CN1487946A - 阻燃剂 - Google Patents
阻燃剂 Download PDFInfo
- Publication number
- CN1487946A CN1487946A CNA018222013A CN01822201A CN1487946A CN 1487946 A CN1487946 A CN 1487946A CN A018222013 A CNA018222013 A CN A018222013A CN 01822201 A CN01822201 A CN 01822201A CN 1487946 A CN1487946 A CN 1487946A
- Authority
- CN
- China
- Prior art keywords
- compound
- formula
- epoxy
- alkyl
- alkoxyl group
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 54
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 5
- 125000004663 dialkyl amino group Chemical group 0.000 claims abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 3
- 239000004634 thermosetting polymer Substances 0.000 claims abstract 2
- 239000011347 resin Substances 0.000 claims description 47
- 239000004593 Epoxy Substances 0.000 claims description 46
- 229920005989 resin Polymers 0.000 claims description 46
- -1 4-epoxycyclohexyl methyl Chemical group 0.000 claims description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- 239000003351 stiffener Substances 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 14
- 239000003063 flame retardant Substances 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002966 varnish Substances 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims 1
- 229920001169 thermoplastic Polymers 0.000 abstract description 3
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 3
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 6
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 6
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000002585 base Substances 0.000 description 13
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 235000013824 polyphenols Nutrition 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000008614 2-methylimidazoles Chemical class 0.000 description 5
- FLROJJGKUKLCAE-UHFFFAOYSA-N 3-amino-2-methylphenol Chemical compound CC1=C(N)C=CC=C1O FLROJJGKUKLCAE-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- KPRZOPQOBJRYSW-UHFFFAOYSA-N o-hydroxybenzylamine Natural products NCC1=CC=CC=C1O KPRZOPQOBJRYSW-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- BMLIZLVNXIYGCK-UHFFFAOYSA-N monuron Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C=C1 BMLIZLVNXIYGCK-UHFFFAOYSA-N 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- HREXIBFZDJHFCF-UHFFFAOYSA-N 2,6-dibromo-4-propylphenol Chemical compound CCCC1=CC(Br)=C(O)C(Br)=C1 HREXIBFZDJHFCF-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- MWGATWIBSKHFMR-UHFFFAOYSA-N 2-anilinoethanol Chemical compound OCCNC1=CC=CC=C1 MWGATWIBSKHFMR-UHFFFAOYSA-N 0.000 description 2
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-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
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- SVLTVRFYVWMEQN-UHFFFAOYSA-N 5-methylcyclohex-3-ene-1,2-dicarboxylic acid Chemical compound CC1CC(C(O)=O)C(C(O)=O)C=C1 SVLTVRFYVWMEQN-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005494 Chlorotoluron Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000005510 Diuron Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- JXCGFZXSOMJFOA-UHFFFAOYSA-N chlorotoluron Chemical compound CN(C)C(=O)NC1=CC=C(C)C(Cl)=C1 JXCGFZXSOMJFOA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- WJSATVJYSKVUGV-UHFFFAOYSA-N hexane-1,3,5-triol Chemical compound CC(O)CC(O)CCO WJSATVJYSKVUGV-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
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Abstract
式(I)或(II)的化合物，其中，R1是C1－C18烷基、未取代的或被一个或多个C1－C6烷基或C1－C6烷氧基取代的C5－C12环烷基、未取代的或被一个或多个C1－C6烷基或C1－C6烷氧基取代的C5－C22芳基、未取代的或被一个或多个C1－C6烷基或C1－C6烷氧基取代的C7－C30芳烷基、R2到R13基团是相互独立的氢、－NO2、二烷基胺基、烷硫基、烷基磺酰基、卤素、C1－C18烷基、C1－C18烷氧基、C1－C18烷氧基烷基、未取代的或被一个或多个C1－C6烷基或C1－C6烷氧基取代的C5－C12环烷基、未取代的或被一个或多个C1－C6烷基或C1－C6烷氧基取代的C5－C22芳基、未取代的或被一个或多个C1－C6烷基或C1－C6烷氧基取代的C7－C30芳烷基，这些化合物适合用作热塑性或热固性聚合物的阻燃剂。
Description
本发明涉及新的苯并噁嗪、其中间体及其制备方法；涉及包含苯并噁嗪的组合物以及这些组合物在制造预浸料坯和层合物中的应用。
由于燃烧产物的毒性和释放出的卤化氢的腐蚀作用，在密封和层合树脂中使用含卤素的阻燃剂是成问题的。因此，这些应用最近更多地采用含磷的阻燃剂。
例如，当用2-(6-氧化物-6H-二苯并-1，2-氧杂磷杂环己-6-基)-1，4-二羟基苯预延长缩水甘油醚时，得到有很好阻燃性和高玻璃转变温度Tg的树脂(C.-S.Wang，M.-C.Lee：“含2-(6-氧化物-6H-二苯并(c，e)(1，2)-氧杂磷杂环己-6-基)-1，4-苯二酚的环氧树脂的合成与性质(II)”，Polymer，41，3631-3638(2000))。
类似的好结果用含磷的环氧树脂也能得到，该环氧树脂由环氧酚醛清漆与9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)反应制备(C.-S.Wang，C.-H.Lin：“新型含磷环氧树脂，第二部分：固化动力学”Polymer，41，8579-8586(2000))。
然而，就重要的层合物性质来说，如介电强度(高压锅测试)，那些阻燃树脂不能满足所有需要。
现已经发现向环氧树脂中加入较少量的特定DOPO衍生物得到有阻燃性的层合树脂，该树脂具有高的玻璃转变温度并且在高压锅测试中得到好的结果。
本发明涉及式I或II的化合物
其中R1是C1-C18烷基；未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C12环烷基；未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C22芳基；未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C7-C30芳烷基，R2到R13基团是相互独立的氢；-NO2；二烷基胺基；烷硫基；烷基磺酰基；卤素；C1-C18烷基；C1-C18烷氧基；C1-C18烷氧基烷基；未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C12环烷基；未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C22芳基；未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C7-C30芳烷基。
当R2到R13基团是C1-C18烷基或C1-C18烷氧基时，这些基团可以是直链的或支链的。
烷基的实例是甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、叔丁基和各种同分异构的戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基和十八烷基。
适合的烷氧基实例是甲氧基、乙氧基、异丙氧基、正丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基和各种同分异构的戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十三烷氧基、十四烷氧基、十五烷氧基、十六烷氧基、十七烷氧基和十八烷氧基。
烷氧基烷基的实例是2-甲氧基乙基、2-乙氧基乙基、2-甲氧基丙基、3-甲氧基丙基、4-甲氧基丁基和4-乙氧基丁基。
环烷基优选C5-C8环烷基，特别是C5-或C6-环烷基。它们的一些实例为环戊基、甲基环戊基、环己基、环庚基和环辛基。
芳基例如是苯基、甲苯基、三甲苯基、isityl、萘基和蒽基。
芳烷基优选含有7到12个碳原子的，特别是7到10个碳原子。例如它可以是苄基、苯乙基、3-苯基丙基、α-甲基苄基、4-苯基丁基或α，α-二甲基苄基。
优选的是式I的化合物，其中R1为C1-C12烷基或C6-C10芳基，特别是异丙基、正戊基或苯基。
优选的是式I的化合物，其中基团R2到R13是氢。
本发明更加优选的实施方案包括式I的化合物，其中R3、R4、R7和R8基团中至少两个是烷氧基、-NO2、二烷基胺基、烷硫基、烷基磺酰基或卤素。
在这些化合物中，特别优选的是其中的R3和R8是烷氧基或二烷基胺基的化合物。
特别优选的是式I的不含卤素的化合物，也就是说式I的化合物中R2到R13都不是卤素。
式I的化合物可以根据本身已知的方法制备。在第一个反应步骤中，式VII的亚氨基甲基苯酚，其中R1、R10、R11、R12和R13是如前所定义的，由式V的已知水杨醛和式VI的胺制备。
通过VII与式VIII的同样已知的DOPO衍生物的反应，得到式III的氨基甲基苯酚，在分子式为VIII的DOPO衍生物中，R2到R9是如前所定义的。
III与甲醛的反应最终产生式I的苯并噁嗪。
式IV的氨基甲基苯酚和式II的苯并噁嗪可以类似地由式IX的二醛合成，其中R12到R13是如前所定义的。
式III和IV的中间产物是新的并且也是本发明所涉及的。本发明还涉及式I或II的化合物的制备方法，在该方法中式III或IV的化合物与甲醛反应。反应可以在有机溶剂中在升高的温度下进行，优选40℃到160℃，特别优选60℃到100℃。然而，也可以使式II的化合物与甲醛在没有溶剂时反应。在该方法中，宜采用固态多聚甲醛与同样是固态的式III或IV的化合物混合形成均匀的粉末。之后熔化该混合物并保持在熔化温度直到停止释放CO2。
式I和II的苯并噁嗪和式III和IV的氨基甲基苯酚以其高固有阻燃性为特征。将它们混入热塑性的或热固性的聚合物中得到具有阻燃性质的基质体系。依据苯并噁嗪或氨基苯酚在树脂混合物中的浓度，参照UL-94标准可能得到从V0到V1级。
本发明还涉及一种组合物，它包含
(a)一种热塑性的或热固性的树脂和
(b)式I、II、III或IV的一种化合物。
根据本发明的这些组合物中的组分(b)的用量宜为5-60重量％，优选10-50重量％，特别优选15-40重量％，以组分(a)+(b)的总量为基准。
对于组分(a)，优选采用热固性树脂，特别是环氧树脂和噁嗪树脂。
例如，在GB-A 1 437 814中描述了噁嗪树脂。
本发明中的苯并噁嗪和氨基苯酚特别适合作为环氧树脂的阻燃剂。
因此本发明还涉及一种组合物，它包含
(a)环氧树脂，
(b)式I或II的化合物或式III或IV的化合物，和
(c)环氧树脂的硬化剂。
根据本发明的组合物中的组分(b)的用量宜为5-60重量％，优选10-50重量％，特别优选15-40重量％，以组分(a)+(b)+(c)的总量为基准。
在本发明的组合物中，式I或II的苯并噁嗪或式III或IV的氨基甲基苯酚可以与其它已知的阻燃剂组合，例如磷酸酯、膦酸酯、氧化膦、三水合铝、煅烧的三水合铝、氢氧化镁、Sb2O3、脱水配合物、和聚磷酸铵。阻燃剂的总量宜为5-60重量％，优选10-50重量％，特别优选15-40重量％，基于总量(环氧树脂+阻燃剂+硬化剂)。
环氧树脂技术中通常使用的环氧树脂适合在本发明组合物的制备中作为组分A。环氧树脂的实例包括：
I)聚缩水甘油基和聚(β-甲基缩水甘油基)酯，它可由分子中有至少两个羧基的化合物与表氯醇或β-甲基表氯醇反应得到。该反应宜在碱存在时进行。
可以用脂肪族的多羧酸作为分子中有至少两个羧基的化合物。该多羧酸的实例有草酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、和二聚或三聚的亚油酸。
但是，也可以用脂环族的多羧酸，例如四氢邻苯二甲酸、4-甲基四氢邻苯二甲酸、六氢邻苯二甲酸或4-甲基六氢邻苯二甲酸。
也可以用芳香族的多羧酸，例如邻苯二甲酸、间苯二甲酸或对苯二甲酸。
II)聚缩水甘油基和聚(β-甲基缩水甘油基)醚，它可由分子中有至少两个自由醇羟基和/或酚羟基的化合物与表氯醇或β-甲基表氯醇反应得到，该反应在碱性条件下或在酸催化剂存在及随后的碱处理下进行。
该类型缩水甘油醚例如得自无环的醇，例如乙二醇、二甘醇或高级聚(氧亚乙基)二醇、1，2-丙二醇或聚(氧亚丙基)二醇、1，3-丙二醇、1，4-丁二醇、聚(氧四亚甲基)二醇、1，5-戊二醇、1，6-己二醇、2，4，6-己三醇、丙三醇、1，1，1-三羟甲基丙烷、季戊四醇、山梨醇以及得自聚表氯醇。
该类型的其它缩水甘油醚得自脂环族醇，例如1，4-环己烷二甲醇、二(4-羟基环己基)甲烷或2，2-二(4-羟基环己基)丙烷，或得自含有芳香族基团和/或其它官能团的醇，例如N，N-二(2-羟基乙基)苯胺或p，p’-二(2-羟基乙基氨基)二苯基甲烷。缩水甘油醚还可以基于单环苯酚，例如间苯二酚或对苯二酚，或基于多环苯酚，例如二(4-羟基苯基)甲烷、4，4’-二羟基联苯、二(4-羟基苯基)砜、1，1，2，2-四(4-羟基苯基)乙烷、2，2-二(4-羟基苯基)丙烷或2，2-二(3，5-二溴4-羟基苯基)丙烷。制备缩水甘油醚的其它合适的羟基化合物是酚醛清漆，它由醛与酚或双酚缩合得到，其中醛是甲醛、乙醛、三氯乙醛或糠醛，酚或双酚是未被取代的或被氯原子或C1-C9烷基取代的，如苯酚、4-氯苯酚、2-甲基苯酚或4-叔丁基苯酚。
III)聚(N-缩水甘油基)化合物，该化合物由表氯醇和含有至少两个胺氢原子的胺的反应产物脱氯得到。这些胺的实例是例如苯胺、正丁胺、二(4-氨基苯基)甲烷、间亚二甲苯基二胺或二(4-甲基氨基苯基)甲烷。
但是，聚(N-缩水甘油基)化合物还包括三缩水甘油异氰脲酸酯、环亚烷基脲的N，N’-二缩水甘油基衍生物，例如亚乙基脲或1，3-亚丙基脲，和乙内酰脲的二缩水甘油基衍生物，如5，5-二甲基乙内酰脲的二缩水甘油基衍生物。
IV)聚(S-缩水甘油基)化合物，例如二-S-缩水甘油基衍生物，它得自二硫醇，例如1，2-乙二硫醇或二(4-巯基甲基苯基)醚。
V)脂环族环氧树脂，例如二(2，3-环氧环戊基)醚、2，3-环氧环戊基缩水甘油醚、1，2-二(2，3-环氧环戊氧基)乙烷或3’，4’-环氧环己烷羧酸3，4-环氧环己基甲脂。
但是，也可以用这样的环氧树脂，该环氧树脂中1，2-环氧化物基团与不同的杂原子或官能团结合；这样的化合物包括例如4-氨基苯酚的N，N，O-三缩水甘油基衍生物、水杨酸的缩水甘油醚-缩水甘油酯，N-缩水甘油基-N’-(2-缩水甘油氧基丙基)-5，5-二甲基乙内酰脲和2-缩水甘油氧基-1，3-二(5，5-二甲基-1-缩水甘油基乙内酰脲-3-基)丙烷。
本发明环氧树脂组合物的制备优选使用双酚的二缩水甘油醚、环氧酚醛清漆、脂环族环氧树脂或聚(N-缩水甘油基)化合物。
特别优选的环氧树脂是双酚A的二缩水甘油醚、双酚F的二缩水甘油醚、环氧苯酚酚醛清漆、环氧甲酚酚醛清漆、3，4-环氧环己基甲基3’，4’-环氧环己烷羧酸酯和N，N，N’，N’-四缩水甘油基二氨基二苯基甲烷。
至于硬化剂(c)，本发明的环氧树脂组合物可以包含在环氧树脂技术中通常使用的硬化剂，例如多羧酸及其酸酐、胺、多胺、聚氨基酰胺、含氨基的加合物、胍、氰基胍、脂肪族或芳香族多元醇或有催化活性的硬化剂。
可以提及的适合的多羧酸包括例如脂肪族多羧酸，如马来酸、草酸、丁二酸、壬基-或十二烷基-丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、和二聚或三聚的亚油酸；脂环族多羧酸，例如四氢邻苯二甲酸、甲基内亚甲基四氢邻苯二甲酸、六氯内亚甲基四氢邻苯二甲酸、4-甲基四氢邻苯二甲酸、六氢邻苯二甲酸和4-甲基六氢邻苯二甲酸；芳香族多羧酸，例如邻苯二甲酸、间苯二甲酸、对苯二甲酸、三聚苯六甲酸、焦苯六甲酸和二苯甲酮-3，3’，4，4’-四-羧酸；和所提到的多羧酸的酸酐。
作为固化用的多胺，可以采用脂肪族、脂环族、芳香族或杂环胺，例如亚乙基二胺、1，2-丙二胺、1，3-丙二胺、N，N-二乙基亚乙基二胺、六亚甲基二胺、二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、N-(2-羟基乙基)-，N-(2-羟基丙基)-和N-(2-氰基乙基)-二乙基三胺、2，2，4-三甲基-1，6-己二胺、2，3，3-三甲基-1，6-己二胺、N，N-二甲基-和N，N-二乙基1，3-丙二胺、乙醇胺、间和对苯二胺、二(4-氨基苯基)甲烷、苯胺-甲醛树脂、二(4-氨基苯基)砜、间亚二甲苯基二胺、二(4-氨基环己基)甲烷、2，2-二(4-氨基环己基)丙烷、2，2-二(4-氨基-3-甲基环己基)丙烷、3-氨基甲基-3，5，5-三甲基环己基胺(异佛乐酮二胺)和N-(2-氨基乙基)哌嗪，作为聚氨基酰胺，例如由脂肪族多胺和二聚的或三聚的脂肪酸得到的聚氨基酰胺。
合适的聚氨基酰胺例如是，由多羧酸与摩尔过量的多胺反应得到的产物，其中多羧酸优选二聚脂肪酸，如在Handbook of Epoxy Resins，1967，10-2到10-10页，作者H.Lee和K.Neville中所述。
胺和聚环氧化合物的含氨基加合物作为环氧树脂的硬化剂是众所周知的，并且可以用来硬化根据本发明的环氧树脂组合物，它由环氧树脂与当量过量的多胺反应得到。该含氨基加合物详细描述在美国专利3 538 184；4 330 659；4 500 582和4 540 750中。
其它适用的胺硬化剂是双氰胺、胍，例如1-邻-甲苯基双胍、氰基胍，例如在美国专利4 859 761或EP-A 306 451中所描述的化合物，或被修饰的多胺，例如Ancamine 2014 S(Anchor Chemical UKLimited，Manchester).
N-酰基咪唑如1-(2’，4’，6’-三甲基苯甲酰基)-2-苯基-咪唑和1-苯甲酰基-2-异丙基咪唑也是适用的。这些化合物例如描述在美国专利4 436 892和4 587 311中。
用于固化本发明环氧树脂组合物的合适的脂肪族多元醇例如是乙二醇、二甘醇和高级聚(氧乙烯基)二醇、1，2-丙二醇和聚(氧丙烯基)二醇、1，3-丙二醇、1，4-丁二醇、聚(氧四亚甲基)二醇、1，5-戊二醇、1，6-己二醇、2，4，6-己三醇、丙三醇、1，1，1-三羟甲基丙烷、季戊四醇、山梨醇、N，N-二(2-羟基乙基)苯胺或p，p’-二(2-羟基乙基氨基)二苯基甲烷。
作为用于固化的芳香族多元醇，可以采用单环苯酚，例如间苯二酚或对苯二酚，或多环苯酚，例如二(4-羟基苯基)甲烷、4，4’-二羟基联苯、二(4-羟基苯基)砜、1，1，2，2-四(4-羟基苯基)乙烷、2，2-二(4-羟基苯基)丙烷、2，2-二(3，5-二溴4-羟基苯基)丙烷，和酚醛清漆，它由醛与酚缩合得到，其中醛例如是甲醛、乙醛、三氯乙醛或糠醛，酚例如是苯酚，或被氯原子或C1-C9烷基取代的酚，如4-氯苯酚、2-甲基苯酚或4-叔丁基苯酚，或与上面提到种类的双酚缩合。
还可以用有催化活性的硬化剂固化本发明的环氧树脂组合物，如叔胺，例如2，4，6-三-(二甲基氨基甲基)苯酚和其它Mannich碱、N-苄基二甲基胺和三乙醇胺；醇的碱金属醇化物，例如2，4-二羟基-3-羟基甲基戊烷的醇钠；链烷酸的锡盐，例如辛酸锡；Friedel-Crafts催化剂，例如三氟化硼及其配合物，例如三氟化硼-胺配合物，和由三氟化硼与1，3-二酮、锍盐或杂环铵盐反应得到的螯合物，其中锍盐公布于欧洲专利0 379 464或美国专利5 013 814，欧洲专利0 580 552或美国专利5 374 697中，杂环铵盐的实例如欧洲专利EP-A-0 066 543中提到的用喹啉盐与苯频哪醇混合。
优选采用酸酐或双氰胺作为硬化剂(c)。
特别优选四氢邻苯二甲酸酐、甲基四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、甲基六氢邻苯二甲酸酐、双氰胺和酚醛清漆。
硬化剂的用量取决于硬化剂的化学性质和可固化混合物和固化产物所希望的性质。本领域的技术人员能够容易地确定最大用量。当硬化剂是一种胺时，通常每当量的环氧使用0.75到1.25当量的胺氢。当采用多羧酸或其酸酐时，通常每当量的环氧使用0.4到1.1当量的羧基或酸酐基团。当采用多元酚作为硬化剂时，每当量的环氧使用0.75到1.25当量的酚羟基。有催化活性的硬化剂通常的用量为每100份重量的环氧树脂使用0.1到40份重量该硬化剂。
合适时，本发明的混合物还可以包含加速剂(d)，它用于与潜在的硬化剂发生交联反应。合适的加速剂的实例有尿素衍生物，例如N，N-二甲基-N’-(3-氯-4-甲基苯基)脲(绿麦隆(chlorotoluron))、N，N-二甲基-N’-(4-氯-苯基)尿素(灭草隆(monuron))或N，N-二甲基-N’-(3，4-二氯苯基)尿素(敌草隆(diuron))、2，4-二(N’，N’-二甲基酰脲基)甲苯或1，4-二(N’，N’-二甲基酰脲基)苯。这些化合物的使用在前面提到的美国专利4 283 520中描述。合适的加速剂是例如在GB-A1 192 790中描述的尿素衍生物。
合适的加速剂还有咪唑，例如咪唑、2-乙基咪唑、2-苯基咪唑、2-甲基咪唑、1-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑或2-乙基-4-甲基咪唑。
其它合适的加速剂还有叔胺、和盐或其季铵化合物，例如苄基二甲基胺、2，4，6-三(二甲基-氨基甲基)苯酚、4-氨基吡啶、苯酚三戊基铵盐、氯化四甲基铵或溴化或氯化苄基三丁基铵；或碱金属醇化物，例如2，4-二羟基-3-羟基甲基戊烷的醇钠。
本发明的环氧树脂组合物还可以包含在环氧树脂技术中通常使用的无机和有机的填料和增强材料。考虑作为填料的实例如下：矿物和纤维填料，例如石英粉、熔融石英、氧化铝、玻璃粉、云母、高岭土、白云石、石墨、碳黑、碳纤维和纺织纤维。优选的填料是石英粉、熔融石英、氧化铝或白云石。合适的增强材料的实例例如是玻璃纤维、碳纤维、凯夫拉尔纤维及它们的混合物。
本发明的环氧树脂组合物根据已知的方法制备，例如使用已知的混合设备如搅拌器、混练机、滚筒或对固体物质使用的干混机。
用环氧树脂技术中常用的方法固化本发明的环氧树脂组合物以形成模塑品、涂层等，如“Handbook of Epoxy Resins”，1967，作者H.Lee和K.Neville中所述。
本发明还涉及得到的固化制品。
采用式I或II的苯并噁嗪或式III和IV的氨基甲基苯酚作为阻燃剂能够制备具有高度的阻燃性、高玻璃转变温度和很好耐热性的树脂。这是令人惊奇的，因为由加入添加剂产生的阻燃效果通常是以机械性能恶化特别是降低玻璃转变温度作为代价而获得的。
式III和IV的化合物以及那些含有至少两个活性氢原子的式I和II的化合物也可以用作环氧树脂的硬化剂。
因此本发明还涉及式III和IV的化合物作为环氧树脂的硬化剂的应用。
本发明的组合物特别适合制造预浸料坯、层合物和RTM(树脂转移模塑)系统。
实施例
在下面实施例中，使用了下列物质：
环氧树脂1：液态双酚A的二缩水甘油醚(环氧含量：5.5eq./kg)
环氧树脂2：液态双酚A的二缩水甘油醚(环氧含量：5.2-5.4eq./kg)
环氧树脂3：四缩水甘油基二氨基二苯基甲烷(环氧含量：7.5-8.5eq./kg)
环氧树脂4：(3，4-环氧环己基)甲基3，4-环氧环己烷羧酸酯(环
氧含量：7.0-7.6eq./kg)
制备实施例
I.1.式IIIa的化合物
把600ml的四氢呋喃置于一个1.5升的具有回流冷凝器、温度计、滴液漏斗和KPG搅拌器的磺化烧瓶中。把110.25g(0.51mol)的Struktol PD 3710随搅拌加入。将白色悬浮液加热到60-65℃的过程中，在内部温度约为40℃时得到略微混浊的无色溶液。在内部温度约为60℃时，将溶于350ml四氢呋喃的102.65g(0.51mol)的2-(苯基亚氨基)甲基苯酚在30分钟期间逐滴加入。反应过程用薄层色谱方法(硅胶，THF/二氯甲烷＝8∶2)每小时进行一次监控。在轻微沸腾回流7小时的过程中，可观察到明显的白色固体沉淀。在此之后，薄层色谱分析表明没有剩余的初始反应物。用烧结玻璃漏斗过滤出白色固体，用旋转蒸发器浓缩母液。其中沉淀的产物和前面分离出的固体在40℃到50℃和0.15毫巴条件下真空干燥10小时。产量：229g(＜95％理论值)。
DSC分析(加热速度10K/min，温度范围-50℃到300℃)：
75℃到140℃吸热，ΔH＝-90J/g和160℃到210℃，ΔH＝-109J/g
IR(KBr压片)：3428.6cm-1，3267.4cm-1，3061.13cm-1，2960.48cm-1，2872.21cm-1，2735.07cm-1，2599.83cm-1，1945.96cm-1，1915.66cm-1，1604.26cm-1，1562.21cm-1，1525.24cm-1，1499.71cm-1，1476.76cm-1，1456.7cm-1，1431.74cm-1，1376.5cm-1，1369.8cm-1，1313.11cm-1，1271cm-1，1224.16cm-1，1206.76cm-1，1146.37cm-1，1117.95cm-1，1083.39cm-1，1047.44cm-1，994.36cm-1，925.02cm-1， 889.51cm-1，850.23cm-1，827.54cm-1，788.96cm-1，755.12cm-1，715.31cm-1，691.38cm-1，633.07cm-1，618.01cm-1，602.96cm-1，570.11cm-1，558.45cm-1.
1
H-NMR，
13
C-NMR，
31
P-NMR：
异构体1：
| 位置 | 1H/ppm | M | J | H | 13C/ppm | 31P/ppm |
| 1234567891011121314151617181920212223242526 | 9.566.767.056.747.505.258.017.557.748.188.137.287.406.99N-H6.916.596.486.596.91 | stttddddddttdddddtdttttt | 8.3Hz7.75Hz7.5Hz7.5Hz10Hz，15Hz7.5Hz，0.5Hz7.5Hz，2.5Hz7.7Hz10Hz，5Hz7.5Hz7.5Hz7.5Hz7.5Hz7.5Hz7.5Hz | 1H1H1H1H1H1H1H1H1H1H1H1H1H1H1H1H | 155.3114.4128.5118.8129.349.0121.0123.7131.81128.2133.9123.3135.1121.1125.3124.9130.4120.2149.3146.9113.1128.6117.0128.6113.1 | 31.271 |
异构体2：
| 位置 | 1H/ppm | M | J | H | 13C/ppm | 31P/ppm |
| 1234567891011121314151617181920212223242526 | 9.436.536.976.747.475.427.307.347.78.138.127.317.407.17N-H6.596.956.486.956.59 | stttddddddttdddddtdddddd | 7.5Hz7.5Hz7.5Hz7.5Hz10Hz，15Hz7.5Hz，1.0Hz7.5Hz，2.5Hz7.5Hz7.5Hz，1Hz7.5Hz7.5Hz | 1H1H1H1H1H1H1H1H1H1H1H1H | 155.1114.4128.6118.5128.742.4121.2123.1130.5127.9133.4123.3135.9122.2125.3124.7130.4119.9148.8147.0113.1128.6117.0128.6113.1 | 27.986 |
产物是非对映异构体IIIa1和IIIa2的混合物。
I.2.式Ia的化合物(Ia)，(Ph＝苯基)
变化1：
实施例I.1.中制备的式IIIa的化合物2.0g(4.8mmol)加入到50ml氯仿中并置于一个100ml的具有回流冷凝器、KPG搅拌器、内置温度计的磺化烧瓶中，沸腾回流得到略微混浊的无色溶液。在加入5-6格令(grains)的UOP分子筛，4A型，2.2-4.9mm后，把0.15g(4.8mmol)的多聚甲醛随搅拌加入。溶液轻微沸腾回流，1小时后薄层色谱显示反应转化完成。产物趁热过滤，得到的澄清无色溶液用旋转蒸发器浓缩。粗产物由2.0g无色晶体组成，该晶体用油泵真空干燥(50℃/0.5毫巴/2小时)。
产量：1.8g白色晶体(88％)。
变化2：
实施例I.1.中制备的式IIIa化合物50g(0.121mol)在研钵中磨碎，然后将7.6g(0.242mol)的多聚甲醛加入其中。两种组分均研磨以形成均匀的粉末。该粉末分置于12个小铝坩埚中，之后将坩埚置于200℃的胶化时间盘(gelling time plate)上。
搅拌约10分钟后，得到澄清的微黄色的溶液。冷却后，得到42.51g(82％)的微白发黄的粉末。
DSC分析(加热速度-50℃到400℃，10K/min)：
Tg＝60℃，预结晶约ΔH＝15J/g，融化期ΔH＝18J/g，反应ΔH＝196J/g
IR(KBr压片)：
3437.08cm-1，3060.31cm-1，2904.92cm-1，1604.9cm-1，1594.3cm-1，1581.01cm-1，
1558.1cm-1，1489.78cm-1，1471.86cm-1，1447.05cm-1，1428.4cm-1，1364.92cm-1，
1313.02cm-1，1268.4cm-1，1256.68cm-1，1225.86cm-1，1211.06cm-1，1202.06cm-1，
1186.64cm-1，1147.61cm-1，1116.19cm-1，1081.49cm-1，1041.29cm-1，1029.37cm-1，
999.42cm-1，976.64cm-1，955.96cm-1，909.71cm-1，876.99cm-1，807.49cm-1，781.05cm-1，
774.10cm-1，761.64cm-1，753.45cm-1，716.86cm-1，709.37cm-1，695.75cm-1，686.85cm-1，
637.21cm-1，612.93cm-1，592.25cm-1，565.20cm-1，552.46cm-1，532.80cm-1，515.19cm-1，
496.76cm-1，465.78cm-1，439.31cm-1.
1
H-NMR(DMSO)：
5.21ppm(d，1H，JH·P＝15Hz)；5.44ppm(dd，1H，J＝12.5Hz，J＝2.5Hz；5.54ppm(d，1H，
J＝12.5Hz)；6.75ppm(d，2H，J＝7.5Hz)；6.84ppm(q，1H，J＝5Hz)；6.86ppm(t，1H，J＝
2.5Hz)；7.01ppm(t，1H，J＝7.5Hz)；7.09ppm(t，2H，J＝7.5Hz)；7.22ppm(t，1H，J＝
7.5Hz)；7.3ppm(d，1H，J＝7.5Hz)；7.35ppm(t，1H，J＝7.5Hz)；7.38ppm(d，1H，J＝
7.5Hz)；7.51ppm(t，1H，J＝7.5Hz)；7.55ppm(dt，1H，J＝2.5Hz，J＝7.5Hz)；7.83ppm(t，
1H，J＝7.5Hz)；7.88ppm(dd，1H，J＝7.5Hz，J＝7.5Hz)；8.27ppm(d，1H，J＝7.5Hz，J＝
1.2Hz)；8.32ppm(dd，1H，J＝5Hz，J＝5Hz)
31
P-NMR(DMSO)：
25.70ppm(s)；25.80ppm(l)；29.109ppm(s)；29.201ppm；32.584ppm(s)
II.应用实施例
测试样品(4mm板)由下列材料制备：四缩水甘油基二氨基二苯基甲烷(TGDADPM，epoxy content：7.5-8.5 eq./kg)、实施例I.2中制备的苯并噁嗪Ia、双氰胺和2-甲基-咪唑，它们的用量，固化条件和胶化时间列于表1中。
从模具中取出后，根据UL 94标准对测试样品进行燃烧性测试。玻璃转变温度Tg用差示扫描量热法(DSC)确定；一些测试样品进行高压锅测试。
测试结果汇总在表1中。
高压锅测试：
测试样品置于高压釜中的架子上。然后加入足够量的蒸馏水，密封装置并加热。通过使用具有恒温器和接触开关的温度计，控制加热量使温度为121℃。压力设置在约2.4到2.6atm。测试板在高压釜中处理1小时。冷却后，测量样品的吸水量。
表1：
| 实施例 | II.1 | II.2 | II.3 | II.4 | II.5 |
| TGDADPM[g]苯并噁嗪Ia[g]双氰胺[g]2-甲基-咪唑[g] | 80203.50.5 | 80203.50.5 | 85153.50.5 | 85153.50.5 | 80203.50.5 |
| 胶化时间(171℃) | 450s(171℃) | 420s(171℃) | 400s(171℃) | 130s(171℃) | 330s(171℃) |
| 固化循环 | 1h/170℃1h/200℃ | 1h/170℃1h/200℃ | 1h/170℃1h/200℃ | 1h/170℃1h/200℃ | 1h/170℃1h/200℃ |
| Tg[℃] | 200 | 197 | 199 | 193 | 195 |
| 吸水量 | 0.48％ | 0.60％ | 0.58％ | 0.30％ | |
| UL 94 | V1 | V1 | V1 | V1 | V1 |
| 总燃烧持续时间 | 109s | 106s | 109s | 104s | 117s |
表1(续)
| 实施例 | II.6 | II.7 | II.8 |
| TGDADPM[g]苯并噁嗪Ia[g]双氰胺[g]2-甲基-咪唑[g] | 80203.50.25 | 80202.0- | 50502.0- |
| 胶化时间(171℃) | 340s(171℃) | 360s(190℃) | 245s(180℃) |
| 固化循环 | 1h/170℃1h/200℃ | 1h/190℃1h/200℃ | 1h/190℃1h/200℃ |
| Tg[℃] | 173 | 178 | |
| 吸水量 | |||
| UL 94 | V1 | V1 | V0 |
| 总燃烧持续时间 | 101s | 129s | 13s |
Claims (17)
1.分子式为I或II的化合物
其中R1是C1-C18烷基、未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C12环烷基、未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C22芳基、未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C7-C30芳烷基，R2到R13基团是相互独立的氢、-NO2、二烷基胺基、烷硫基、烷基磺酰基、卤素、C1-C18烷基、C1-C18烷氧基、C1-C18烷氧基烷基、未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C12环烷基、未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C5-C22芳基、未取代的或被一个或多个C1-C6烷基或C1-C6烷氧基取代的C7-C30芳烷基。
2.权利要求1的式I或II的化合物，其中R1是C1-C12烷基或C6-C10芳基。
3.权利要求1的式I或II的化合物，其中R1是异丙基、正戊基或苯基。
4.前述权利要求的任一项的式I或II的化合物，其中基团R2到R13是氢。
5.权利要求1的式I或II的化合物，其中R3、R4、R7和R8基团中至少两个是烷氧基、-NO2、二烷基胺基、烷硫基、烷基磺酰基或卤素。
6.权利要求1的式I或II的化合物，其中R3和R8是烷氧基或二烷基氨基。
7.式III或IV的化合物，其中R1到R13是如权利要求1中所限定的。
8.权利要求1的式I或II的化合物的制备方法，其中权利要求7的式III或IV的化合物与甲醛反应。
9.一种组合物，其包含
(a)热塑性或热固性的树脂和
(b)权利要求1的式I或II的化合物或权利要求7的式III或IV的化合物
10.权利要求9的组合物，其包含环氧树脂或噁嗪树脂作为组分(a)。
11.权利要求9的组合物，其包含
(a)环氧树脂
(b)权利要求1的式I或II的化合物或权利要求7的式III或IV的化合物，和
(c)环氧树脂的硬化剂。
12.权利要求11的组合物，其包含双酚的二缩水甘油醚、环氧酚醛清漆、脂环族环氧树脂或聚(N-缩水甘油基)化合物作为组分(a)。
13.权利要求11的组合物，其包含双酚A的二缩水甘油醚、双酚F的二缩水甘油醚、环氧苯酚酚醛清漆、环氧甲苯酚酚醛清漆、3，4-环氧环己基甲基3’，4’-环氧环己烷羧酸酯或N，N，N’，N’-四缩水甘油基二氨基二苯基甲烷作为组分(a)。
14.一种固化产物，其可通过固化权利要求9的组合物获得。
15.权利要求1的式I或II的化合物或权利要求7的式III或IV的化合物作为热塑性或热固性聚合物的阻燃剂的用途。
16.权利要求7的式III或IV的化合物作为环氧树脂的硬化剂的用途。
17.权利要求9的组合物在制造预浸料坯、层合物和RTM系统中的用途。
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| CH99/01 | 2001-01-22 | ||
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| US (1) | US7053138B2 (zh) |
| EP (1) | EP1366053B1 (zh) |
| JP (1) | JP4119252B2 (zh) |
| KR (1) | KR100809579B1 (zh) |
| CN (1) | CN1239509C (zh) |
| AT (1) | ATE286506T1 (zh) |
| CA (1) | CA2431426C (zh) |
| DE (1) | DE60108271T2 (zh) |
| EA (1) | EA200300813A1 (zh) |
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| WO (1) | WO2002057279A1 (zh) |
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-
2001
- 2001-11-20 DE DE60108271T patent/DE60108271T2/de not_active Expired - Lifetime
- 2001-11-20 EP EP01273295A patent/EP1366053B1/en not_active Expired - Lifetime
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- 2001-11-20 KR KR1020037008941A patent/KR100809579B1/ko not_active IP Right Cessation
- 2001-11-20 EA EA200300813A patent/EA200300813A1/ru unknown
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| CN113337004A (zh) * | 2021-04-19 | 2021-09-03 | 衡阳师范学院 | 一种新型磷氮dopo衍生物阻燃剂及其合成方法和应用 |
| CN113461734A (zh) * | 2021-04-19 | 2021-10-01 | 衡阳师范学院 | 一种新型含希夫碱dopo磷氮阻燃剂及其合成方法和应用 |
| WO2024021366A1 (zh) * | 2022-07-25 | 2024-02-01 | 潍坊佳诚数码材料有限公司 | 一种防火涂层材料 |
Also Published As
| Publication number | Publication date |
|---|---|
| EA200300813A1 (ru) | 2003-12-25 |
| DE60108271D1 (de) | 2005-02-10 |
| WO2002057279A1 (en) | 2002-07-25 |
| JP2004528285A (ja) | 2004-09-16 |
| US20040054120A1 (en) | 2004-03-18 |
| EP1366053A1 (en) | 2003-12-03 |
| ATE286506T1 (de) | 2005-01-15 |
| JP4119252B2 (ja) | 2008-07-16 |
| KR20030077563A (ko) | 2003-10-01 |
| US7053138B2 (en) | 2006-05-30 |
| KR100809579B1 (ko) | 2008-03-04 |
| ES2233564T3 (es) | 2005-06-16 |
| CA2431426A1 (en) | 2002-07-25 |
| CA2431426C (en) | 2010-08-24 |
| DE60108271T2 (de) | 2006-03-02 |
| CN1239509C (zh) | 2006-02-01 |
| EP1366053B1 (en) | 2005-01-05 |
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