CN1974546B - Diphenol derivative containing aromatic schiff base and ether band structure and its preparation and application - Google Patents
Diphenol derivative containing aromatic schiff base and ether band structure and its preparation and application Download PDFInfo
- Publication number
- CN1974546B CN1974546B CN2006101550926A CN200610155092A CN1974546B CN 1974546 B CN1974546 B CN 1974546B CN 2006101550926 A CN2006101550926 A CN 2006101550926A CN 200610155092 A CN200610155092 A CN 200610155092A CN 1974546 B CN1974546 B CN 1974546B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- containing epoxy
- epoxy
- schiff base
- diphenol derivative
- 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.)
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- -1 aromatic schiff base Chemical class 0.000 title claims abstract description 54
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical class OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002262 Schiff base Substances 0.000 title claims abstract description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003822 epoxy resin Substances 0.000 claims abstract description 35
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims description 120
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 39
- 229920001187 thermosetting polymer Polymers 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000003063 flame retardant Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000470 constituent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 229910052728 basic metal Inorganic materials 0.000 claims 1
- 150000003818 basic metals Chemical class 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 22
- 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 21
- 238000000034 method Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 17
- 239000002585 base Substances 0.000 description 17
- 229920003986 novolac Polymers 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 239000003292 glue Substances 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 150000004753 Schiff bases Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 125000003710 aryl alkyl group Chemical group 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 10
- 229960004756 ethanol Drugs 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 229930185605 Bisphenol Natural products 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical compound [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000002118 epoxides Chemical class 0.000 description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000005181 nitrobenzenes Chemical class 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OIVCDGADLLNZMZ-UHFFFAOYSA-N Nc1ccc([O])cc1 Chemical compound Nc1ccc([O])cc1 OIVCDGADLLNZMZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WEVJWWOGQMMQDE-UHFFFAOYSA-N [O].C1(=CC=CC=C1)C1=C(C=CC=C1)O Chemical compound [O].C1(=CC=CC=C1)C1=C(C=CC=C1)O WEVJWWOGQMMQDE-UHFFFAOYSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011152 fibreglass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- PYZLRNMGUBDIHK-UHFFFAOYSA-N molecular hydrogen;nickel Chemical compound [Ni].[H][H] PYZLRNMGUBDIHK-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920003987 resole Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OPPFIPBEHRZBOT-UHFFFAOYSA-N 1,1-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(O)(CC)OCC1CO1 OPPFIPBEHRZBOT-UHFFFAOYSA-N 0.000 description 1
- SKYBRLALUDNCSM-UHFFFAOYSA-N 1,1-dimethyl-2-phenylhydrazine Chemical class CN(C)NC1=CC=CC=C1 SKYBRLALUDNCSM-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000500881 Lepisma Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- PTXRXGQLWLINGT-UHFFFAOYSA-N cyanic acid;urea Chemical class OC#N.NC(N)=O PTXRXGQLWLINGT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- QKVIAQUPPCPXBX-UHFFFAOYSA-N n,n-dimethyl-1h-pyrrol-2-amine Chemical compound CN(C)C1=CC=CN1 QKVIAQUPPCPXBX-UHFFFAOYSA-N 0.000 description 1
- OVBRYLBVLSAOAS-UHFFFAOYSA-N n,n-dimethyl-2-phenylethanamine;hydron;chloride Chemical compound Cl.CN(C)CCC1=CC=CC=C1 OVBRYLBVLSAOAS-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
Abstract
The present invention discloses one kind of diphenol derivative containing aromatic Schiff base and ether band structure of the general expression as shown. The diphenol derivative may be used in preparing nitrogenous epoxy resin, other diphenol derivative and nitrogenous epoxy resin composition. The nitrogenous epoxy resin is used in making high performance laminate.
Description
Technical field
The present invention relates to a class and contain the diphenol derivative of aromatic schiff base and diether linkage structure and the technology of application thereof.Be specifically related to have excellent over-all propertieies such as high heat-resisting, high glass-transition temperature, UV barrier functionality and flame retardant resistance, can be used as the epoxy resin component of insulating material in the electric field, and their manufacture method.
Background of invention:
Thermostability, insulativity, cohesiveness, good mechanical performance, good building-up properties reach lower advantages such as cost to epoxy resin cured product owing to have preferably, be widely used in bonding, the encapsulation of electronic devices and components and the manufacturing of printed circuit board (PCB), being one of present of paramount importance electron chemistry material, is the mainstay that supports electric industry.Yet the same with most of macromolecular materials, the curable epoxide thing is inflammable, and the fire that the annual whole world therefore causes has caused huge loss of life and personal injury and property damage, therefore necessary the curable epoxide thing that is applied in electric field is carried out fire-retardant finish.
In recent decades, widely used in electric field is to be monomeric brominated Resins, epoxy with tetrabromo-bisphenol, with bromine flame retardant epoxy cured article.Yet brominated Resins, epoxy discharges toxic substance in burning or waste treatment, as produces a large amount of dense smokes and irritating toxic gas.Therefore need to seek the environment friendly flame retardant that substitutes bromine.The Resins, epoxy that is used for electric field at present also suffers from another huge predicament.Because plumbous baneful influence to environment and human health, traditional slicker solder weldprocedure is eliminated gradually.European Union " electric and electronics offal treatment method (Waste Electrical and Electronic Equipment; WEEE) " and " in the electronic electric equipment restriction use some objectionable impurities instruction (Restriction of certain HazardousSubstances; RoHS) " draft for amendments, to Halogen, unleaded environmental protection electronic material standard in addition.Clearly regulation lead, mercury, cadmium, chromium (6 valency), Polybrominated biphenyl (PBB) and six kinds of chemical substances of polybromodiphenyl ether (PBDE) forbade using in electronic and electrical equipment from July 1st, 2006.This means and in various electronic products, must use leadless process that base material is processed, cause unpredictable harm in the product to avoid lead is incorporated into.Because the welding temperature of lead-free solder has the welding temperature of lead solder apparently higher than tradition, so require the thermosetting resin base material of carrying electric elements to have higher thermostability.Thereby this regulation (comprises second-order transition temperature T to the thermostability that the curable epoxide thing that is used for electronic substrate has proposed more harsh performance requriements, particularly material
g, initial heat decomposition temperature T
d, thermal linear expansion coefficient Z-CTE etc.) and processing characteristics.The manufacturing issue of the curable epoxide thing that fire-retardant a, high heat resistance and workability have both to sum up, has in fact been proposed.
The WEEE/RoHS of European Union instruction has begun to carry out, and the Resins, epoxy of consumption maximum needs to change as early as possible to satisfy these requirements in the electronic material.This comprises that " unleaded " that must carry out of regulation requires (needing to improve the thermal stability of material) in the RoHS instruction, comprise that also " non-halogen " that RoHS instruction suggestion is carried out requires (need satisfy the Environmental compatibility in material use and the degradation process, notice that tetrabromo-bisphenol is not among above-mentioned forbidden six kinds of materials, can continue to use about it, environmentalist and industrial community are also among debating actively, but electronic substrate " non-halogen " is the megatrend in this field).For tackling these requirements, the phosphorous epoxy resin system of flame retardant properties excellence just is widely studied since the middle and later periods nineties in last century as the principal item of " Halogen " Resins, epoxy, as patent patent US6403220, US6500546 and EP1312638 etc.But it is big more that the shortcoming of this resinoid system is phosphorus content, and the thermal characteristics of material is just poor more, be difficult to take into account thermotolerance and flame retardant resistance simultaneously, and preparation cost is higher relatively, and industrialization is difficulty relatively.The phosphate ester structure of facile hydrolysis threatens its stable usability in hygrothermal environment in the product in addition.In recent years, the nitrogen flame retardant comes into one's own gradually owing to have advantage such as low toxicity, efficient, high heat resistance.But most nitrogen flame retardants are additive flame retardant, and are poor with the epoxy systems consistency, are difficult to widely apply the epoxy systems that is used for electric field.Patent US20030099839, US6617029 etc. introduce triazine structure (being mainly derived from trimeric cyanamide) in the epoxy systems with the covalent linkage form, be used with phosphorous resin, obtain better flame retardant effect, yet cause fragility to be difficult to adapt to general procedure for processing greatly.The nitrogen-containing epoxy thermoset of the employing introducing unsymmetrical structure method manufacturing that we invent in patent (ZL200410053181.0) can to a certain degree reduce the fragility of high nitrogen-containing epoxy thermoset cured article.Therefore for nitrogenous fire retarding epoxide resin system, improving to satisfy the service requirements of electronic product in the time of the epoxy resin cured product over-all properties, is the research topic that this area needs to be resolved hurrily.
At present electric equipment products needs used resin to have the UV barrier functionality satisfying the procedure for processing requirement as copper-clad plate in addition, and most resin combinations of using at present need add the UV blocking agent, cause the product cost rising.
Summary of the invention:
At problems of the prior art, two amphyls that contain aromatic schiff base structure and fragrant ehter bond provided by the invention, the manufacturing that can be used for making nitrogen-containing epoxy thermoset, combustion-proof epoxide resin composition and be applied to veneer sheet.Use this veneer sheet can take into account the thermotolerance of product, flame retardant resistance and processibility (as the UV block).
The present invention is to realize by such technical scheme for reaching above purpose:
Manufacturing contains the diphenol derivative of aromatic schiff base and diether linkage structure: be starting raw material with the bisphenol compound, obtain diphenol derivative with nitrophenols, hydrazine hydrate and hydroxy benzaldehyde reaction successively.
The feature such as the general expression (1) of dihydric phenols derivative that wherein contains aromatic schiff base and diether linkage structure is represented:
R wherein
1Expression straight chain, branched-chain alkyl, aryl or aralkyl, R is:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Make two amphyls represented, at first will obtain the aromatic diamine derivative that contain aromatic oxide bond structure represented as general expression (2) as general expression (1):
R is in the formula:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Need two-step reaction synthetic as the ether-containing key aromatic diamines that general expression (2) is represented: the one, utilize halogenated nitrobenzene and bisphenol compound and under alkaline condition, prepared in reaction obtains under nitrogen protection and comparatively high temps in polar solvent.Wherein halogenated nitrobenzene is preferably parachloronitrobenzene, p-Nitrobromobenzene, m-chloro-nitrobenzene, a bromo nitrobenzene, o-chloronitrobenzene and o-bromonitrobenzene; Bisphenol compound is preferably the compound of following expression:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, or R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Solvent is preferably dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone and dimethyl sulfone for this reaction is the inert high boiling solvent.Basic catalyst is preferably salt of wormwood, yellow soda ash, saleratus and sodium bicarbonate; The mole proportioning of halogenated nitrobenzene and bisphenol compound reaction is 2～3: 1, is preferably 2～2.5: 1.The consumption of basic catalyst with can with halogenated nitrobenzene equivalent the best; Temperature of reaction is 60-180 ℃, is preferably 130-160 ℃; Reaction times is 5-10 hour, is preferably 8-10 hour.
Another is the reduction of above-mentioned dinitro compound, and the system that any suitable reduction nitro is an amido all is fit to this system, be not particularly limited, but wherein preferable with hydrazine hydrate/iron trichloride/gac system and Raney nickel-hydrogen reducing system.Hydrazine hydrate/iron trichloride/gac the system that adopts, wherein hydrazine hydrate is the aqueous solution of hydrazine, its weight percent concentration is 10-90wt%, be preferably 50-85wt%, hydrazine hydrate need be excessive during use, its molar equivalent be dinitro compound 2-10 doubly, preferred 2-4 is doubly preferable, the adding method of hydrazine hydrate is preferably progressively addition method to avoid its too much hydrolysis.The iron trichloride consumption is the 0.1-10wt% of dinitro compound weight, and activated carbon dosage is the 0.1-10wt% of dinitro compound weight.The solvent that uses is the solvent to this reactionlessness, is mainly alcohols and cyclic ethers class, and alcohols is preferably methyl alcohol, ethanol, propyl alcohol and butanols; The cyclic ethers class is preferably tetrahydrofuran (THF), dioxane.Temperature of reaction is 0-120 ℃, is preferably 50-110 ℃; Reaction times is 2-10 hour, is preferably 4-6 hour.The aromatic diamine derivative of gained recrystallization in methyl alcohol, ethanol or dioxane can obtain pure compound.Raney nickel-hydrogen reducing the system that adopts, wherein Raney nickel and hydrogen all can be buied, and get final product according to the routine operation method of this method.
The aromatic diamines that contains fragrant ehter bond of above-mentioned preparation and following general expression (3):
R in the formula
1Expression straight chain, branched-chain alkyl, aryl or aralkyl.
The hydroxy benzaldehyde reaction of expression can make two amphyls that contain aromatic schiff base and diether linkage structure represented as general expression (1).Reaction solvent is the solvent to this reactionlessness, can be methyl alcohol, ethanol, propyl alcohol, butanols, tetrahydrofuran (THF), dioxane, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfone etc., is preferably ethanol, dioxane and dimethyl formamide.This reaction also can be used acid as catalyst, with zinc chloride, more excellent to the acid of methylbenzene semi-annular jade pendant.Temperature of reaction is generally 0-150 ℃, is preferably 20-100 ℃.Reaction times is 0.5-24 hour, is preferably 4-6 hour.After reaction finishes, filtration, the dry goods that form.Also can utilize process for purification commonly used to make with extra care as required.
Can produce two amphyls that contain aromatic schiff base and diether linkage structure of described general expression (1) expression thus, this derivative has the phenolic group hydroxyl.The invention provides a kind of its method of making nitrogen-containing epoxy thermoset of using, promptly be to make itself and epoxy compounds direct reaction, or itself and epoxyhalopropane are reacted under alkaline condition.
Below nitrogen-containing epoxy thermoset provided by the invention and manufacture method thereof are described.
The bicyclic oxygen compound that is characterized as the structural unit that contains described general expression (4) expression of nitrogen-containing epoxy thermoset of the present invention:
R wherein
1Expression straight chain, branched-chain alkyl, aryl or aralkyl, R is:
Wherein, (a) in X for-(being biphenyl structural) ,-C (CH
3)
2-,-SO
2-,-CH
2-and-O-; (b) and (c) R in
1, R
2And R
3Expression hydrogen atom, straight chain, branched-chain alkyl, aryl or aralkyl, R
2And R
3Can be both combinations arbitrarily in hydrogen atom, alkyl, the aryl or aralkyl.
Method as the structural unit of introducing described general expression (4) expression has: two amphyls that contain fragrant ehter bond and schiff base structure of described general expression (1) expression and functionality are more than or equal to the direct chain extending reaction of 2 epoxy compounds (hereinafter referred to as implementation method 1), or two amphyls that contain fragrant ehter bond and schiff base structure reaction (hereinafter referred to as implementation method 2) under basic catalyst exists that described general expression (1) is represented.
Implementation method 1: wherein said epoxy compounds comprises Racemic glycidol ethers monomer and the oligopolymer that contains 2 epoxy group(ing) in 1 molecule at least, as: bisphenol type epoxy, tetrabromo-bisphenol type epoxy, Bisphenol F type epoxy, bisphenol S type epoxy, biphenyl type epoxy, naphthalene type epoxy, ortho-cresol type phenolic aldehyde epoxy, phenol type phenolic aldehyde epoxy, bisphenol A-type phenolic aldehyde epoxy, bromination phenolic aldehyde epoxy, diglycidyl ether of ethylene glycol and propanetriol-diglycidyl-ether etc., aromatic amine and nitrogen heterocyclic derive two N-Racemic glycidol amine monomer and oligopolymer, for example: N, N '-diglycidylaniline, triglycidyl group isourea cyanates etc. also can be above-mentioned several mixing.The reaction mole proportioning of described general expression (1) expression diphenol derivative and epoxy compounds is generally and is 0-1: 1, be preferably 0.1-0.5: 1.Temperature of reaction is generally 0-200 ℃, is preferably 60-180 ℃, and the reaction times is 0.5-12 hour, is preferably 2-6 hour.Reaction also can be carried out in the presence of catalyzer, is preferably organic alkali catalyst, and is Phosphorus as triphenyl phosphorus, three (2, the 6-Dimethoxyphenyl) phosphorus etc., tertiary amines such as phenyl dimethylamino, ammonium salt classes such as tetraethylammonium bromide, benzyl trimethyl ammonium chloride etc.Be reflected at and carry out under the vacuum condition obtaining better reaction result.Also can use solvent according to reaction, spendable solvent for example has: halo alkanes such as chloroform, methylene dichloride, N-Methyl pyrrolidone, dimethyl formamide, dioxane etc.The gained nitrogen-containing epoxy thermoset is generally yellow powder shape solid, and molecular weight is generally 500-2000.
Implementation method 2:
Described epoxyhalopropane is epoxy chloropropane, epoxy bromopropane, methyl epichlorohydrin, is preferably epoxy chloropropane cheap and easy to get.The usage quantity of epoxyhalopropane is generally normal 2～20 times of diphenol derivative of described general expression (1) expression.Used basic catalyst is if any inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, triethylamine, Trimethylamine 99, N, N '-dimethylcyclohexylamine, pyridine, 2-picoline, 4-picoline, to dimethylamino pyrrole, Tetraethylammonium bromide, benzyl trimethyl ammonia chloride etc., can mix use, have no particular limits.The usage quantity of alkali must make the phenolic hydroxyl group activation of the diphenol derivative of described general expression (1) expression, and can eliminate the by-product hydrogen halide that reaction generates.The 1-10 that common alkali consumption is the phenolic hydroxyl group number doubly.Use mineral alkali such as sodium hydroxide and quaternary ammonium salt such as Tetraethylammonium bromide to be used, can obtain preferable reaction effect, in the case, the usage quantity of quaternary ammonium salt is 0.1～2mol% of phenolic hydroxyl group.Reaction is solvent usually with the epoxyhalopropane, also can add other inert solvent as required.Temperature of reaction is generally 30-120 ℃; Be preferably 80～120 ℃.Reaction times is generally 0.5～24 hour, is preferably 0.5～5 hour.After reaction finished, the nitrogen-containing epoxy thermoset that is generated was dissolved in toluene, the methylene dichloride equal solvent, makes with extra care by methods such as washing, distillations.The nitrogen-containing epoxy thermoset that obtains is yellow thick liquid or solid, and molecular weight is 300～1500.
It is a kind of by the application of described general expression (1) expression diphenol derivative with the nitrogen-containing epoxy thermoset of the diphenol derivative modular construction that contains described general expression (4) expression that uses its manufacturing that the present invention also provides.Promptly be to form combustion-proof epoxide resin composition, and be used for the manufacturing of veneer sheet with Resins, epoxy, solidifying agent, curing catalyst, fire retardant and solvent etc.
Fire-retarded epoxy resin constituent of the present invention is characterised in that: contain by a kind of of described general expression (1) expression diphenol derivative at least or contain a kind of by in the nitrogen-containing epoxy thermoset of the diphenol derivative modular construction of described general expression (4) expression.Its composition of fire-retarded epoxy resin constituent provided by the invention and content are:
Resins, epoxy: 20～80 parts (in constituent solid content);
Solidifying agent: 1～80 part (in constituent solid content);
Curing catalyst: 0.01～2wt.% of resin total solid content;
Fire retardant: 0～40wt.% of weight resin;
Solvent: 15～60wt.% of resin total solid content.
Described Resins, epoxy is except nitrogen-containing epoxy thermoset provided by the present invention, also comprise all Resins, epoxy well known in the art, as contain brominated Resins, epoxy such as tetrabromo-bisphenol type Resins, epoxy, brominated phenols formaldehyde epoxy resin, contain annular phosphate group (as following formula 5-8) and contain the phosphorous epoxy resin of phosphine structure (as following formula 9-10):
Or general commercial Resins, epoxy such as bisphenol type epoxy, Bisphenol F type epoxy, bisphenol S type epoxy, biphenyl type epoxy, naphthalene type epoxy, ortho-cresol type phenolic aldehyde epoxy, phenol type phenolic aldehyde epoxy, bisphenol A-type phenolic aldehyde epoxy.The use of above-mentioned Resins, epoxy is not particularly limited, and also can be wherein several mixing as required.
Described solidifying agent can use all materials well known in the art except diphenol derivative provided by the invention.Particularly: aromatic amine such as mphenylenediamine, Ursol D, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenyl oxide, 4,4 '-diamino diphenyl sulfone etc., phenolic solidifying agent such as phenol molded lines resol, cresols molded lines resol, bromination linear phenolic resin and bisphenol A-type linear phenolic resin, and Dyhard RU 100, cyanurotriamide modified novolac phenolic aldehyde etc.Above-mentioned solidifying agent can be used alone, but also also mix together.The usage quantity of described solidifying agent preferably adds according to total epoxy equivalent (weight) of used Resins, epoxy.
Described curing catalyst uses all materials well known in the art.Be preferably glyoxaline compound, triphenyl phosphorus etc. such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole.
Described solvent uses all materials well known in the art.As toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, acetone, pimelinketone, Propylene Glycol Dimethyl Ether etc.These solvents can use separately also can mix use.
Described fire retardant uses all materials well known in the art, and the present invention is preferably hydrated metal oxide, as aluminium hydroxide, magnesium hydroxide and nitrogenous or phosphorus type flame retardant, as melamine derivative, phosphoric acid ester derivant, ammonium polyphosphate.
Combustion-proof epoxide resin composition of the present invention can be used for the manufacturing of veneer sheet.Fire-retarded epoxy resin constituent provided by the invention is mixed with the epoxy resin adhesive liquid that solid content is 40-85%, with the alkali-free glass cloth is strongthener, by impregnation, semicure and heat pressing process compacting, obtain woven fiber glass enhanced epoxy matrix composite, i.e. veneer sheet.Wherein said solvent uses all materials well known in the art, is preferably to be toluene, dimethylbenzene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, methyl ethyl ketone, acetone and pimelinketone etc., and these solvents can use separately also can mix use.
Remarkable advantage of the present invention and effect:
The present invention is from the angle of molecular structure, two amphyls or the Resins, epoxy that design, synthesized a class rigid chain segment (aromatic oxide bond structure) and hard and soft segment (being the aromatic schiff base structure) and deposit, and with component epoxy constituents such as Resins, epoxy, solidifying agent, curing catalyst, obtain epoxy resin cured product fire-retardant, heat-resisting and that processing characteristics is excellent by simple, economic preparation route, and be applied to the making of veneer sheet.
Embodiment:
Utilize embodiment to describe the present invention in detail below, the present invention is not limited to this.
Embodiment 1:2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane:
Synthetic:
With 0.1mol dihydroxyphenyl propane, 0.22mol parachloronitrobenzene, 0.22mol K
2CO
3, 200ml DMF adds in the 500ml four-hole boiling flask, under nitrogen protection, stirring heating is warming up to 145-150 ℃ of constant temperature back flow reaction 10h.After reaction finishes while hot vacuum filtration remove impurity such as inorganic salt, slowly add the 80ml deionized water, have yellow solid to separate out after the cooling, vacuum filtration uses deionized water and washing with alcohol for several times more successively, vacuum-drying gets the khaki color powdery solid.With synthetic dinitrobenzene product, 200ml ethanol, 2.0g gac and 0.6g FeCl above the 0.1mol
36H
2O adds flask successively, and the preheating certain hour is warming up to 80 ℃.The hydrazine hydrate solution of 60ml 85wt.% slowly is added dropwise to system, drips off back isothermal reaction 4h.Filtered while hot is removed inorganic salt and gac, filtrate is cooled off gradually again, separates out precipitation.To precipitate and use ethyl alcohol recrystallization, vacuum-drying gets yellow needle-like crystal, obtain containing the aromatic diamine compound of ehter bond, the 0.10mol diamines is dissolved in DMF, and join in the constant pressure funnel, the 0.21mol p-Hydroxybenzaldehyde is added four-hole boiling flask, add ethanol, in N
2Atmosphere slowly stirs, and is heated to when refluxing to begin to drip above-mentioned two amine aqueous solutions, and about 1h drips off.Dropwise the back and continue isothermal reaction 6-8h, reaction soln is poured in the 1000ml deionized water, get yellow mercury oxide.Leave standstill, suction filtration gets yellow powdery solid, and recrystallization in dehydrated alcohol obtains target product, productive rate 95%.Yield:95%, mp:125～127 ℃; IR (KBr, cm
-1): 3415 (Ar-OH), 1604 (CH=N), 1235 (Ar-O-Ar). ultimate analysis: C
41H
46N
2O
4(618.7): Cal:C, 79.59%; H, 5.54%, N, 4.53%; Found:C, 79.04%; H, 5.85%, N, 4.56%.
Embodiment 2:1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene:
Synthetic:
Replace dihydroxyphenyl propane with Resorcinol, reaction obtains yellow powder shape solid.Productive rate: 97%.M.p.278～280 ℃; IR (KBr, cm
-1): 3368 (Ar-OH), 1605 (HC=N), 1245 (Ar-O-Ar). ultimate analysis: C
32H
24N
2O
4(500.6): Cal:C, 76.79%; H, 5.83%, N, 5.60%; Found:C, 76.04%; H, 4.98%, N, 5.63%.
Embodiment 3: the diphenol that contains phthalazone/schiff bases structure:
Synthetic:
With 23.8g phthalazone (0.10mol), 34.6g parachloronitrobenzene (0.22mol), 31.0g salt of wormwood (0.22mol) join in the 500ml four neck flasks, and 150ml DMF makes solvent, N
2Following stirring and dissolving.Be warming up to boiling reflux (about 145-150 ℃) then, keep back flow reaction 8～10h.Be cooled to room temperature then, with product pour into water/ethanol (50/50, v/v) wash in the mixing solutions, suction filtration gets yellow solid, for containing the dinitro compound of naphthyridine ketone structure, recrystallization in the ethanol.With 48.0g previous step synthetic dinitrobenzene product D NP (0.1mol), 1.50g gac, 0.6g FeCl
36H
2O and 300ml dioxane add flask successively, rise to reflux temperature.Hydrazine hydrate solution with 60ml 85wt.% slowly drops in the flask then, isothermal reaction 4h again after 2h drips.Filtered while hot is fallen inorganic salt and gac, filtrate is cooled off gradually again, separates out precipitation, filter crude product.Recrystallization in dioxane/water then obtains containing the aromatic diamines of naphthyridine ketone structure.With the above-mentioned diamines of 0.1mol, the ZnCl of 4-hydroxy benzaldehyde and catalytic amount
2Join in the 500ml four-hole boiling flask, 150ml adds solvent DMF,, after 8 hours product solution is poured in the big water gaging in 100 ℃ of following stirring reactions, obtains the khaki color throw out.Leave standstill suction filtration and get yellow powdery solid.Recrystallization gets target product in the DMF/ ethanol.Productive rate is 95wt.%, mp:304～306 ℃.IR(KBr，cm
-1)：3369(Ar-OH)，1646(C＝O)，1626(C＝N)，1235(Ar-O-Ar，Ar-OH)。C
40H
28O
4N
4(628.7)：Cal：C，76.42％；H，4.49％，N，8.91％；Found：C，76.55％；H，4.40％，N，8.99％。
Embodiment 4: by 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane and the synthetic nitrogen-containing epoxy thermoset of epichlorohydrin reaction.
Take by weighing 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 10.0g, add in the 50g epoxy chloropropane, after being heated to dissolving, add the 0.1g benzyl trimethyl ammonium chloride again, keep temperature of reaction in 90 ℃ after about 30 minutes, with the 1.68g dissolution of sodium hydroxide in 3.0ml water, be divided into three batches, every interval joined in the reaction system in 10 minutes.Then in about 100 minutes of 90 ℃ of reactions.Most of epoxy chloropropane is removed in decompression, the cooling after washing, joins in a large amount of methyl alcohol and obtains yellow solid.Productive rate: 80%.Molecular weight 400-900, IR (KBr, cm
-1): 3400 (OH), 1624 (C=N), 1240 (aryl oxide keys), 911 (epoxide groups).
Embodiment 5: by 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene and epichlorohydrin reaction synthesize nitrogen-containing epoxy thermoset.
Synthetic method is with embodiment four.Product is a yellow solid.Molecular weight 400-1000, IR (KBr, cm
-1): 3330 (OH), 1620 (C=N), 1240 (aryl oxide keys), 911 (epoxide groups).
Embodiment 6: by 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } methane and the synthetic nitrogen-containing epoxy thermoset of Resins, epoxy chain extending reaction
Take by weighing 2 respectively, the triphenyl phosphorus of 2 '-two { 4-[4-(hydroxyl) phenyl Schiff base] phenol oxygen base phenyl } methane 30g, 100g E51 and 0.1wt.%, add and be equipped with in the three-necked bottle of thermometer, agitator and vacuum system coupling device, vacuumize in the bottle (740～750mmHg) and slow heated and stirred, 100 ℃ of following heating under vacuum to eliminate the small molecular weight impurity in the system.Diphenol is dissolved in the Resins, epoxy gradually simultaneously, and when no bubble, beginning slowly is warming up to 140 ℃, reacts 2 hours.Obtain being the nitrogen-containing epoxy thermoset of red solid under the normal temperature, molecular weight is about 500, and is suitable with calculated value.This reaction can dimethyl formamide be that solvent reacts also, and the gained reactant solution can be directly used in configuration fire retarding epoxide resin glue.Molecular weight 600-2000.IR (KBr, cm
-1): 1622 (C=N), 1240 (aryl oxide keys), 912 (epoxide groups).
Embodiment 7: by the diphenol and the epichlorohydrin reaction synthetic epoxy resin of phthalazone/schiff bases structure.
Synthetic method is with embodiment four.Product is a yellow solid.Molecular weight 600-1500.IR (KBr, cm
-1): 3330 (OH), 1646 (C=O), 1626 (C=N), 1240 (aryl oxide keys), 915 (epoxide groups).
Combustion-proof epoxide resin composition
Embodiment 8: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 30g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 40g, 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 23.8g, 2,2 '-two [4-(amino) phenyl phenol oxygen base] propane: 31.6g, solvent is the mixing solutions of dimethyl formamide and acetone, makes solid content and be 60% glue.
Embodiment 9: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 38g, phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.32g/eq) 25g, 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 43g, 2,2 '-two [4-(amino) phenyl phenol oxygen base] propane: 21.3g, solvent is an acetone, makes solid content and be 60% glue.
Embodiment 10: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 35g, phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.32g/eq) 23g, 2,2 '-two 4-[4-(hydroxyl) phenyl Schiff base] and phenol oxygen base phenyl } propane 59.2g, 2,2 '-two [4-(amino) phenyl phenol oxygen base] propane: 13g, solvent is an acetone, makes solid content and be 60% glue.
Embodiment 11: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 30g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 50g, 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 22g, 1,4-two (p-aminophenyl oxygen base) benzene: 25.7g, solvent is a dimethyl formamide, makes solid content and be 55% glue.
Embodiment 12: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 35 g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 35g, 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 38.5g, 1,4-two (p-aminophenyl oxygen base) benzene: 16.8g, solvent is a dimethyl formamide, makes solid content and be 55% glue.
Embodiment 13: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 45g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 20g, 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 54g, 1,4-two (p-aminophenyl oxygen base) benzene: 10.5g, solvent is a dimethyl formamide, makes solid content and be 55% glue.
Embodiment 14: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 20g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 50g, the diphenol 24g that contains phthalazone/schiff bases structure, the diamines that contains phthalazone/schiff bases structure: 32.5g, solvent is an acetone, makes solid content and be 55% glue.
Embodiment 15: bisphenol A type epoxy resin (epoxy equivalent (weight) 0.51g/eq) 32g, phosphorated ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 30g, the diphenol 43g that contains phthalazone/schiff bases structure, the diamines that contains phthalazone/schiff bases structure: 21.5g, solvent is an acetone, makes solid content and be 50% glue.
Embodiment 16: phosphorous phenol type novolac epoxy (epoxy equivalent (weight) 0.35g/eq) 65g, and 2,2 '-two { 4-[4-(hydroxyl) phenyl Schiff base] phenol oxygen base phenyl } propane 56g, solvent is a dimethyl formamide, makes solid content and be 60% glue.
Embodiment 17: phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.35g/eq) 67g, and 1,4 '-two [4-(4-hydroxyl) phenyl Schiff base] phenoxy group benzene 47g, solvent is a dimethyl formamide, makes solid content and be 45% glue.
Embodiment 18: phosphorated phenol type novolac epoxy (epoxy equivalent (weight) 0.35g/eq) 85g, contain the diamines 32g of phthalazone/schiff bases structure, and solvent is a dimethyl formamide, makes solid content and be 40% glue.
Embodiment 19: phosphorous ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 80g, by embodiment 4 synthetic nitrogen-containing epoxy thermoset 20g, be dissolved in the dimethyl formamide, and add carbamide-phenol Lip river furac solidifying agent 17g, be 55% adding butanone adjusting glue solid content.
Embodiment 20: phosphorous ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 80g, by embodiment 5 synthetic nitrogen-containing epoxy thermoset 20g, be dissolved in the dimethyl formamide, and add carbamide-phenol Lip river furac solidifying agent 17g, be 55% adding butanone adjusting glue solid content.
Embodiment 21: phosphorous ortho-cresol type novolac epoxy (epoxy equivalent (weight) 0.3g/eq) 80g, by embodiment 7 synthetic nitrogen-containing epoxy thermoset 20g, be dissolved in the dimethyl formamide, and add cyanurotriamide modified novolac phenolic aldehyde (laboratory is from synthetic) 17g, be 60% adding butanone adjusting glue solid content.
It is the epoxy resin adhesive liquid of 40-85% that the foregoing description 8-18 is become solid content by formulated, with alkali-free 7628 type woven fiber glass is strongthener, (the prepreg solid content is controlled at 38～45wt.%) by impregnation, semicure, in the vacuum hotpressing machine,, obtain woven fiber glass enhanced epoxy matrix composite in 175 ℃ of compacting 2.0h.The naturally cooling depanning obtains the sample of long 130mm * wide * 13mm * thick 1.6mm after cutting out, carry out the experiment of oxygen index and vertical combustion, utilizes the second-order transition temperature of DSC method test cured article, the results are shown in Table 1.
Composition epoxy resin in the foregoing description does not need to add the UV blocking agent, can reach UV barrier functionality preferably, and prepared double-sided copper-clad paper tinsel plate adapts to whole procedure for processing of printed circuit board fully.
Table 1
| Embodiment | Second-order transition temperature (℃, DSC) | Oxygen index (LOI) | Vertical combustion (UL94) |
| 8 9 10 11 12 13 14 15 16 17 18 19 20 21 | 153 146 139 147 136 125 153 156 157 135 157 174 165 185 | 28.8 30.5 33.0 26.4 28.5 31.6 30.8 31.2 29.0 28.5 35.8 34.5 33.0 36.0 | V-0 V-0 V-0 V-1 V-0 V-0 V-0 V-0 V-1 V-1 V-0 V-0 V-0 V-0 |
Claims (8)
1. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure, described diphenol derivative is represented by following general expression (1):
R in the formula
1Be the straight or branched alkyl; R is:
R wherein
1, R
2And R
3Be H.
2. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure according to claim 1 is characterized in that nitrogen-containing epoxy thermoset is to comprise as the described modular construction bicyclic oxygen of following general formula (4) compound:
R in the formula
1Be the straight or branched alkyl; R is:
R wherein
1, R
2And R
3Be H.
3. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure according to claim 1, it is characterized in that, when making nitrogen-containing epoxy thermoset, by two amphyls of general expression (1) expression and functionality more than or equal to 2 epoxy compounds under the vacuum condition under 0-200 ℃ temperature chain extending reaction, the reaction mole proportioning of diphenol derivative and epoxy compounds is 0-1: 1, and the reaction times is 0.5～12 hour.
4. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure according to claim 1, it is characterized in that, make two amphyls of described general expression (1) expression under basic catalyst exists, make nitrogen-containing epoxy thermoset with the epoxyhalopropane reaction, the usage quantity of epoxyhalopropane is normal 2～20 times of the diphenol derivative of described general expression (1) expression, basic catalyst is the oxyhydroxide of basic metal or alkaline-earth metal, organic amine, organic phosphine or quaternary ammonium salt, temperature of reaction is 30～120 ℃, and the reaction times is 0.5～24 hour.
5. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure according to claim 1 is characterized in that described nitrogen-containing epoxy thermoset is used to make the fire-retarded epoxy resin constituent.
6. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure according to claim 5, it is characterized in that, described fire-retarded epoxy resin constituent, by a kind of composition the in the nitrogen-containing epoxy thermoset that contains described general expression (1) expression diphenol derivative at least, the component of this constituent and constituent solid content are as follows:
Resins, epoxy accounts for the constituent solid content: 20～80 parts;
Solidifying agent accounts for the constituent solid content: 1～80 part;
Curing catalyst: 0.01～2wt.% of resin total solid content;
Fire retardant: 0～40wt.% of weight resin;
Solvent: 15～60wt.% of resin total solid content.
7. the application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure according to claim 1 is characterized in that, nitrogen-containing epoxy thermoset is used for the making layer pressing plate.
8. by the described application of diphenol derivative in making nitrogen-containing epoxy thermoset that contains aromatic schiff base and diether linkage structure of claim 7, it is characterized in that being, the fire-retarded epoxy resin constituent is mixed with the epoxy resin adhesive liquid that solid content is 40-85%, with the alkali-free glass cloth is strongthener, by obtaining veneer sheet after impregnation, semicure and the hot pressing.
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| CN114907213A (en) * | 2022-05-09 | 2022-08-16 | 河北海力香料股份有限公司 | Preparation method of high-quality p-chloronitrobenzene |
| CN115558185B (en) * | 2022-10-17 | 2023-09-05 | 安徽杰蓝特新材料有限公司 | HDPE hollow wall winding pipe |
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| US5066765A (en) * | 1990-04-11 | 1991-11-19 | Nippon Steel Chemical Co., Ltd. | Poly(azomethine-ester) having film-forming ability, and heat resistance pre and regulated monomer sequences in the polymer backbone |
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| US5066765A (en) * | 1990-04-11 | 1991-11-19 | Nippon Steel Chemical Co., Ltd. | Poly(azomethine-ester) having film-forming ability, and heat resistance pre and regulated monomer sequences in the polymer backbone |
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