CN1621443A - Flame-retardant epoxy resin and flame-retardant epoxy resin composition - Google Patents
Flame-retardant epoxy resin and flame-retardant epoxy resin composition Download PDFInfo
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- CN1621443A CN1621443A CN 200310115435 CN200310115435A CN1621443A CN 1621443 A CN1621443 A CN 1621443A CN 200310115435 CN200310115435 CN 200310115435 CN 200310115435 A CN200310115435 A CN 200310115435A CN 1621443 A CN1621443 A CN 1621443A
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- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 26
- 239000003063 flame retardant Substances 0.000 title abstract description 35
- 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 title abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 239000003351 stiffener Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 230000000979 retarding effect Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- 238000005538 encapsulation Methods 0.000 claims 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 8
- 125000003700 epoxy group Chemical group 0.000 abstract description 7
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 3
- 125000003367 polycyclic group Chemical group 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 230000004048 modification Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- -1 phosphate ester Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 208000034189 Sclerosis Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 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 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002576 ketones Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 235000010292 orthophenyl phenol Nutrition 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- XKIWZZJNBVOFIE-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1.NC1=CC=C(O)C=C1 XKIWZZJNBVOFIE-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 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
- 150000001412 amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 150000004693 imidazolium salts Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant epoxy resin, which utilizes a reactive phosphorus-containing compound to react with epoxy groups in an epoxy resin with more than two epoxy groups, wherein the epoxy resin has a polycyclic structure and comprises the following components: aromatic, aliphatic, naphthalene and other structures are mixed with a specific curing agent to be cured, so that the flame-retardant epoxy resin composition with excellent flame retardance and physical properties can be obtained.
Description
Invention field
The present invention is relevant a kind of fire-retarded epoxy resin, its utilization has the epoxy reaction in the Resins, epoxy of reactive P contained compound and two above epoxy group(ing), wherein Resins, epoxy has polynuclear plane, many rings comprise: structures such as aromatic series, aliphatics, naphthalene can obtain to have raising second-order transition temperature (Tg) and improvement heat-resistant resin.
The also relevant a kind of flame retardant resin composition of the present invention, it comprises the many rings ethoxyline resin antiflaming composition that contains reactive P contained compound modification, the not halogen-containing composition of said composition, and need not add inorganic substance such as silicon-dioxide, aluminium hydroxide improves flame retardant effect, and can reach the flame-retardant standard of UL 94U-0.
Background of invention
Conventional flame retardant is to be main additive with the halogen, but recently suffer exit gradually because of the environmental protection factor, this is can produce acrid hydrogen halide and a large amount of smog because halogen is heated again, though can reach the flame retardant effect of expection, but can be detrimental to health and damage the ozone layer.
So develop novel fire retardant and usually replace halogen, and then to make green product be recent global fire retardant development trend with other yuan.
Making with the printed circuit board (PCB) that attracts attention at present, often give ethoxyline resin antiflaming with the tetrabormated third diphenol A (tetrabromobishenol A), along with global electronic, the non-halogen demand of electric equipment products raises, and light, thin, short, littleization of communication products trend, as the fire-retardant substrate of use in printed circuit board, except that non-halogen, the requirement of high Tg rises year by year, and is problem anxious to be solved.
Known, United States Patent (USP) the 5th, 458, No. 978 patent cases, it uses epoxy phosphate ester, the composition that nitrogen-containing epoxy thermoset and metal composite stiffening agent form, and it has second-order transition temperature is about 175 ℃, United States Patent (USP) the 4th, 973,631 and 5,086, in No. 156 patent cases, use separately to have the trihydrocarbyl phosphine oxide compound of active hydrogen substituting group (for example amido) or cooperate other amine type hardeners in order to hardening epoxy resin.
The technology that above-mentioned known patent case discloses often need be added the standard that multiple P contained compound or inorganics just can reach flame retardant resistance, makes the method processing conditions wayward or the quality of product is reduced but multiple extra additive adds regular meeting.
Though being compound, addition type phosphorus can improve flame retardant resistance, but can reduce the basic physical properties of resin, as thermotolerance, shortcomings such as wet fastness, so manyly just arise at the historic moment about the stiffening agent that improves this type of shortcoming, all excellent with its thermotolerance of hot type phenol resins and water tolerance, but than melamine (melamine) resin poor fire, so with both advantage thermotolerances, the resin formula of water tolerance and flame retardant resistance unification is inquired into widely.
The spy opens the composition that clear 64-79253 mentions phenol (phenol) class and melamine, and it is poorly soluble for MEK's, is not suitable for the processing of glass copper foil laminates, and can contains the volume unreacted reactant.
Summary of the invention
The present invention discloses a kind of many rings Resins, epoxy that contains reactive phosphorus compound modification, rigid structures such as Ppolynuclear aromatic, aliphatics, naphthalene are mainly arranged in structure, flame retardant resistance and water tolerance have been strengthened, aspect stiffening agent, reduce to increase nitrogen or to put content, the phosphorus content of flame-retardant epoxy resin omposition, and import the solvent solubility that aromatic structure improves the stiffening agent of phenol-melamine-formaldehyde condensation products, and improve the vitrifying transition point and the flame retardant resistance of laminated plates.
Detailed description of the invention
The relevant a kind of flame retardant resin of the present invention has the polycyclic Resins, epoxy that contains reactive P contained compound, and the resin that can replace halogen contained compound or bromination is as the flame retardant resistance composition.
The present invention is about a kind of flame retardant resin composition again, and it comprises
(1) Resins, epoxy of the polynuclear plane of P contained compound.
(2) not halogen-containing stiffening agent, its have active hydrogen can with the epoxy reaction in the Resins, epoxy.
(3) hardening accelerator.
Above-mentioned flame retardant resin composition has the excellent thermotolerance and the improved characteristics of flame retardant resistance, and it makes flame retardant resin composition have the phosphorus effect more excellent than known technology because of phosphorus-nitrogen, fire-retardant effect and the importing special chemical structure taken advantage of altogether of phosphorus-silicon.
The present invention discloses a kind of Resins, epoxy and composition thereof of P contained compound modification, disclosed is with
9, the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is hereinafter to be referred as HCA) react with the polynuclear plane Resins, epoxy that contains more than two epoxy group(ing), to make the Resins, epoxy of P contained compound modification.
The Resins, epoxy of the P contained compound modification that the present invention discloses is suc as formula shown in (A) to (E) formula:
(A)
The integer of n=0-12 in the formula; And R1=CH3, H; And X=A or B, and have at least an X be B wherein
Wherein E is
(B)
The X definition is the same in the formula; And the integer of m=0-12:
(C)
The X definition is the same in the formula; And the R1 definition is the same; And the integer of p=0-12;
(D)
The X definition is the same in the formula; And the R1 definition is the same; And the integer of q=0-12.
Above-mentioned Resins, epoxy can use separately or two kinds or multiple form of mixtures use, or uses with the epoxy resin composition formation of two epoxy group(ing).Wherein the Resins, epoxy of two epoxy group(ing) also can comprise shown in (E) formula:
(E)
The X definition is the same in the formula; And
The integer of k=0-12; And Y is
Above-mentioned (A)-(D) formula contains the Resins, epoxy of phosphide modification: (A)-(D) Resins, epoxy of P contained compound modification accounts for all Resins, epoxy to form 5-100 weight % is good.
Make the Resins, epoxy of P contained compound modification of the present invention, wherein the equivalent ratio is that the equivalent ratio of Resins, epoxy: HCA is 100: 5 to 100: 150, is good with 100: 50.
Make the Resins, epoxy of P contained compound modification of the present invention, its reactive mode can be fusion addition reaction or back flow reaction mode, wherein back flow reaction is the reactive mode of solvent refluxing, and suitable solvent is ketone, organic fragrant same clan, aprotic solvent, ethers, reaches ester class etc.
Organic fragrant same clan is preferable with toluene, dimethylbenzene, ketone is preferable with acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), aprotic solvent is with N, N-dimethylformamide, N, N-diethylformamide, dimethyl sulfoxide (DMSO) are preferable, and the ester class is preferable with ethyl acetate, isopropyl acid ethyl ester, propylene glycol monomethyl ether ethyl ester.
The temperature of reaction of making the Resins, epoxy of P contained compound modification of the present invention is generally 50 to 350 ℃, is preferable with 50 to 300 ℃.
Fire-proof resin composition of the present invention except the Resins, epoxy of P contained compound of the present invention, also can contain other not phosphorated Resins, epoxy.
Stiffening agent in the composition epoxy resin with flame retardant resistance of the present invention comprises and contains compound bearing active hydrogen, can with the phosphorous or nitrogen of epoxy reaction or the stiffening agent of crossing, and other not halogen-containing stiffening agents.
In the flame retardant resin composition of the present invention, the stiffening agent of spendable phosphorous or nitrogen or silicon has following (F)-(I) shown in the formula:
(F)
The E definition is the same in the formula;
(G)
The E definition is the same in the formula;
(H)
The E definition is the same in the formula; And the integer of s=0-12;
(I)
The integer of L=0-12 in the formula; Reach R2=NH2, CH3, C6H5; And
R3=H, adjacent CH3, a CH3, to CH3, adjacent C6H5, a C6H5, to C6H5.
Contained stiffening agent in the above-mentioned flame retardant resin composition, except that independent use or with two kinds or multiple form of mixtures use, or not halogen-containing and can use with other with the stiffening agent form of mixtures of epoxy reaction, comprise Dicyanodiamide, two amido ditans, two amido sulfobenzides, resol etc.
Contained stiffening agent content is according to the epoxy equivalent (weight) of the reactive behavior hydrogen equivalent of stiffening agent and Resins, epoxy and decide in the flame retardant resin composition of the present invention; The epoxy equivalent (weight) of Resins, epoxy is 100% o'clock, and the equivalent of the reactive hydrogens of stiffening agent is that 20-140% is preferable.
Contained hardening accelerator specific examples comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compounds in the flame retardant resin composition of the present invention; Or its mixture etc.
The usage quantity of hardening accelerator is the 50-50000ppm of composition total weight, is preferable with 100-30000ppm.
Flame retardant resin composition of the present invention has excellent thermotolerance and flame-retardant nature, after the stiffening agent sclerosis, can be used as high heat-stable material, for example: adhesive sheet or dipping body, the Copper Foil tackiness agent of matrix material, laminated plates, printed circuit board (PCB), coated with resins Copper Foil, the plain compound of the Resins, epoxy in the semiconductor sealing material, high heat-resisting powder body coating, engineering plastics etc. can be according to each compositions in the different purposes allotment compositions.
The present invention has the composition epoxy resin of the P contained compound modification of thermotolerance and flame retardant resistance can be in order to make laminated plates or adhesive sheet, it can use the impregnation fiber base material of organic or inorganic material, for example glass metal, carbon fiber, aromatic polyamide, boride, Mierocrystalline cellulose etc.
Embodiment
The present invention will describe in detail with the following example and comparative example, for therefore not limiting the scope of the invention.
Used each detailed description is as follows in embodiment and the comparative example:
Embodiment 1:(A) the formula compound is synthetic
With organo phosphorous compounds HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) 216g and Resins, epoxy (HP-7200, the Dicyclopenthadiene type, big Japanese ink goods) 1325g drops in the four-hole glass reaction still, elevate the temperature and after 110 ℃, evenly stir, add triethylamine 0.5g again, temperature of reaction is risen to 160 ℃ again, and reacted 2.5 hours, can obtain its epoxy equivalent (weight) of Resins, epoxy after the cooling is 381g/eq (the epoxy equivalent (weight) theoretical value is 385g/eq).
Embodiment 2:(B) the formula compound is synthetic
With 1-phenol 865g how, polyoxymethylene 150.15g, water 800g and oxalic acid 1g drop in the four-hole glass reaction still, fully stir, elevate the temperature to 80 ℃, react underpressure distillation removal moisture after 3 hours, add epoxy chloropropane 110g again, elevate the temperature to 130 ℃, slowly be added dropwise in the reactor about 3 hours with the sodium hydroxide 534g of 45 weight %, in the underpressure distillation mode excessive epoxy chloropropane is removed again, add 200g toluene dissolving after-filtration, add HCA216g and triethylamine 1g again, make temperature rise to 140 ℃, in about 3 hours of reaction times, toluene is removed in underpressure distillation, and can obtain its epoxy equivalent (weight) of Resins, epoxy after the cooling is 195g/eq (the epoxy equivalent (weight) theoretical value is 202g/eq).
Embodiment 3:(C) the formula compound is synthetic
With biphenyl 308g, phenol 180g, polyoxymethylene 90g, water 300g and tosic acid 0.2g drop in the four-hole glass reaction still, fully stir, elevate the temperature to 80 ℃, react underpressure distillation removal moisture after 3 hours, add epoxy chloropropane 555g again, elevate the temperature to 130 ℃, slowly be added dropwise in the reactor about 3 hours with the sodium hydroxide 534g of 45 weight %, in the underpressure distillation mode excessive epoxy chloropropane is removed again, add 100g toluene dissolving after-filtration, add HCA 216g and triethylamine 0.5g again, make temperature rise to 140 ℃, in about 3 hours of reaction times, toluene is removed in underpressure distillation, and can obtain its epoxy equivalent (weight) of Resins, epoxy after the cooling is 497g/eq (the epoxy equivalent (weight) theoretical value is 481g/eq).
Embodiment 4:(D) the formula compound is synthetic
With Organophosphorous compounds HCA 216g and Resins, epoxy (NPP-638, Phenol novolac type, the South Asia plastics) 900g drops in the four-hole glass reaction still, elevate the temperature and after 110 ℃, evenly stir, add triethylamine 0.5g again, temperature of reaction is risen to 160 ℃ again, and reacted 2.5 hours, can obtain its epoxy equivalent (weight) of Resins, epoxy after the cooling is 275g/eq (the epoxy equivalent (weight) theoretical value is 279g/eq).
Embodiment 5:(F) the formula compound is synthetic
With (HCA-HQ (2-(6-epoxy-6H-hexichol (c.e) (1.2) oxa-Buddhist quinoline-6-yl) 1,4-benzene-glycol) (HCA-HQ (2-(6-oxido-6H-dibenz (c.e) (1.2) oxaphorin-6-yl)-1,4-benzenediol)) 38.9g, tetramethoxy-silicane 4.56g, methyl alcohol 9g, propylene glycol 150g, hydrochloric acid 0.07g drops in the four-hole glass reaction still, fully stir, elevate the temperature to about 1 hour of 80-110 ℃ of reaction times, temperature of reaction is risen to 100-120 ℃ again, about 1 hour of reaction times, again temperature of reaction is risen to about 4 hours of 140 ℃ of reaction times, cooling adds methyl alcohol 200g, it is dry that throw out takes out the back universe later, can obtain stiffening agent hydrogen-oxygen valency 153KOH mg/g (stiffening agent hydrogen-oxygen valence theory value is 155KOH mg/g).
Embodiment 6:(G) the formula compound is synthetic
With 4,4 '-dihydroxy benaophenonel (4,4 ' Dihydroxybenzophenone) 21.44g, HCA 43.2g and dimethylbenzene 100g drop in the four-hole glass reaction still, stir, elevate the temperature to 130-135 ℃, distillation concentrates after about 3 hours of reaction times, can obtain stiffening agent hydrogen-oxygen valency 170KOH mg/g.(stiffening agent hydrogen-oxygen valence theory 174KOH mg/g).
Embodiment 7:(H) the formula compound is synthetic
With benzophenone 3,3 ', 4,4 '-tetracarboxylic dianhydride (Benzophenone-3,3 '-4,4 '-tetracarboxylic dianhydride) 32.2g, HCA 43.2g and dimethylbenzene 100g drop in the four-hole glass reaction still, stir, elevate the temperature, about 3 hours of reaction times to 130-135 ℃, add N,N-DIMETHYLACETAMIDE 30g again, 4-amino-phenol (4-Aminophenol) 21.8g and tosic acid 0.5g, make temperature remain on 130-135 ℃, in 4 hours reaction times, the cooling back is with the yellow soda ash alkali cleaning of 2% (weight percent), remove solvent to be washed to neutral underpressure distillation again, can obtain stiffening agent hydrogen-oxygen valency 174KOH mg/g.(stiffening agent hydrogen-oxygen valence theory value is 176KOH mg/g).
Embodiment 8:(I) the formula compound is synthetic
Benzo guanamine (Benzoguanamine) 187.2g, orthoxenol (o-phenyl phenol) 187g, polyoxymethylene 66.07g, water 90g and triethylamine 100g are dropped in the four-hole glass reaction still, stir, elevate the temperature to 80 ℃, about 3 hours of reaction times, temperature rises to 100-130 ℃ making gradually, removal moisture also reacted 2 hours, can obtain stiffening agent hydrogen-oxygen valency 152KOH mg/g.(stiffening agent hydrogen-oxygen valence theory value is 154KOH mg/g).
Comparative example 1:
With Resins, epoxy and stiffening agent, smash with mechanical beating crusher, and it is levigate with mortar, and then with equivalence ratio 1: 1 and with the 0.1%TPP thorough mixing, Hou be poured into again in the mould and, make its even melting mixing with baking oven for heating to 130 ℃, and then with 160 ℃ of pre-hardening 1 hour, 180 ℃ of sclerosis 2 hours, 220 ℃ of post-hardening 2 hours just can obtain the required test piece of physical property measurement afterwards.
Table one UL-94 flame retardant test and second-order transition temperature (Tg)
Resins, epoxy/stiffening agent P% N% Si% UL-94 Tg (℃)
(A)/(F) 5.61 - 1.03 V-0 170
(A)/(G) 5.65 - - V-0 152
(A)/(H) 5.69 2.01 - V-0 157
(A)/(I) 1.02 8.59 - V-0 176
(B)/(F) 7.17 - 1.37 V-0 208
(B)/(G) 3.85 - - V-0 173
(B)/(H) 3.83 2.74 - V-0 176
(B)/(I) 1.05 11.42 - V-0 215
(C)/(F) 5.83 - 0.89 V-0 186
(C)/(G) 5.87 - - V-0 160
(C)/(H) 5.90 1.73 - V-0 172
(C)/(I) 1.85 7.44 - V-0 191
(D)/(F) 6.54 - 1.20 V-0 189
(D)/(G) 6.64 - - V-0 165
(D)/(H) 6.69 2.37 - V-0 178
(D)/(I) 1.18 10.01 - V-0 197
Comparative example 2
Resins, epoxy with (A)-(D) formula compound, with two epoxy group(ing) naphthalene type Resins, epoxy (HP-4032, big Japanese ink goods), bisphenol A type epoxy resin (NPW-704, the South Asia plastics) mixing in varing proportions cooperates different stiffening agents, finds out to reach UL-94, the combination of the minimum phosphorus content of V-0 standard, and water-intake rate; The water-intake rate testing method is for to put into pressure cooker with above-mentioned test piece, with under 2 normal atmosphere and the 120 ℃ of situations through 0.5 hour, take out the weight difference of surveying before and after its steam heating, and calculate its water-intake rate.
The fire-retardant test piece test of table two
Epoxy resin hardener P% Tg (℃) water-intake rate %
(A)/HP-4032 (I) 0.7 186 0.5
(B)/HP-4032 (I) 0.7 210 0.3
(B)/HP-4032 (I) 1.6 160 0.3
(C)/HP-4032 (I) 0.6 195 0.4
(D)/HP-4032 (I) 0.65 193 0.2
(D)/EPEL-127 Dicyanodiamide 2.1 142 1.3
(D)/NPLN-704 (I) 0.75 180 0.4
(D)/NPLN-704 diamines sulfobenzide 1.8 156 0.6
(D)/HP-4032 (F) 1.5 187 0.3
The present invention has cooperated above-mentioned specific embodiment and comparative example to be described, and those skilled in the art can make multiple variation based on above description.Scope of the present invention comprises those variations in claim scope of the present invention and spirit thereof.
Claims (15)
1. fire retarding epoxide resin, it has one and is selected from (A) chemical structure to (E) formula:
The integer of n=0-12 in the formula; And R1=CH3, H; And
X=A or B, and have at least an X be B wherein
Wherein E is
The X definition is the same in the formula; And
The integer of m=0-12;
The X definition is the same in the formula; And the R1 definition is the same; And
The integer of p=0-12;
The X definition is the same in the formula; And the R1 definition is the same; And
The integer of q=0-12;
The integer of k=0-12 in the formula; And Y is
Wherein the E definition is the same.
2. fire retarding epoxide resin according to claim 1, wherein said (A) formula compounds content is 10 to the 90 weight % that account for composition.
3. fire retarding epoxide resin according to claim 1, wherein said (B) formula compounds content is 10 to the 90 weight % that account for composition.
4. fire retarding epoxide resin according to claim 1, wherein said (C) formula compounds content is 10 to the 90 weight % that account for composition.
5. fire retarding epoxide resin according to claim 1, wherein said (D) formula compounds content is 10 to the 90 weight % that account for constituent.
6. fire retarded epoxy resin composition is characterized in that it comprises:
(1) according to claim 1, it has one and is selected from (A) chemical structure to (E) formula,
(2) not halogen-containing stiffening agent, its have active hydrogen can with the epoxy reaction in the Resins, epoxy,
(3) hardening accelerator.
7. fire retarded epoxy resin composition according to claim 6, the not halogenous stiffening agent of its composition (2) is a compound nitrogenous or phosphorus or silicon, has following (F) to the structure shown in (I) formula:
The E definition is the same in the formula:
The E definition is the same in the formula;
The E definition is the same in the formula; And
The integer of s=0-12;
(I)
The integer of L=0-12 in the formula; Reach R2=NH2, CH3, C6H5; And
R3=H, adjacent CH3, a CH3, to CH3, adjacent C6H5, a C6H5, to C6H5.
8. stiffening agent according to claim 7, it can use separately or mix use with other stiffening agent.
9. stiffening agent according to claim 8, wherein said composition (F) formula compounds content is 5 to the 100 weight % that account for stiffening agent.
10. stiffening agent according to claim 8, wherein said composition (G) formula compounds content is 5 to the 100 weight % that account for stiffening agent.
11. stiffening agent according to claim 8, wherein said composition (H) formula compounds content is 5 to the 100 weight % that account for stiffening agent.
12. stiffening agent according to claim 8, wherein said composition (I) formula compounds content is 5 to the 100 weight % that account for stiffening agent.
13. fire retarded epoxy resin composition according to claim 6, wherein said composition (3) hardening accelerator are selected from tertiary amine, three grades of phosphines, quaternary ammonium salt, quaternary alkylphosphonium salt, boron trifluoride complex, lithiumation thing and imidazolium compoundss; Or its mixture.
14. according to each described fire retarding epoxide resin of claim 1 to 5, its in order to substrate of making adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method and using, copper clad laminate with tackiness agent, partly lead encapsulation.
15. according to each described fire retarded epoxy resin composition of claim 6 to 13, its in order to substrate of making adhesive sheet, matrix material, laminated plates, printed circuit board (PCB), Layer increasing method and using, copper clad laminate with tackiness agent, partly lead encapsulation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307170A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | A kind of flame-retardant phosphorus-containing epoxy powder composition |
| CN101195676B (en) * | 2007-12-27 | 2012-08-22 | 东莞理工学院 | Phosphorus-containing bisphenol A novolac epoxy resin and preparation method thereof |
| CN103421273A (en) * | 2012-05-22 | 2013-12-04 | 中山台光电子材料有限公司 | Halogen-free resin composition |
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2003
- 2003-11-25 CN CN 200310115435 patent/CN1621443A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195676B (en) * | 2007-12-27 | 2012-08-22 | 东莞理工学院 | Phosphorus-containing bisphenol A novolac epoxy resin and preparation method thereof |
| CN101307170A (en) * | 2008-07-10 | 2008-11-19 | 天津市凯华绝缘材料有限公司 | A kind of flame-retardant phosphorus-containing epoxy powder composition |
| CN101307170B (en) * | 2008-07-10 | 2011-08-10 | 天津市凯华绝缘材料有限公司 | Fire retardant phosphorus-containing epoxy powder composition |
| CN103421273A (en) * | 2012-05-22 | 2013-12-04 | 中山台光电子材料有限公司 | Halogen-free resin composition |
| CN103421273B (en) * | 2012-05-22 | 2016-02-10 | 中山台光电子材料有限公司 | Halogen-free resin composition |
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