CN103865066A - Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer - Google Patents
Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer Download PDFInfo
- Publication number
- CN103865066A CN103865066A CN201410081245.1A CN201410081245A CN103865066A CN 103865066 A CN103865066 A CN 103865066A CN 201410081245 A CN201410081245 A CN 201410081245A CN 103865066 A CN103865066 A CN 103865066A
- Authority
- CN
- China
- Prior art keywords
- polymkeric substance
- formula
- preparation
- another preference
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title abstract description 3
- CVBYFTWZGHDVHC-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-4-(2,2,3,3,4,4-hexafluorocyclobutyl)oxycyclobutane Chemical compound FC1(C(C(C1OC1C(C(C1(F)F)(F)F)(F)F)(F)F)(F)F)F CVBYFTWZGHDVHC-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- -1 trifluoro vinyl Chemical group 0.000 claims description 24
- 239000003880 polar aprotic solvent Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 150000001282 organosilanes Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 9
- JLGADZLAECENGR-UHFFFAOYSA-N 1,1-dibromo-1,2,2,2-tetrafluoroethane Chemical compound FC(F)(F)C(F)(Br)Br JLGADZLAECENGR-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 238000003379 elimination reaction Methods 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 230000035484 reaction time Effects 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229960001701 chloroform Drugs 0.000 description 9
- 125000005375 organosiloxane group Chemical group 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 239000003989 dielectric material Substances 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229940090668 parachlorophenol Drugs 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 0 *c(cc1)ccc1OC(F)(F)Br=C Chemical compound *c(cc1)ccc1OC(F)(F)Br=C 0.000 description 2
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- KVBKAPANDHPRDG-UHFFFAOYSA-N dibromotetrafluoroethane Chemical compound FC(F)(Br)C(F)(F)Br KVBKAPANDHPRDG-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YGHMOOKDWGSWJI-UHFFFAOYSA-N Cc(cc1)ccc1OC(F)=C(F)F Chemical compound Cc(cc1)ccc1OC(F)=C(F)F YGHMOOKDWGSWJI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- 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
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as a preparation and application of the low-dielectric-constant polymer and particularly provides a polymer prepared by heating and curing a polymer represented by a formula I as well as a preparation method and an application of the polymer. The polymer has good electrical properties and heat resistance, is simple in preparation method and is applied to an encapsulating material taken as an insulation coating layer and an electronic component in electronic and electrical industries.
Description
Technical field
The invention belongs to high-performance polymer manufacturing technology field, particularly, the present invention relates to the low dielectric constant polymer containing hexafluoro cyclobutyl ether and siloxanes of a kind of mechanical property excellence, low water absorption and low-k, and its preparation method and application.
Background technology
Traditionally, the interlayer dielectric materials in unicircuit adopts silicon-dioxide or silicone based material.Although these materials have very high thermostability and thermomechanical property, its specific inductivity, often higher than 3.0, can not meet the requirement of high-frequency communication equipment.Polyimide-type materials is good because of thermotolerance, by pore-creating, can obtain the film that specific inductivity is lower, as the substitute of silicon-dioxide and be widely used.But, the second-order transition temperature of common polyimide is often lower than the processing temperature of surface-mounted integrated circuit, and this material easily carries out ordered arrangement along metal or silicon face in film process, thereby make polyimide dielectric materials there is anisotropy, comprising the anisotropy of thermal conduction, resistance to shearing resistance and dielectric properties.Therefore, industrial sector and institute have further developed many organic polymer class dielectric materials.But, the common thermostability deficiency of these materials, poor with the surface adhesion of metal or silicon.Along with the development of microelectronics industry, the production of 90 nano chips based on copper interconnection technology proposes many demands to material industry, and above-described pure siliceous and organic polymer will face the situation being eliminated gradually.The most pressing problem that people face is need to develop and not only have low-k but also have high stable on heating material.
Poly-hexafluoro cyclobutyl arylene ethers material has excellent thermotolerance and photoelectric properties because of it, and from the nineties in 20th century, people are just studied it.So far, owing to thering is higher transmission efficiency and minimum light loss, they by abundant exploitation as organic light-guide material (referring to Macromolecules2004,37,5724 and Macromolecules2005,38,8278).On the other hand, because C-F key has less polarizable rate, contain trifluoro vinyl ether structure as performed polymer taking three-functionality-degree, preparing by hot setting thermosetting resin that main chain contains hexafluoro cyclobutyl arylene ether functional group has been developed and has been used as advanced low-k materials and (seen Mat.Res.Soc.Symp.Proc.1997,443,177).In recent years, come from the perfluorocyclobutane base aryl ethers (polyperfluorocyclobutane of tetrafluoroethylene, PFCB) base polymer is subject to people's great attention, reason is, this base polymer not only cost is relatively low, and has excellent electric property and low rate of moisture absorption (seeing WO9015043).But, thermostability and the adhesive property deficiency based on the organic framework structured dielectric materials of PFCB completely.Therefore it is necessary, being devoted to improve and eliminating these defects.
Summary of the invention
The object of this invention is to provide the organic framework structured dielectric materials of PFCB that a kind of thermostability and adhesive property improve.
A first aspect of the present invention, provides a kind of suc as formula the polymkeric substance shown in I:
In formula, n >=2; Preferably, n=5～100; More preferably, n=10～20.
In another preference, described formula I polymkeric substance is liquid, is preferably colourless thick liquid.
In another preference, the number-average molecular weight of described polymkeric substance is 2,300～4,600.
In another preference, the weight-average molecular weight of described polymkeric substance is 4,300～8,600.
In another preference, described formula I polymkeric substance can be heating and curing, and preferably, the solidification value of described formula I polymkeric substance is 150 DEG C～250 DEG C.
A second aspect of the present invention, a kind of preparation method of the formula I polymkeric substance as described in first aspect present invention is provided, described method comprises step: in inert solvent, use as shown in the formula shown in II containing the organosilane monomer of the trifluoro vinyl ether unit polyreaction that is hydrolyzed, obtain formula I polymkeric substance;
Wherein, R is selected from lower group: C1-C4 alkyl; The definition of n is as noted before.
In another preference, described hydrolytic-polymeric reaction is carried out in the solvent that is selected from lower group: benzene,toluene,xylene, or its combination.
In another preference, the temperature of reaction of described hydrolytic-polymeric reaction is 0-100 DEG C.
In another preference, the described hydrolytic-polymeric reaction time is 5～36 hours.
In another preference, the described hydrolytic-polymeric reaction time is 12～36 hours.
In another preference, described hydrolytic-polymeric reaction an acidic catalyst and/or water carry out under existing.
In another preference, described an acidic catalyst is selected from lower group: hydrochloric acid, sulfuric acid, acetic acid, formic acid, or its combination.
In another preference, in described hydrolytic-polymeric reaction, the mol ratio of the organosilane monomer shown in water, an acidic catalyst and formula II is 50～100:1～10:1～10.
In another preference, the organosilane monomer shown in described formula II is prepared by following step:
(1) in polar aprotic solvent, under basic catalyst exists, use halogenated phenol is reacted under room temperature with tetrafluorodibromoethane, prepare 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-halogeno-benzene;
(2) in polar aprotic solvent, described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene is carried out to elimination reaction, obtain 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene;
(3), in polar aprotic solvent, with methyl trialkoxysilane and the reaction of 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene, obtain suc as formula the organosilane monomer shown in II;
Above-mentioned various in, X is halogen; R is selected from lower group: C1-C4 alkyl.
In another preference, in described step (1), described basic catalyst is selected from lower group: salt of wormwood, potassium hydroxide, or its combination.
In another preference, in described step (1), described polar aprotic solvent is selected from lower group: N-Methyl pyrrolidone, DMSO, or its combination.
In another preference, in described step (1), described is selected from lower group to halogenated phenol: p bromophenol, para-chlorophenol, or its combination.
In another preference, in described step (1), the described reaction times is 5～30 hours.
In another preference, in described step (1), described is 1:1～10 to the mol ratio of halogenated phenol and tetrafluorodibromoethane.
In another preference, in described step (2), described polar aprotic solvent is acetonitrile.
In another preference, in described step (2), described elimination reaction is carried out under existing at zinc powder.
In another preference, in described step (2), the described reaction times is 5～30 hours.
In another preference, in described step (2), the mol ratio of described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene and zinc powder is 1:1～5.
In another preference, in described step (3), described polar aprotic solvent is selected from lower group: tetrahydrofuran (THF), ether, or its combination.
In another preference, in described step (3), described reaction is carried out under magnesium chips exists.
In another preference, in described step (3), the alkoxyl group that described alkoxyl group is C1-C4, preferably, described alkoxyl group is selected from lower group: methoxy or ethoxy.
In another preference, in described step (3), described 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene adds in the following manner: after being formulated as tetrahydrofuran solution, drip.
In another preference, in described step (3), the described reaction times is 12～36 hours.
In another preference, in described step (3), described temperature of reaction is 0-50 DEG C.
A third aspect of the present invention, provides a kind of formula I polymkeric substance as described in first aspect present invention for being heating and curing, thereby prepares the purposes of cure polymer.
In another preference, the described temperature that is heating and curing is 150 DEG C～250 DEG C.
A fourth aspect of the present invention, provides a kind of polymkeric substance, and described polymkeric substance is to use suc as formula the polymkeric substance described in I to be cured preparation: preferably, described being cured as is heating and curing.
In another preference, described polymkeric substance has the structure as shown in formula III:
In formula, m is positive integer, and m≤n.
In another preference, described polymkeric substance (final cured product) Si-PFCB is crosslinked reticulated structure.
In another preference, described polymkeric substance has following one or more features:
The specific inductivity of described polymkeric substance is≤2.5, is preferably≤2.4 (measuring under 30MHz);
Under nitrogen atmosphere, 5% heat decomposition temperature of described polymkeric substance is >=450 DEG C, is preferably >=470 DEG C;
The hardness of described polymkeric substance is >=0.35GPa to be preferably >=0.38GPa;
The Young's modulus of described polymkeric substance is >=8.00GPa, is preferably >=9.00GPa to be more preferably >=10.00GPa;
The bonding strength of described polymkeric substance and silicon chip is >=4.5GPa, is preferably >=4.8GPa to be more preferably >=4.90GPa.
A fifth aspect of the present invention, provides a kind of preparation method of the polymkeric substance as described in fourth aspect present invention, and described polymkeric substance is prepared by the following method: heating is suc as formula the polymkeric substance shown in I, thereby obtains the polymkeric substance as described in fourth aspect present invention.
In another preference, the temperature range of described heating is 150～250 DEG C.
A sixth aspect of the present invention, a kind of goods are provided, described goods contain just like the formula I polymkeric substance described in first aspect present invention or the polymkeric substance as described in fourth aspect present invention, or described goods are to use the formula I polymkeric substance as described in first aspect present invention or the polymkeric substance as described in fourth aspect present invention to prepare.
In another preference, described goods are selected from lower group: advanced low-k materials, plain conductor outer cladding insulating material, polymer sheet, polymeric film.
In another preference, the attach most importance to polymeric film of doped silicon wafer-as described in fourth aspect present invention of described goods.
In another preference, described goods are the polymer composites of glass fibre-as described in fourth aspect present invention.
In another preference, described goods are printed circuit board (PCB).
In another preference, described goods are polymer sheet or the polymeric film that contains the polymkeric substance described in fourth aspect present invention, and described goods are prepared by the following method:
Carry out room temperature mold pressing with the formula I polymkeric substance described in first aspect present invention and obtain the sheet material that contains formula I polymkeric substance; Or with formula I polymkeric substance described in organic solvent dissolution and carry out film forming, obtain the film that contains formula I polymkeric substance;
Above-mentioned polymer sheet or polymeric film are heating and curing, obtain containing polymer sheet or polymeric film just like the polymkeric substance described in fourth aspect present invention.
In another preference, described film-forming process is spin-coating film or drips painting film forming.
In another preference, described organic solvent is toluene, dimethylbenzene, trimethylbenzene, phenyl ether, pimelinketone, trichloromethane, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, or its combination.
A seventh aspect of the present invention, provides a kind of as shown in the formula the organosilane monomer shown in II:
Wherein, R is selected from lower group: C1-C4 alkyl.
A eighth aspect of the present invention, provides a kind of preparation method of the organosilane monomer as described in seventh aspect present invention, prepares by following step:
(1) in polar aprotic solvent, under basic catalyst exists, use halogenated phenol is reacted under room temperature with tetrafluorodibromoethane, prepare 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-halogeno-benzene;
(2) in polar aprotic solvent, described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene is carried out to elimination reaction, obtain 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene;
(3), in polar aprotic solvent, with methyl trialkoxysilane and the reaction of 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene, obtain suc as formula the organosilane monomer shown in II;
Above-mentioned various in, X is halogen; R is selected from lower group: C1-C4 alkyl.
In another preference, in described step (1), described basic catalyst is selected from lower group: salt of wormwood, potassium hydroxide, or its combination.
In another preference, in described step (1), described polar aprotic solvent is selected from lower group: N-Methyl pyrrolidone, DMSO, or its combination.
In another preference, in described step (1), described is selected from lower group to halogenated phenol: p bromophenol, para-chlorophenol, or its combination.
In another preference, in described step (1), the described reaction times is 5～30 hours.
In another preference, in described step (1), described is 1:1～10 to the mol ratio of halogenated phenol and tetrafluorodibromoethane.
In another preference, in described step (2), described polar aprotic solvent is acetonitrile.
In another preference, in described step (2), described elimination reaction is carried out under existing at zinc powder.
In another preference, in described step (2), the described reaction times is 5～30 hours.
In another preference, in described step (2), the mol ratio of described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene and zinc powder is 1:1～5.
In another preference, in described step (3), described polar aprotic solvent is selected from lower group: tetrahydrofuran (THF), ether, or its combination.
In another preference, in described step (3), described reaction is carried out under magnesium chips exists.
In another preference, in described step (3), the alkoxyl group that described alkoxyl group is C1-C4, preferably, described alkoxyl group is selected from lower group: methoxy or ethoxy.
In another preference, in described step (3), described 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene adds in the following manner: after being formulated as tetrahydrofuran solution, drip.
In another preference, in described step (3), the described reaction times is 12～36 hours.
In another preference, in described step (3), described temperature of reaction is 0-50 DEG C.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can combining mutually between specifically described each technical characterictic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tire out and state no longer one by one at this.
Embodiment
Long-term and the deep research of inventor's process is found, contains the organo-siloxane of trifluoro vinyl ether functional group after hydrolysis, and the prepolymer obtaining, through direct hot setting, can obtain a kind of organo-siloxane material of novel structure.Described material has good electric property, thermostability and adhesive property, is suitable as a kind of high-performance coating and packaged material of high heat-resisting, low-k, is applied to the fields such as microelectronics industry, aerospace and national defence.Based on above-mentioned discovery, contriver has completed the present invention.
Term
As used herein, term " cured product of formula II polymkeric substance ", " Si-PFCB polymkeric substance of the present invention " or " containing the low dielectric constant polymer of hexafluoro cyclobutyl ether and organo-siloxane " all refer to that a kind of preferably structure is as shown in formula III with the formula II polymkeric substance of the present invention prepared polymkeric substance that is heating and curing:
Unless stated otherwise, term " halo " refers to that the one or more hydrogen atoms on group are replaced by halogen atom, and wherein, described halogen atom is selected from lower group: fluorine, chlorine, bromine, iodine.
Term " C1-C4 alkyl " refers to have the straight or branched alkyl of 1～4 carbon atom, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or similar group.
Term " C1-C4 alkoxyl group " refers to have the straight or branched alkoxyl group of 1-4 carbon atom, for example methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert.-butoxy or similar group.
Flucride siloxane performed polymer
The invention provides a kind of can be for the preparation of the performed polymer of the low dielectric constant polymer containing hexafluoro cyclobutyl ether and organo-siloxane, described performed polymer is suc as formula shown in I:
In formula, n >=2; Preferably, n=5～100; More preferably, n=10～20.
In another preference, the number-average molecular weight of described polymkeric substance is 2,300～4,600.
In another preference, the weight-average molecular weight of described polymkeric substance is 4,300～8,600.
In preference of the present invention, described formula I polymkeric substance can for example, be hydrolyzed polymerization preparation of monomer:
In inert solvent, use as shown in the formula shown in II containing the organosilane monomer of the trifluoro vinyl ether unit polyreaction that is hydrolyzed, obtain formula I polymkeric substance;
Wherein, R is selected from lower group: C1-C4 alkyl; N >=2; Preferably, n=5～100; More preferably, n=10～20.
In another preference, described hydrolytic-polymeric reaction is carried out in the solvent that is selected from lower group: benzene,toluene,xylene, or its combination.
The temperature of reaction of described hydrolytic-polymeric reaction is not particularly limited, for example can be under the reflux temperature of solvent, or carry out under the boiling point of ROH.In preference of the present invention, described temperature of reaction is 0-100 DEG C, is preferably 4-95 DEG C.
In another preference, the described hydrolytic-polymeric reaction time is 5～20 hours.
Described hydrolytic-polymeric reaction can be carried out under catalyzer exists, and for example, in a preference of the present invention, described reaction is carried out under an acidic catalyst and/or water existence.Wherein, described an acidic catalyst comprises that (but being not limited to) is selected from the acid of lower group: hydrochloric acid, sulfuric acid, acetic acid, formic acid, or its combination.
In another preference, in described hydrolytic-polymeric reaction, the mol ratio of the organosilane monomer shown in water, an acidic catalyst and formula II is 50～100:5～10:1.
Organosilane monomer shown in described formula II can, by the ordinary method preparation of this area, for example, can be prepared by following step:
(1) in polar aprotic solvent, under basic catalyst exists, use halogenated phenol is reacted under room temperature with tetrafluorodibromoethane, prepare 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-halogeno-benzene;
In another preference, in described step (1), described basic catalyst is selected from lower group: salt of wormwood, potassium hydroxide, or its combination.
In another preference, in described step (1), described polar aprotic solvent is selected from lower group: N-Methyl pyrrolidone, DMSO, or its combination.
In another preference, in described step (1), described is selected from lower group to halogenated phenol: p bromophenol, para-chlorophenol, or its combination.
The reaction times of described step (1) is not particularly limited, and can determine reaction end by TLC method, and in a preference of the present invention, the described reaction times is 10～30 hours.
In another preference, in described step (1), described is 1:1～10 to the mol ratio of halogenated phenol and tetrafluorodibromoethane.
(2) in polar aprotic solvent, described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene is carried out to elimination reaction, obtain 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene;
Wherein, described polar aprotic solvent is not particularly limited, and can be preferably acetonitrile.
Described elimination reaction can be in optional catalyst condition, or carries out under the reaction conditions of any appropriate, for example, can under zinc powder effect, carry out.
The reaction times of described step (2) is not particularly limited, and can determine reaction end by TLC method, and in a preference of the present invention, the described reaction times is 5～30 hours.
In another preference, in described step (2), the mol ratio of described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene and zinc powder is 1:1～5.
(3), in polar aprotic solvent, with methyl trialkoxysilane and the reaction of 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene, obtain suc as formula the organosilane monomer shown in II.
In another preference, in described step (3), described polar aprotic solvent is selected from lower group: tetrahydrofuran (THF), ether, or its combination.
In another preference, in described step (3), described reaction is carried out under magnesium chips exists.
In another preference, in described step (3), the alkoxyl group that described alkoxyl group is C1-C4, preferably, described alkoxyl group is selected from lower group: methoxy or ethoxy.
In another preference, in described step (3), described 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene adds in the following manner: after being formulated as tetrahydrofuran solution, drip.
In another preference, in described step (3), the described reaction times is 12～36 hours.
In another preference, in described step (3), described temperature of reaction is 0-50 DEG C.
In another preference, in described step (3), the mol ratio of described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene and zinc powder is 1:1～5.
Described formula I polymkeric substance (or performed polymer) can be heating and curing, thereby preparation contains the low dielectric constant polymer of hexafluoro cyclobutyl ether and organo-siloxane, and a kind of preferred described polymkeric substance is the polymkeric substance as shown in formula III.
Containing the low dielectric constant polymer of hexafluoro cyclobutyl ether and organo-siloxane
Based on organosilyl high heat resistance, workability and with the good adhesion of silicon chip, and the low-dielectric energy of hexafluoro cyclobutyl arylene ether, as both are combined, can obtain good heat resistance, the good advanced low-k materials of mechanical property in theory.The present invention is the present Research based on above-mentioned dielectric materials just, from molecular design theory, hexafluoro cyclobutyl arylene ether and organo-siloxane is combined to the heat cured material of acquisition.
Particularly, the invention provides the above-mentioned formula I polymkeric substance of one and be heating and curing, thus the polymkeric substance (being Si-PFCB polymkeric substance of the present invention) of preparation.A kind of structure of preferred described polymkeric substance is as shown in formula III:
In formula, m is positive integer, and m≤n.
In the preferred embodiment of the present invention, Si-PFCB polymkeric substance of the present invention is crosslinked reticulated structure.
In another preference, described polymkeric substance has following one or more features:
The specific inductivity of described polymkeric substance is≤2.5, is preferably≤2.4 (measuring under 30MHz);
Under nitrogen atmosphere, 5% heat decomposition temperature of described polymkeric substance is >=450 DEG C, is preferably >=470 DEG C;
The hardness of described polymkeric substance is >=0.35GPa to be preferably >=0.38GPa;
The Young's modulus of described polymkeric substance is >=8.00GPa, is preferably >=9.00GPa to be more preferably >=10.00GPa;
The bonding strength of described polymkeric substance and silicon chip is >=4.5GPa, is preferably >=4.8GPa to be more preferably >=4.90GPa.
In the present invention, preferably preparation by the following method of described polymkeric substance:
Heat suc as formula the polymkeric substance shown in I, thereby obtain Si-PFCB polymkeric substance of the present invention.Prepare Si-PFCB polymkeric substance of the present invention with aforesaid method, there is preparation method simple, the feature of the polymer performance excellence making.
The condition of described heating has no particular limits, and preferably, is heating at 150～250 DEG C in temperature range.
Contain the application of the low dielectric constant polymer of hexafluoro cyclobutyl ether and organo-siloxane
Polymkeric substance described in formula I polymkeric substance and fourth aspect present invention described in first aspect present invention can be for the preparation of a series of goods, in another preference, described goods are selected from lower group: advanced low-k materials, plain conductor outer cladding insulating material, polymer sheet, polymeric film.
Wherein, the preferred goods of one class are the goods that contain Si-PFCB polymkeric substance of the present invention, and described goods are preparation by the following method preferably: carry out moulding with formula I polymkeric substance, obtain preform, then described preform is heating and curing, obtains the goods that contain Si-PFCB polymkeric substance of the present invention.
In a preference of the present invention, the described goods that contain Si-PFCB polymkeric substance of the present invention are polymer sheet or polymeric film, and described goods are to prepare by the following method
Carry out room temperature mold pressing with formula I polymkeric substance and obtain polymer sheet; Or with formula I polymkeric substance described in organic solvent dissolution and carry out film forming and obtain polymeric film, then described polymer sheet or polymeric film are heating and curing, obtain the polymer sheet or the polymeric film that contain Si-PFCB polymkeric substance of the present invention.
In another preference, described film-forming process is spin-coating film or drips painting film forming.
In another preference, described organic solvent is toluene, dimethylbenzene, trimethylbenzene, phenyl ether, pimelinketone, trichloromethane, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, or its combination.
Major advantage of the present invention comprises:
(1) Si-PFCB polymkeric substance provided by the invention has good electric property and thermotolerance, in a preference of the present invention, prepared Si-PFCB polymkeric substance of the present invention has low 2.33 the specific inductivity (30MHz) that reaches, 5% heat decomposition temperature reaches 471 DEG C, hardness is 0.392GPa, Young's modulus is 10.06GPa, with the bonding strength of silicon chip be 4.93GPa.
(2) the synthetic cost of dielectric materials provided by the present invention is lower, preparation process is simple, can be used as high performance electronic packaging material or plain conductor coating that a class has superior heat-stability, low water absorption and low-k, be applied to the field such as microelectronics processing industry and large electric manufacturing.
(3) performed polymer provided by the present invention can be used for preparing the polymkeric substance with good electric property, resistance toheat and mechanical property, and preparation method is simple, is applicable to suitability for industrialized production.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
The preparation of embodiment 1 intermediate 14-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-bromobenzene
Under argon shield, in reaction unit, add 51.9 grams of bromo-phenol of 4-(0.3mol), 147 gram 1, 2-dibromotetrafluoroethane (0.57mol) and 300 milliliters of existing DMSO (dimethyl sulfoxide (DMSO)) that steam, under ice-water bath, stir 30 minutes, then add 80 grams of Anhydrous potassium carbonates (0.6mol), remove ice-water bath, room temperature reaction 6 hours, reaction mixture is poured into water, vigorous stirring 20 minutes, with chloroform, product is extracted in batches, extraction liquid revolves after washing with saturated sodium-chloride water solution to steam removes chloroform, concentrated solution rectifying is collected 65 DEG C/0.23mmHg component and is obtained 98 grams of products, yield 93%.226～246 DEG C of atmospheric boiling points, hydrogen stave levy (
1h NMR, 300MHz, CDCl
3, δ in ppm): 7.51～7.53 (d, 2H), 7.11～7.13 (d, 2H); Fluorine stave levy (
19f NMR, 282MHz, CDCl
3, δ in ppm) :-86.2, (dt, 2F)-68.2 (dt, 2F).
The preparation of embodiment 2 intermediate 14-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-bromobenzene
Under argon shield, in reaction unit, add 51.9 grams of bromo-phenol of 4-(0.3mol), 147 gram 1, 2-dibromotetrafluoroethane (0.57mol) and 300 milliliters of existing N-Methyl pyrrolidone that steam, under ice-water bath, stir 30 minutes, then add 33.6 grams of potassium hydroxide (0.6mol), remove ice-water bath, room temperature reaction 6 hours, reaction mixture is poured into water, vigorous stirring 20 minutes, with chloroform, product is extracted in batches, extraction liquid revolves after washing with saturated sodium-chloride water solution to steam removes chloroform, concentrated solution rectifying is collected 65 DEG C/0.23mmHg component and is obtained 84 grams of products, yield 80%.246～256 DEG C of atmospheric boiling points, hydrogen stave levy (
1h NMR, 300MHz, CDCl
3, δ in ppm): 7.51～7.53 (d, 2H), 7.11～7.13 (d, 2H); Fluorine stave levy (
19f NMR, 282MHz, CDCl
3, δ in ppm) :-86.2, (dt, 2F)-68.2 (dt, 2F).
The preparation of embodiment 3 intermediate 2:4-(1,2,2-trifluoro-ethylene oxygen base)-1-bromobenzene
Under argon shield, the 76 grams of 4-(2-bromo-1,1 that adds embodiment 2 to obtain in reaction flask; 2,2-tetrafluoro oxyethyl group)-1-bromobenzene (0.22mol), 480 milliliters of new acetonitriles that steam; agitation and dilution, adds 30 grams of zinc powders (0.5mol), temperature rising reflux reaction 24 hours.Reaction solution is poured in 600 ml waters, stirred more than 15 minutes, use in batches chloroform extraction, combined chloroform extraction liquid, with saturated sodium-chloride water solution washing, anhydrous sodium sulfate drying is more than 12 hours.Revolve to steam and remove chloroform, concentrated solution rectifying is collected 56.2 DEG C/0.6mmHg component and is obtained 43.8 grams of products, yield 61%.Product atmospheric boiling point is 242～252 DEG C, hydrogen stave levy (
1h NMR, 300MHz, CDCl
3, δ in ppm): 7.47～7.49 (d, 2H), 6.99～7.01 (d, 2H); Fluorine stave levy (
19f NMR, 282MHz, CDCl
3, δ in ppm) :-134.2～-134.7 (dd, 1F) ,-126.4～-125.8 (dd, 1F) ,-119.4～-119.0 (dd, 1F).
The preparation of embodiment 4 monomer 4-(1,2,2-trifluoro-ethylene oxygen base)-1-(methyl diethoxy is silica-based)-benzene
Under argon shield; in reaction flask, add 64.2 grams of Union carbide A-162s (0.36mol) and 200 milliliters of new tetrahydrofuran (THF)s that steam; agitation and dilution; add 15 grams of magnesium chips; vigorous stirring under room temperature, the intermediate 24-(1,2 that dropwise adds 31 grams of embodiment 3 to obtain; 2-trifluoro-ethylene oxygen base)-1-bromobenzene, add at room temperature stirring reaction 24 hours of rear continuation.Revolve to steam and remove tetrahydrofuran (THF) and excessive Union carbide A-162, concentrated solution rectifying is collected 62.7 DEG C/0.6mmHg component and is obtained 23 grams of products, yield 59%.Product atmospheric boiling point is 258～262 DEG C, hydrogen stave levy (
1h NMR, 300MHz, CDCl
3, δ in ppm): 7.64～7.66 (d, 2H), 7.10～7.12 (d, 2H), 3.79～3.82 (q, 4H), 1.22～1.25 (t, 6H), 0.35 (s, 3H); Fluorine stave levy (
19f NMR, 282MHz, CDCl
3, δ in ppm) :-133.8～-134.2 (dd, 1F) ,-126.2～-126.7 (dd, 1F) ,-119.4～-119.9 (dd, 1F); Carbon stave levy (
13c NMR, 75MHz, CDCl
3, δ in ppm): 156.7,136.1,131.5,129.7,115.2,111.4,58.3,18.0 ,-4.4.
Embodiment 5 performed polymers gather the preparation of methyl-(1,2,2-trifluoro-ethylene oxygen base phenyl) siloxanes
Under argon shield; in reaction flask, add 72mL toluene; 36mL water; 12mL acetic acid (0.21mol); 13.8 grams of monomer 4-that obtained by embodiment 4 (methyl diethoxy is silica-based)-(1,2,2-trifluoro-ethylene oxygen base) benzene (45mmol); first at room temperature stir 4 hours, then slaking 5 hours at 85 DEG C.Separatory, be washed to neutrality, revolve and steam except desolventizing, quantitatively obtain product.Hydrogen stave levy (
1h NMR, 300MHz, CDCl
3, δ in ppm): 7.62～7.69 (m, 2H), 7.08～7.19 (m, 2H), 3.78～3.88 (m, 4H), 1.21～1.29 (m, 6H), 0.22～0.61 (m, 3H); Fluorine stave levy (
19f NMR, 282MHz, CDCl
3, δ in ppm) :-134.1～-133.5 (m, 1F) ,-125.6～-126.4 (m, 1F) ,-119.1～-119.6 (m, 1F).
Embodiment 6 performed polymers gather the preparation of methyl-(1,2,2-trifluoro-ethylene oxygen base phenyl) siloxanes
Under argon shield; in reaction flask, add 36mL toluene; 18mL water; 3mL concentrated hydrochloric acid (0.25mol); 6.9 grams of 4-that prepared by embodiment 4 (methyl diethoxy is silica-based)-(1,2,2-trifluoro-ethylene oxygen base) benzene (22.5mmol); first at room temperature stir 4 hours, then slaking 5 hours at 85 DEG C.Separatory, be washed to neutrality, revolve and steam except desolventizing, quantitatively obtain product.Hydrogen stave levy (
1h NMR, 300MHz, CDCl
3, δ in ppm): 7.62～7.69 (m, 2H), 7.08～7.19 (m, 2H), 3.78～3.88 (m, 4H), 1.21～1.29 (m, 6H), 0.22～0.61 (m, 3H); Fluorine stave levy (
19f NMR, 282MHz, CDCl
3, δ in ppm) :-134.1～-133.5 (m, 1F) ,-125.6～-126.4 (m, 1F) ,-119.1～-119.6 (m, 1F).
Embodiment 7 performed polymers gather the spin coating masking of methyl-(1,2,2-trifluoro-ethylene oxygen base phenyl) siloxanes and solidify
Get 0.5 gram of embodiment 6 prepolymer that obtains, be dissolved in 15 milliliters of toluene, the solution of acquisition, with after 2 microns of membrane filtrations, under room temperature, is under 1000～4000rpm, to drip to (resistivity 2 × 10 on the strict heavy doping silicon chip cleaning at rotating speed
-3Ω .cm).So adopt spin-coating method to obtain after the film of surfacing, be placed in the tube furnace of nitrogen protection, first at 150 DEG C, desolventize 3 hours, be then warming up to 180 DEG C and keep keeping 4 hours at 18 hours or 250 DEG C.So obtain cured film.
Heat-resisting, the dielectric properties of embodiment 8 polymkeric substance and mechanical property
The polymeric film that is 170 nanometers by obtained embodiment 7 thickness is put in vacuum drying oven, in 200 DEG C of heating 2 hours, in nitrogen atmosphere, be chilled to after room temperature, the aluminium electrode that is 1mm in film surface evaporation diameter, and in the metallic aluminium of the back side of silicon chip evaporation 200 nano thickness, so obtain Standard Thin membrane capacitance.By the electric capacity of testing film electrical condenser, calculate specific inductivity and the dielectric loss factor of film.
The above-mentioned film obtaining by spin coating mode is smashed to pieces, be placed in thermogravimetric analyzer, with the temperature rise rate of 10 DEG C/min, the heat decomposition temperature of test polymer and carbon residue amount.
The above-mentioned film obtaining by spin coating mode is done to nanometer mechanics test with the comprehensive mechanical system of nanometer, obtain nano hardness, Young's modulus and bonding strength.
Concrete data are as shown in the table:
Embodiment 9 polymkeric substance are as the purposes of printed circuit board (PCB) insulating resin
Get 50 grams of embodiment 6 prepolymers that obtains, be dissolved in 200 milliliters of toluene, under room temperature, solution is brushed in advance with (600g/m on the alkali-free glass cloth of Silane coupling agent KH550 processing with hairbrush
2), at 120 DEG C, desolventizing after 3 hours, the glass fibre prepreg lamination (4 layers) obtaining, is then placed in compression molding instrument, in 20Kg/cm
2pressure and 180 DEG C of temperatures make type.Glass mat after moulding keeps within 4 hours, obtaining curing glass fiber compound material at 250 DEG C, can be directly used in manufacture printed circuit board (PCB).
The glass mat water-intake rate 0.12% obtaining, the specific inductivity under the operating frequency (50Hz) of electrical equipment is 2.8, tangent of the dielectric loss angle 4 × 10
-3, lower than current industrial glass fibre reinforced composion used, that prepared for matrix resin by epoxy and polyimide etc.
All documents of mentioning in the present invention are all quoted as a reference in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. one kind suc as formula the polymkeric substance shown in I:
In formula, n >=2; Preferably, n=5～100; More preferably, n=10～20.
2. the preparation method of formula I polymkeric substance as claimed in claim 1, is characterized in that, comprises step:
In inert solvent, use as shown in the formula shown in II containing the organosilane monomer of the trifluoro vinyl ether unit polyreaction that is hydrolyzed, obtain formula I polymkeric substance;
Wherein, R is selected from lower group: C1-C4 alkyl; The definition of n is described in claim 1;
Preferably, described hydrolytic-polymeric reaction an acidic catalyst and/or water carry out under existing.
3. one kind as shown in the formula the organosilane monomer shown in II:
Wherein, R is selected from lower group: C1-C4 alkyl.
4. the preparation method of organosilane monomer as claimed in claim 3, is characterized in that, prepares by following step:
(1) in polar aprotic solvent, under basic catalyst exists, use halogenated phenol is reacted under room temperature with tetrafluorodibromoethane, prepare 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-halogeno-benzene;
(2) in polar aprotic solvent, described 4-(2-bromo-1,1,2,2-tetrafluoro oxyethyl group)-1-1-halogeno-benzene is carried out to elimination reaction, obtain 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene;
(3), in polar aprotic solvent, with methyl trialkoxysilane and the reaction of 4-(1,2,2-trifluoro-ethylene oxygen base)-1-halogeno-benzene, obtain suc as formula the organosilane monomer shown in II;
Above-mentioned various in, X is halogen; R is selected from lower group: C1-C4 alkyl.
5. the purposes of formula I polymkeric substance as claimed in claim 1, is characterized in that, for being heating and curing, thereby prepares cure polymer.
6. a polymkeric substance, is characterized in that, described polymkeric substance is to use suc as formula the polymkeric substance described in I to be cured preparation.
7. the preparation method of polymkeric substance as claimed in claim 6, is characterized in that, described polymkeric substance is prepared by the following method: heat suc as formula the polymkeric substance shown in I, thereby obtain polymkeric substance as claimed in claim 6.
8. method as claimed in claim 7, is characterized in that, the temperature range of described heating is 150～250 DEG C.
9. goods, is characterized in that, described goods contain formula I polymkeric substance as claimed in claim 1 or polymkeric substance as claimed in claim 6, or described goods are prepared with formula I polymkeric substance as claimed in claim 1 or polymkeric substance as claimed in claim 6.
10. goods as claimed in claim 9, is characterized in that, described goods are sheet material or the film that contains polymkeric substance claimed in claim 6, and described goods are prepared by the following method:
Carry out room temperature mold pressing with formula I polymkeric substance claimed in claim 1 and obtain the sheet material that contains formula I polymkeric substance; Or with formula I polymkeric substance described in organic solvent dissolution and carry out film forming, obtain the film that contains formula I polymkeric substance;
Above-mentioned polymer sheet or polymeric film are heating and curing, obtain the sheet material or the film that contain polymkeric substance as claimed in claim 6.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410081245.1A CN103865066B (en) | 2014-03-06 | 2014-03-06 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
| PCT/CN2015/073718 WO2015131839A1 (en) | 2014-03-06 | 2015-03-05 | Low dielectric constant polymer containing hexafluorocyclobutyl ether and organic siloxane, preparation and application thereof. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410081245.1A CN103865066B (en) | 2014-03-06 | 2014-03-06 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103865066A true CN103865066A (en) | 2014-06-18 |
| CN103865066B CN103865066B (en) | 2017-04-19 |
Family
ID=50904113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410081245.1A Expired - Fee Related CN103865066B (en) | 2014-03-06 | 2014-03-06 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN103865066B (en) |
| WO (1) | WO2015131839A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448320A (en) * | 2014-11-20 | 2015-03-25 | 中国科学院上海有机化学研究所 | Preparation method and application of trifluoroethyleneoxyphenyl-containing silicone resin |
| WO2015131839A1 (en) * | 2014-03-06 | 2015-09-11 | 中国科学院上海有机化学研究所 | Low dielectric constant polymer containing hexafluorocyclobutyl ether and organic siloxane, preparation and application thereof. |
| CN105418926A (en) * | 2014-09-12 | 2016-03-23 | 中国科学院上海高等研究院 | Fluorine-containing naphthalene ethyl silicon resin, preparation method and applications thereof |
| CN105461744A (en) * | 2014-09-12 | 2016-04-06 | 中国科学院上海高等研究院 | Fluorine-containing naphthylethyl organosilicon monomer, preparation method and uses thereof |
| CN105837617A (en) * | 2016-04-20 | 2016-08-10 | 中国科学院上海有机化学研究所 | Preparation and application of trifluorovinyl-ether-containing cyclosiloxane capable of direct heat curing |
| CN106831361A (en) * | 2015-12-04 | 2017-06-13 | 中昊晨光化工研究院有限公司 | A kind of method that dihalo HFC-143a prepares trifluoro vinyl virtue ether compound |
| CN111405751A (en) * | 2020-04-22 | 2020-07-10 | 上海科谷纳新材料科技有限公司 | Structure for improving performance of MPI (Multi-layer printed Circuit) base material FPC (Flexible printed Circuit) antenna and preparation method |
| CN114605838A (en) * | 2022-03-30 | 2022-06-10 | 韶关方舟长顺有机硅有限公司 | High-water-resistance electronic silica gel and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050107561A1 (en) * | 2003-11-18 | 2005-05-19 | Jae-Suk Lee | Siloxane monomer containing trifluorovinylether group and sol-gel hybrid polymer prepared by using the same |
| CN101362691A (en) * | 2008-09-19 | 2009-02-11 | 中国科学院上海有机化学研究所 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
| CN101492520A (en) * | 2009-03-04 | 2009-07-29 | 中国科学院上海有机化学研究所 | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7538160B2 (en) * | 2005-07-01 | 2009-05-26 | Bausch & Lomb Incorporated | Trifluorovinyl aromatic containing poly(alkyl ether) prepolymers |
| US7402634B2 (en) * | 2005-07-01 | 2008-07-22 | Bausch And Lamb Incorporated | Perfluorocyclobutane copolymers |
| CN103865066B (en) * | 2014-03-06 | 2017-04-19 | 中国科学院上海有机化学研究所 | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer |
-
2014
- 2014-03-06 CN CN201410081245.1A patent/CN103865066B/en not_active Expired - Fee Related
-
2015
- 2015-03-05 WO PCT/CN2015/073718 patent/WO2015131839A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050107561A1 (en) * | 2003-11-18 | 2005-05-19 | Jae-Suk Lee | Siloxane monomer containing trifluorovinylether group and sol-gel hybrid polymer prepared by using the same |
| CN101362691A (en) * | 2008-09-19 | 2009-02-11 | 中国科学院上海有机化学研究所 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
| CN101492520A (en) * | 2009-03-04 | 2009-07-29 | 中国科学院上海有机化学研究所 | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof |
Non-Patent Citations (3)
| Title |
|---|
| J. RIZZO, F.W. HARRIS: "Synthesis and thermal properties of fluorosilicones containing perfluorocyclobutane rings", 《POLYMER》 * |
| X.GONG ET AL.: "High-Performance plymer light-smitting diodes fabricated with a polymer hole injection layer", 《APPLIED PHYSICS LETTERS》 * |
| 龚锴等: "低介电常数聚合物材料的研究进展", 《高分子材料科学与工程》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015131839A1 (en) * | 2014-03-06 | 2015-09-11 | 中国科学院上海有机化学研究所 | Low dielectric constant polymer containing hexafluorocyclobutyl ether and organic siloxane, preparation and application thereof. |
| CN105418926A (en) * | 2014-09-12 | 2016-03-23 | 中国科学院上海高等研究院 | Fluorine-containing naphthalene ethyl silicon resin, preparation method and applications thereof |
| CN105461744A (en) * | 2014-09-12 | 2016-04-06 | 中国科学院上海高等研究院 | Fluorine-containing naphthylethyl organosilicon monomer, preparation method and uses thereof |
| CN105461744B (en) * | 2014-09-12 | 2018-04-06 | 中国科学院上海高等研究院 | A kind of organic silicon monomer of ethyl containing fluoronaphthalene and its production and use |
| CN104448320A (en) * | 2014-11-20 | 2015-03-25 | 中国科学院上海有机化学研究所 | Preparation method and application of trifluoroethyleneoxyphenyl-containing silicone resin |
| CN104448320B (en) * | 2014-11-20 | 2017-11-07 | 中国科学院上海有机化学研究所 | A kind of manufacture method of silicones of phenyl containing trifluoro-ethylene and application |
| CN106831361A (en) * | 2015-12-04 | 2017-06-13 | 中昊晨光化工研究院有限公司 | A kind of method that dihalo HFC-143a prepares trifluoro vinyl virtue ether compound |
| CN106831361B (en) * | 2015-12-04 | 2019-06-25 | 中昊晨光化工研究院有限公司 | A kind of method that dihalo trifluoroethane prepares trifluoro vinyl virtue ether compound |
| CN105837617A (en) * | 2016-04-20 | 2016-08-10 | 中国科学院上海有机化学研究所 | Preparation and application of trifluorovinyl-ether-containing cyclosiloxane capable of direct heat curing |
| CN111405751A (en) * | 2020-04-22 | 2020-07-10 | 上海科谷纳新材料科技有限公司 | Structure for improving performance of MPI (Multi-layer printed Circuit) base material FPC (Flexible printed Circuit) antenna and preparation method |
| CN111405751B (en) * | 2020-04-22 | 2021-04-27 | 上海科谷纳新材料科技有限公司 | Structure for improving performance of MPI (Multi-layer printed Circuit) base material FPC (Flexible printed Circuit) antenna and preparation method |
| CN114605838A (en) * | 2022-03-30 | 2022-06-10 | 韶关方舟长顺有机硅有限公司 | High-water-resistance electronic silica gel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015131839A1 (en) | 2015-09-11 |
| CN103865066B (en) | 2017-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865066A (en) | Low-dielectric-constant polymer containing hexafluoro-cyclobutyl ether and organic siloxane as well as preparation and application of low-dielectric-constant polymer | |
| CN105385106B (en) | A kind of preparation method of high heat conductivity insulation composite | |
| CN104311756B (en) | Silicone containing bismaleimide resin and its preparation | |
| Wang et al. | Phthalonitrile-terminated silicon-containing oligomers: synthesis, polymerization, and properties | |
| CN107459652B (en) | Heat-resistant silicone resin capable of being cured at room temperature and preparation method thereof | |
| JP6198685B2 (en) | Polybenzoxazine-silica composite and method for producing the same | |
| CN102575032A (en) | Process for production of glass-cloth-based base material, and printed wiring board | |
| CN105837617B (en) | Can directly heat cure the ether containing trifluoro vinyl cyclosiloxane preparation and application | |
| CN104559061A (en) | High-thermal conductivity insulated carbon filler, high-thermal conductivity insulated epoxy resin composite material and preparation method thereof | |
| Zhou et al. | Synchronously improved wave-transparent performance and mechanical properties of cyanate ester resins via introducing fluorine-containing linear random copolymer | |
| CN105347788B (en) | The microwave composite dielectric materials and preparation method of low-dielectric loss | |
| CN105061764B (en) | A kind of thermoset polyimide resin and its composite laminate and their preparation method and application | |
| CN102558513A (en) | Oxazine and alkyne compound modified silicon-containing aryne resin and preparing method thereof | |
| CN105778096A (en) | Manufacturing method and application of benzocyclobutenyl containing silicon resin | |
| CN102658704B (en) | Production process of environment-friendly microwave ceramic copper-clad plate | |
| CN104211944B (en) | Multi-fluorine polyarylether, preparation method and application thereof | |
| CN110239164B (en) | High-heat-resistance middle-Tg copper-clad plate and preparation method thereof | |
| CN101962372A (en) | Biphenyl-containing compound liquid crystal epoxy resin and preparation method thereof | |
| CN104448320B (en) | A kind of manufacture method of silicones of phenyl containing trifluoro-ethylene and application | |
| CN103819308B (en) | A kind of curable poly-isophthalic and its preparation method and application | |
| CN104311401B (en) | Containing benzocyclobutene and the thermosetting monomer of Freon C318 unit, preparation method and application thereof | |
| Huang et al. | Fluorinated intrinsic low-k materials at high frequency with good dielectric performance and excellent hydrophobicity | |
| US9518151B2 (en) | Low dielectric constant polymer containing dinaphthyl and hexafluorocyclobutyl ether unit, preparation method and use | |
| CN103755735B (en) | Curable fluorine-containing polyarylether | |
| CN105924601B (en) | It can the directly phenolic resin of the aryl of ether containing trifluoro vinyl of heat cure, preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170419 Termination date: 20210306 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |