invention takes dihydric phenol, diamine, monoamine containing active functional groups and formaldehyde as raw materials, successfully synthesizes benzoxazine prepolymer containing polymerizable end groups through Mannich condensation reaction, adopts a casting film forming method and heats to lead oxazine ring to open and polymerize, and the polymerizable end groups self-polymerize or take dealcoholization condensation reaction to obtain the benzoxazine copolymer resin with high heat resistance and low dielectric property, and has the following remarkable advantages:
1. the benzoxazine copolymer resin containing the polymerizable end group shows higher heat resistance due to the improvement of the crosslinking density of the benzoxazine copolymer resin crosslinking network and the existence of a high aromatic structure;
2. because of the introduction of a high-regularity structure, a large-volume low-polarity structure, a hydrocarbon-like resin structure and a benzocyclobutene-like resin structure and the reduction of the content of the phenolic hydroxyl groups of the strong polar groups, the benzoxazine copolymer resin containing the polymerizable end groups shows excellent high-frequency dielectric properties;
3. the synthesized benzoxazine copolymer resin with high heat resistance and low dielectric property has potential application value in the fields of high-frequency and high-speed circuit substrate materials, composite material matrix resins and electronic packaging materials.
Detailed Description
The invention will be further illustrated with reference to the following examples, which are to be understood as merely further illustrating and explaining the invention and are not to be construed as limiting the invention.
Unless defined otherwise, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the materials and methods are described herein below. In case of conflict, the present specification, including definitions therein, will control and materials, methods, and examples, will control and be in no way limiting. The invention is further illustrated below in connection with specific examples, which are not intended to limit the scope of the invention.
In one aspect, the present invention provides a novel benzoxazine prepolymer having a structure according to formula (I):
wherein the method comprises the steps of
R 1 Selected from the group consisting of
R 2 Selected from the group consisting of single bonds,
R 3 is a group capable of polymerizing to form a crosslinked structure having a double bond, a triple bond, a cyano group, benzocyclobutene, or an alkoxysilane.
In certain embodiments, the R 3 Selected from the group consisting of
In the structure of the novel benzoxazine prepolymer provided by the invention, in particular, when R is 1 Selected from the group consisting ofWhen in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use; r is R 3 Is->
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use; r is R 3 Is->
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use; r is R 3 Is->
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use; r is R 3 Is->
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use; r is R 3 Is->
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
Specifically, when said R 1 Selected from the group consisting of When in use;
R 2 selected from the group consisting of single bonds,when in use;
R 3 is that
More specifically, when R 1 Is thatR 2 Is->R 3 Is->In the process, the structural formula of the benzoxazine prepolymer of the invention is shown as follows,
more specifically, when R 1 Is thatR 2 Is->R 3 Is->In the process, the structural formula of the benzoxazine prepolymer of the invention is shown as follows,
/>
more specifically, when R 1 Is thatR 2 Is->R 3 Is->In the process, the structural formula of the benzoxazine prepolymer of the invention is shown as follows,
more specifically, when R 1 Is thatR 2 Is->R 3 Is->In the process, the structural formula of the benzoxazine prepolymer of the invention is shown as follows,
more specifically, when R 1 Is thatR 2 Is->R 3 Is->In the process, the structural formula of the benzoxazine prepolymer of the invention is shown as follows,
the invention further provides a method for preparing the benzoxazine prepolymer shown in the formula (I), which comprises the following steps:
a step of preparing a benzoxazine prepolymer represented by the formula (I) by reacting a dihydric phenol compound, a diamine compound, and a monoamine compound having an active functional group in the presence of an aldehyde compound and a solvent.
The dihydric phenol compound is a compound having two-OH groups, and examples include, but are not limited to, bisphenol A (2, 2-bis (4-hydroxyphenyl) propane, BPA), bisphenol AP (1, 1-bis (4-hydroxyphenyl) -1-phenylethane), bisphenol AF (2, 2-bis (4-hydroxyphenyl) hexafluoropropane), bisphenol B (2, 2-bis (4-hydroxyphenyl) butane), bisphenol BP (bis (4-hydroxyphenyl) diphenylmethane), bisphenol C (2, 2-bis (3-methyl-4-hydroxyphenyl) propane), bisphenol C (bis (4-hydroxyphenyl) -2, 2-dichloroethylene), bisphenol E (1, 1-bis (4-hydroxyphenyl) ethane), bisphenol F (bis (4-hydroxyphenyl) methane), bisphenol G (2, 2-bis (4-hydroxy-3-isopropylphenyl) propane), bisphenol M (1, 3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene), bisphenol S (4-hydroxyphenyl) -bisphenol S (4-hydroxyphenyl) sulfone, bisphenol S (2, 4-hydroxyphenyl) -2-sulfone (2-bisphenol P-2-hydroxyphenyl) sulfone, bisphenol PH (5, 5'- (1-methylethylidene) -bis [1,1' - (biphenyl) -2-ol ] propane), 4 '-dihydroxydiphenyl ether, dicyclopentadiene diphenol, bisphenol fluorene, 4' -dihydroxybiphenyl bisphenol TMC (1, 1-bis (4-hydroxyphenyl) -3, 5-trimethyl-cyclohexane), and bisphenol Z (1, 1-bis (4-hydroxyphenyl) cyclohexane).
In certain preferred embodiments of the present invention, the dihydric phenol compound has the structure shown in formula (II),
further, the dihydric phenol compound is preferably bisphenol A, bisphenol F, 4 '-dihydroxydiphenyl ether, bisphenol S, dicyclopentadiene diphenol, bisphenol fluorene or 4,4' -dihydroxybiphenyl.
The diamine compound has two-NH 2 Examples of the compound of the group include, but are not limited to, diaminodiphenylmethane, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, benzidine, furanmethanamine, 1, 4-diaminobenzene, 2-aminobenzylamine, 4' -diaminodiphenylmethane, 4'diaminodiphenyl, 4' -methylenedianiline, 4 '-diaminodiphenyl ether, 4' -diaminodiphenyl sulfone, 4 '-diaminodiphenyl sulfide, and 4,4' -oxydiphenylamine; alicyclic diamines including 1, 4-diaminocyclohexane; 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 10-diaminodecane, 1, 12-diaminododecane, 1, 14-diaminotetradecane and 1, 18-diaminooctadecane.
In certain preferred embodiments of the present invention, the diamine compound has a structure represented by formula (III),
H 2 N-R 1 —NH 2
(III)
further, the diamine compound is preferably 4,4' -diaminodiphenyl ether, 4' -diaminodiphenyl sulfide, 4' -diaminobiphenyl or p-phenylenediamine.
The monoamine compound is a compound having an-NH group 2 Examples of compounds of the group that may be cited include, but are not limited to, ethanolamine, allylamine, methylamine, ethylamine, propylamine, butylamine, isopropylamine, hexylamine, octadecylamine, cyclohexylamine, 2-aminofluorene and aniline, allylamine, propargylamine, 4-cyanoaniline, 4-aminobenzocyclobutene, 4-vinylaniline, 3-vinylaniline, 2-vinylaniline, 4-ethynylaniline, 3-ethynylaniline, 2-ethynylaniline or diethoxymethyl aminopropyl silane.
The monoamine compound in the present invention is a monoamine compound having a mobile functional group.
The structure of the monoamine compound is shown as a formula (IV),
R 3 -NH 2
(IV)
further, the monoamine compound is preferably allylamine, propargylamine, 4-cyanoaniline, 4-aminobenzocyclobutene, 4-vinylaniline, 4-maleimidophenol or 4-norbornene dicarboximidophenol, 3-vinylaniline, 2-vinylaniline, 4-ethynylaniline, 3-ethynylaniline, 2-ethynylaniline or diethoxymethyl aminopropyl silane or dimethoxy methylaminopropyl silane. .
The aldehyde compound can be selected from one or more than two of polyoxymethylene, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde and polyoxymethylene.
In certain preferred embodiments of the present invention, the aldehyde compound is formaldehyde or paraformaldehyde.
Further, the aldehyde compound is preferably an aqueous formaldehyde solution or paraformaldehyde with a mass concentration of 37%.
Further, the solvent is preferably water, ethanol, tetrahydrofuran, acetone, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, dioxane, chloroform or toluene.
In the method for preparing the benzoxazine prepolymer of the present invention as described above, in certain preferred embodiments, the reaction process is as shown in formula (VI),
further, in the production method as described in any one of the above, in parts by weight,
the dihydric phenol compound is 30 to 80 parts, for example, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, preferably 40 to 80 parts;
15 to 40 parts of the diamine compound, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, preferably 20 to 40 parts of the diamine compound;
the monoamine compound may be 15 to 40 parts, for example, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, and preferably 20 to 40 parts;
the aldehyde compound may be 20 to 50 parts, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 50 parts, and preferably the solvent is 70 to 95 parts;
the solvent is 40 to 100 parts, for example, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, preferably 70 to 95 parts.
In certain preferred embodiments of the present invention, the dihydric phenol compound is 40 to 80 parts, the diamine compound is 20 to 40 parts, the monoamine compound is 20 to 40 parts, the aldehyde compound is 30 to 50 parts, and the solvent is 70 to 95 parts.
In the method for producing a benzoxazine prepolymer according to the present invention as described above, the reaction temperature is 50 to 110 ℃, and may be, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃.
In certain preferred embodiments from 75 to 100 ℃.
In certain further preferred embodiments from 80 to 95 ℃.
In the method for producing a benzoxazine prepolymer according to the present invention, the reaction time is 1 to 24 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours.
In certain preferred embodiments from 3 to 20 hours.
In certain further preferred embodiments from 5 to 18 hours.
Further, in the method for preparing a benzoxazine prepolymer of the present invention as described above, the method further comprises a step of washing the benzoxazine monomer.
The washing solvent is optionally selected from ethanol, methanol, petroleum ether or n-hexane.
Further, in the method for preparing the benzoxazine prepolymer of the present invention as described above, the method further comprises a step of vacuum-drying the benzoxazine monomer.
The drying temperature may be 50 to 90℃and may be, for example, 50℃55℃60℃65℃70℃75℃80℃85℃90 ℃.
The drying time is 6 to 24 hours, and may be, for example, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours.
The invention also provides a benzoxazine copolymer resin which is crosslinked by itself after the oxazine ring of the benzoxazine prepolymer shown in the formula (I) is opened; and
R 3 double bonds, triple bonds, cyano groups or cyclobutene in the groups are polymerized to form a crosslinked structure; or (b)
R 3 The ethoxy of the group and phenolic hydroxyl generated after oxazine ring opening generate dealcoholization condensation reaction to form Si-O-Ph bond crosslinking structure;
solidifying to obtain the final product.
In the invention, the benzoxazine copolymer resin has a double cross-linking structure, wherein one is a cross-linking structure formed by self-crosslinking after the oxazine ring of the benzoxazine prepolymer shown in the formula (I) is opened, and the other is R 3 The reactive functional groups in the groups react to generate another cross-linked structure, and the cross-linked density of the benzoxazine copolymer resin is improved due to the existence of the two cross-linked structures.
The invention further provides a method for preparing any benzoxazine copolymer resin, which comprises the steps of dissolving any benzoxazine prepolymer in a solvent, forming a film by a casting method, and thermally curing to obtain the benzoxazine copolymer resin.
The solvent may be any solvent used in the art including, but not limited to, toluene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, methylene chloride, chloroform, dioxane, or tetrahydrofuran.
The casting method (casting) is a molding method. Refers to a method of injecting a liquid monomer, resin or a mixture thereof into a mold and making it into an article without pressurization or with slight pressurization. The casting method used in the invention is a method commonly used in the field, and the benzoxazine copolymer resin is obtained by heating and thermally curing at the same time.
The invention further provides application of any benzoxazine copolymer resin in the fields of high-frequency high-speed circuit substrate materials, microwave and millimeter wave communication, vehicle-mounted radars, matrix resins of other composite materials and electronic packaging materials.
Examples
The invention is further illustrated by the following specific preparation examples.
The components and amounts of the examples are shown in the following Table
Example 1
Preparation of benzoxazine copolymer resins based on bisphenol A, 4' -diaminodiphenyl ether and allylamine
The specific synthesis steps are as follows:
6.31g of paraformaldehyde and 12.00g of bisphenol A are dissolved in 20mL of dioxane and the temperature is raised to 90 ℃. Then 5.26g of 4,4' -diaminodiphenyl ether was added dropwise and reacted for 3 hours. Finally, 3.00g of allylamine was added dropwise to react for 3 hours. Post-treatment: washing with alkali, washing with water, drying with anhydrous sodium sulfate to remove water, filtering, rotary evaporating the solvent to remove the solvent, and vacuum drying the product at 60 ℃ to obtain pale yellow powder with 89% yield.
The obtained benzoxazine prepolymer is BZP1, and the structural formula is
1 H NMR.(300MHz,DMSO-d6)δ7.23(s,4H),7.02(d,4H),6.79(d,4H),6.73(d,4H),6.68(d,4H),5.85(m,2H),5.37(s,4H),5.15-5.19(m,4H),4.85(s,4H),4.63(s,4H),3.97(s,4H),3.03(d,4H),1.54(s,12H).
13 C NMR(75MHz,DMSO-d6)δ155.8,155.1,146.3,143.9,142.6,134.3,130.7,130.1,126.7,126.3,121.6,121.1,117.2,116.4,114.1,112.2,111.9,93.1,85.1,59.5,59.1,56.2,43.1,30.8.
LC-MS m/z:866.67[M+H] + .
Weighing 10.0g of the benzoxazine prepolymer, grinding, dissolving in dichloromethane, pouring into a polytetrafluoroethylene flat plate die, and carrying out gradient heating solidification, wherein the heating program is as follows: 150 ℃ (120 min), 180 ℃ (120 min), 200 ℃ (120 min), 220 ℃ (60 min) to obtain reddish brown bulk solid.
The Tg of the resulting copolymer resin was 230℃and the dielectric constant at 5GHz was 2.93, and the dielectric loss was 0.0065.
Example 2
Preparation of benzoxazine copolymer resins based on bisphenol fluorene, 4' -diaminodiphenyl ether and gamma-aminopropyl methyldiethoxysilane
The specific synthesis steps are as follows:
4.11g of paraformaldehyde and 12.00g of bisphenol fluorene were dissolved in 20mL of dioxane and heated to 90 ℃. Then 3.43g of 4,4' -diaminodiphenyl ether was added dropwise and reacted for 3 hours. Finally, 6.55g of gamma-aminopropyl methyl diethoxy silane is added dropwise for reaction for 3 hours. Post-treatment: washing with alkali, washing with water, drying with anhydrous sodium sulfate to remove water, filtering, rotary evaporating the solvent, and vacuum drying at 60deg.C to obtain pale yellow powder with 80% yield.
The obtained benzoxazine prepolymer is BZP2, and the structural formula is
1 H NMR(300MHz,DMSO-d6)δ7.91(d,4H),7.54(d,4H),7.39(t,4H),7.26(t,4H),7.20(s,4H),7.14(d,4H),6.79(d,4H),6.70(d,4H),6.68(d,4H),5.38(s,4H),4.86(s,4H),4.62(s,4H),3.96(s,4H),3.81(q,8H),2.45(t,4H),1.33(m,4H),1.20(t,12H),0.63(t,4H),0.12(s,6H).
13 C NMR(75MHz,DMSO-d6)δ155.8,154.9,143.9,142.5,141.8,141.1,139.6,130.7,130.1,128.5,127.9,127.3,126.5,126.0,121.8,121.1,116.2,114.1,112.0,92.9,85.0,63.4,59.8,58.3,56.1,53.0,27.1,18.6,16.8.
LC-MS m/z:1379.23[M+H] + .
Weighing 10.0g of the benzoxazine prepolymer, grinding, dissolving in dichloromethane, pouring into a polytetrafluoroethylene flat plate die, and carrying out gradient heating solidification, wherein the heating program is as follows: 150 ℃ (120 min), 180 ℃ (120 min), 200 ℃ (120 min), 220 ℃ (60 min) to obtain reddish brown bulk solid.
The Tg of the resulting copolymer resin was 250℃and the dielectric constant at 5GHz was 2.90, and the dielectric loss was 0.0071.
Example 3
Preparation of benzoxazine copolymer resins based on 4,4 '-dihydroxydiphenyl ether, 4' -diaminodiphenyl sulfide and gamma-aminopropyl methyldiethoxysilane
The specific synthesis steps are as follows:
7.12g of paraformaldehyde and 12.00g of 4,4' -dihydroxydiphenyl ether are dissolved in 20mL of dioxane and the temperature is raised to 90 ℃. Then, 6.42g of 4,4' -diaminodiphenyl sulfide was added dropwise and reacted for 3 hours. Finally, 11.36g of gamma-aminopropyl methyl diethoxy silane is added dropwise for reaction for 3h. Post-treatment: washing with alkali, washing with water, drying with anhydrous sodium sulfate to remove water, filtering, rotary evaporating the solvent to remove the solvent, and vacuum drying the product at 60 ℃ to obtain pale yellow powder with the yield of 83%.
The obtained benzoxazine prepolymer is BZP3, and the structural formula is
1 H NMR(300MHz,DMSO-d6)δ7.28(d,4H),7.05(d,4H),7.00(s,4H),6.94(d,4H),6.54(d,4H),5.37(s,4H),4.85(s,4H),4.63(s,4H),3.97(s,4H),3.85(q,8H),2.45(t,4H),1.36(m,4H),1.20(t,12H),0.60(t,4H),0.15(s,6H).
13 C NMR(75MHz,DMSO-d6)δ151.4,150.5,149.2,149.1,148.0,128.8,125.0,121.6,120.9,120.7,117.2,116.1,114.4,114.2,110.8,110.6,92.8,85.1,59.6,58.5,56.1,53.0,27.1,18.5,16.7.
LC-MS m/z:1098.99[M+H] + .
Weighing 10.0g of the benzoxazine prepolymer, grinding, dissolving in dichloromethane, pouring into a polytetrafluoroethylene flat plate die, and carrying out gradient heating solidification, wherein the heating program is as follows: 150 ℃ (120 min), 180 ℃ (120 min), 200 ℃ (120 min), 220 ℃ (60 min) to obtain reddish brown bulk solid.
The Tg of the resulting copolymer resin was 240℃and the dielectric constant at 5GHz was 2.78, and the dielectric loss was 0.0061.
Example 4
Preparation of benzoxazine copolymer resins based on dicyclopentadiene diphenol, 4' -diaminodiphenyl sulfide and allylamine
The specific synthesis steps are as follows:
4.49g of paraformaldehyde and 12.00g of 4,4' -dicyclopentadiene diphenol are dissolved in 20mL of dioxane, and the temperature is raised to 90 ℃. 4.05g of 4,4' -diaminodiphenyl sulfide were then added dropwise and reacted for 3 hours. Finally, 2.14g of allylamine was added dropwise to react for 3 hours. Post-treatment: washing with alkali, washing with water, drying with anhydrous sodium sulfate to remove water, filtering, rotary evaporating the solvent to remove the solvent, and vacuum drying the product at 60 ℃ to obtain pale yellow powder with the yield of 88%.
The obtained benzoxazine prepolymer is BZP4, and the structural formula is
1 H NMR(300MHz,DMSO-d6)δ7.35(d,4H),7.33(s,4H),7.05(d,4H),6.77(d,4H),6.54(d,4H),5.82(m,2H),5.38(s,4H),5.16-5.20(m,4H),4.84(s,4H),4.60(s,4H),3.96(s,4H),3.01(d,4H),2.77(m,2H),2.63(q,2H),1.62-2.14(m,20H),1.15(m,4H).
13 C NMR(75MHz,DMSO-d6)δ155.7,154.5,148.3,141.5,136.6,134.3,129.3,128.7,128.3,126.3,126.1,125.1,121.2,121.0,120.2,117.5,111.3,93.1,85.2,59.6,59.1,56.4,47.0,46.3,45.1,43.3,42.0,40.6,39.2,38.9,34.8,33.6.
LC-MS m/z:1066.93[M+H] + .
Weighing 10.0g of the benzoxazine prepolymer, grinding, dissolving in dichloromethane, pouring into a polytetrafluoroethylene flat plate die, and carrying out gradient heating solidification, wherein the heating program is as follows: 150 ℃ (120 min), 180 ℃ (120 min), 200 ℃ (120 min), 220 ℃ (60 min) to obtain reddish brown bulk solid.
The Tg of the resulting copolymer resin was 220℃and the dielectric constant at 5GHz was 2.81, and the dielectric loss was 0.0060.
Example 5
Preparation of benzoxazine copolymer resins based on bisphenol A, 4' -diaminobiphenyl and gamma-aminopropyl methyldiethoxysilane
The specific synthesis steps are as follows:
6.31g of paraformaldehyde and 12.00g of bisphenol A are dissolved in 20mL of dioxane and the temperature is raised to 90 ℃. 4.84g of 4,4' -diaminobiphenyl were then added dropwise and reacted for 3 hours. Finally, 10.06g of gamma-aminopropyl methyl diethoxy silane is added dropwise for reaction for 3h. Post-treatment: washing with alkali, washing with water, drying with anhydrous sodium sulfate to remove water, filtering, rotary evaporating the solvent to remove the solvent, and vacuum drying the product at 60 ℃ to obtain pale yellow powder with the yield of 85%.
The benzoxazine prepolymer is BZP5 and has the structural formula of
1 H NMR(300MHz,DMSO-d6)δ7.42(d,4H),7.20(s,4H),7.02(d,4H),6.91(d,4H),6.79(d,4H),5.39(s,4H),4.83(s,4H),4.62(s,4H),3.96(s,4H),3.81(q,8H),2.47(t,4H),1.54(s,12H),1.33(m,4H),1.22(t,12H),0.62(t,4H),0.13(s,6H).
13 C NMR(75MHz,DMSO-d6)δ155.7,155.1,148.3,146.2,146.1,133.2,130.8,130.1,128.7,126.5,126.3,121.6,121.1,112.5,112.0,111.9,93.1,85.1,59.5,58.6,56.1,53.0,43.2,30.7,27.1,18.6,16.7.
LC-MS m/z:1119.00[M+H] + .
Weighing 10.0g of the benzoxazine prepolymer, grinding, dissolving in dichloromethane, pouring into a polytetrafluoroethylene flat plate die, and carrying out gradient heating solidification, wherein the heating program is as follows: 150 ℃ (120 min), 180 ℃ (120 min), 200 ℃ (120 min), 220 ℃ (60 min) to obtain reddish brown bulk solid.
The Tg of the resulting copolymer resin was 245℃and the dielectric constant at 5GHz was 2.87, and the dielectric loss was 0.0069.
Compared with the glass transition temperature (180 ℃) and the high-frequency dielectric loss (0.025 at 5 GHz) of the common benzoxazine resin, the benzoxazine copolymer resin in the embodiment of the invention has higher glass transition temperature (more than or equal to 220 ℃) and lower high-frequency dielectric loss (less than or equal to 0.0071). They are therefore more suitable for applications where high heat resistance and low loss are required, such as: high frequency high speed circuit substrate material, microwave and millimeter wave communication, vehicle radar, electronic packaging material, etc.
The foregoing merely illustrates the principles of the invention, it being understood that the scope of the invention is not intended to be limited to the exemplary aspects described herein, but rather to include all equivalents that are presently known and that are developed in the future. In addition, it should be noted that several improvements and modifications may be made without departing from the technical principle of the present invention, and these improvements and modifications should also be considered as the scope of the present invention.
Claims (18)
1. A benzoxazine prepolymer characterized by the following structure:
。
2.a method of preparing the benzoxazine prepolymer of claim 1, comprising the steps of:
the benzoxazine prepolymer according to claim 1 is prepared by reacting a dihydric phenol compound, a diamine compound, and a monoamine compound containing an active functional group in the presence of an aldehyde compound and a solvent, wherein the dihydric phenol compound is bisphenol a, the diamine compound is 4,4' -diaminobiphenyl, the monoamine compound is diethoxymethyl aminopropyl silane, and the aldehyde compound is formaldehyde or paraformaldehyde.
3. The method according to claim 2, wherein the aldehyde compound is an aqueous formaldehyde solution or paraformaldehyde having a mass concentration of 37%.
4. The method of claim 2, wherein the solvent is water, ethanol, tetrahydrofuran, acetone, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, dioxane, chloroform, or toluene.
5. The process according to claim 2, wherein the composition comprises, in parts by weight,
30-80 parts of dihydric phenol compound, 15-40 parts of diamine compound, 15-40 parts of monoamine compound, 20-50 parts of aldehyde compound and 40-100 parts of solvent.
6. The method according to claim 2, wherein the dihydric phenol compound is 40 to 80 parts, the diamine compound is 20 to 40 parts, the monoamine compound is 20 to 40 parts, the aldehyde compound is 30 to 50 parts, and the solvent is 70 to 95 parts.
7. The process according to claim 2, wherein the reaction temperature is 50 to 110 ℃.
8. The process according to claim 2, wherein the reaction temperature is 75 to 100 ℃.
9. The process according to claim 2, wherein the reaction temperature is 80 to 95 ℃.
10. The process according to claim 2, wherein the reaction time is 1 to 24 hours.
11. The process according to claim 2, wherein the reaction time is 3 to 20 hours.
12. The process according to claim 2, wherein the reaction time is 5 to 18 hours.
13. The preparation method according to claim 2, further comprising the step of washing the benzoxazine prepolymer by the following method,
the prepared benzoxazine prepolymer is washed by ethanol, methanol, petroleum ether or n-hexane.
14. The preparation method according to claim 2, further comprising a step of vacuum-drying the benzoxazine prepolymer at a temperature of 50 to 90 ℃ for a time of 6 to 24 hours.
15. A benzoxazine copolymer resin characterized by self-crosslinking after ring opening from the oxazine ring of the benzoxazine prepolymer according to claim 1; and
the ethoxy of methyl aminopropyl silane group and phenolic hydroxyl generated after oxazine ring opening generate dealcoholization condensation reaction to form Si-O-Ph bond crosslinking structure; solidifying to obtain the final product.
16. A method of preparing the benzoxazine-based copolymer resin according to claim 15, comprising the steps of:
the benzoxazine prepolymer according to claim 1 is dissolved in a solvent, formed into a film by a casting method, and thermally cured to obtain the benzoxazine copolymer resin.
17. The method of claim 16, wherein the solvent is toluene, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, dichloromethane, chloroform, dioxane, or tetrahydrofuran.
18. The use of the benzoxazine copolymer resin according to claim 15 in the fields of high frequency high speed circuit substrate materials, microwave and millimeter wave communications, vehicle radar and other composite matrix resins and electronic packaging materials.
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