WO2014206487A1 - A halogen free flame retardant epoxy resin composition - Google Patents
A halogen free flame retardant epoxy resin composition Download PDFInfo
- Publication number
- WO2014206487A1 WO2014206487A1 PCT/EP2013/063658 EP2013063658W WO2014206487A1 WO 2014206487 A1 WO2014206487 A1 WO 2014206487A1 EP 2013063658 W EP2013063658 W EP 2013063658W WO 2014206487 A1 WO2014206487 A1 WO 2014206487A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- compound
- resin composition
- formula
- cured epoxy
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 124
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 113
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 113
- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 31
- -1 flame retardant halogen Chemical class 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 61
- 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 claims description 39
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 20
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 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 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000004848 polyfunctional curative Substances 0.000 claims description 11
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 150000002118 epoxides Chemical class 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002113 nanodiamond Substances 0.000 claims description 5
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 5
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012802 nanoclay Substances 0.000 claims description 4
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 150000008064 anhydrides Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- KUCLDWMEXXSGQT-UHFFFAOYSA-N n-[[1-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]methyl]-1-(oxiran-2-yl)-n-(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1(CN(CC2OC2)CC2OC2)CCCCC1)CC1CO1 KUCLDWMEXXSGQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 239000000779 smoke Substances 0.000 abstract description 8
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 49
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 34
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- 239000000047 product Substances 0.000 description 30
- 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 28
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 21
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 16
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 7
- 239000012263 liquid product Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- MLOZFLXCWGERSM-UHFFFAOYSA-N 8-oxabicyclo[5.1.0]octane Chemical compound C1CCCCC2OC21 MLOZFLXCWGERSM-UHFFFAOYSA-N 0.000 description 3
- 0 CC(CC(COC(*CI(c1ccccc1)(OCC(*)CNC1COC1)=Cl)=Cl)O)[U]CC1ClC1 Chemical compound CC(CC(COC(*CI(c1ccccc1)(OCC(*)CNC1COC1)=Cl)=Cl)O)[U]CC1ClC1 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- TWQUDMBKCVTHLR-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]oxypropanoic acid Chemical compound OC(=O)CCOP(O)(=O)C1=CC=CC=C1 TWQUDMBKCVTHLR-UHFFFAOYSA-N 0.000 description 1
- KKVCZKZPPWRTNU-UHFFFAOYSA-N C(C1[ClH]C1)[ClH]C1C[ClH]C1 Chemical compound C(C1[ClH]C1)[ClH]C1C[ClH]C1 KKVCZKZPPWRTNU-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1415—Compounds containing the structure P-O-acyl, P-O-heteroatom, P-O-CN
- C07F9/1417—Compounds containing the structure P-O-C(=X)- (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
- C07F9/4093—Compounds containing the structure P(=X)-X-C(=X)- (X = O, S, Se)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/65502—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a three-membered ring
- C07F9/65505—Phosphonic acids containing oxirane groups; esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the invention relates to a halogen free flame/fire retardant epoxy resin composition with excellent mechanical properties, thermal resistance, low smoke release and good processability.
- the invention also refers to the process of obtaining said epoxy resin composition. Moreover, the present invention relates to the use of the halogen free flame/fire retardant epoxy resin composition as adhesive.
- the present invention relates to articles comprising halogen free flame/fire retardant epoxy resin composition and their uses as an electric or electronic circuit component or a structural element for transportation and building.
- Epoxy resins are widely-used matrix resins due to their superior thermal, chemical-resistance, electrical-resistance and mechanical properties.
- the flammability of epoxy resins greatly restricts their applications.
- improving the flame retardancy has been the key challenge for epoxy resins research.
- halogenated flame retardants such as tetrabromobisphenol A (TBBPA)
- TBBPA tetrabromobisphenol A
- they produce a poisonous and corrosive smoke and may generate super-toxic halogenated dibenzodioxins and dibenzofurans during combustion, which is forbidden in the new environmental legislations Registration, Evaluation, Authorisation and Restriction of Chemical substances (REACH), Waste Electrical and Electronic Equipment Directive (WEEE) and Restriction of Hazardous Substances (RoHS).
- REACH Registration, Evaluation, Authorisation and Restriction of Chemical substances
- WEEE Waste Electrical and Electronic Equipment Directive
- RoHS Restriction of Hazardous Substances
- Flame retardants can either be physically mixed with the base material (additive flame retardants) or chemically bonded to it (reactive flame retardants).
- New additive non-halogen flame retardants formulations are, for example, ammonium polyphosphate (APP), triphenyl phosphate (TPP), dimethyl methylphosphonate (DMMP), tricresyl phosphate (TCP), cresyldiphenyl phosphate (CDP), resorcinol bis(diphenyl phosphate) (RDP) and bisphenol A bis(diphenyl phosphate) (BDP), which are described in the corresponding patents US5945467, US5919844, US4918122, US5932637, US6348523, US6713163 and EP1359174.
- the flame retardancy of epoxy resins has been improved in some extent; however, this effect sacrifices application performances such as water resistance, mechanical resistance and transparency due to the high percentage addition and the poor chemical compatibility with the polymer structure.
- organophosphoruses compounds are commonly incorporated to epoxy resins due to its thermal and hydrolytic stability [US6353080 and US6403690].
- other phosphorus element-containing compounds are described as difunctional or trifunctional phosphine oxide crosslinkers, that is, as effective curing agents [US0065869].
- Reactive flame retardants as 9, 10-Dihydro-9-oxa- 10-phosphaphenanthrene 10-oxide (DOPO) and their derivatives are also examples to mention [US4280951].
- the present invention discloses a novel halogen free flame retardant epoxy resin composition with excellent mechanical properties, thermal resistance, fire retardancy, low smoke release and good processability. Its flame retardancy derives from the flame retardant halogen free phosphorous ingredient.
- the invention also refers to the process of obtaining said epoxy resin composition.
- the present invention relates to the use of the halogen free flame/fire retardant epoxy resin composition as adhesive.
- a first aspect of the present invention relates to a halogen free cured epoxy resin composition that comprises the following components:
- At least one epoxy resin matrix selected from the list comprising a glycidyl ether/ester type epoxy resin, a glycidyl amine type epoxy resin and a combination thereof, wherein the glycidyl amine type epoxy resin has at least one of the following molecular group,
- a preferred embodiment of the present invention provides a cured epoxy resin composition, wherein the glycidyl ether/ester type epoxy resin is selected from the list consisting of
- n is a value between 0 and 10. More preferably, the glycidyl ether/ester type epoxy resins have n values between 1 a 5.
- the glycidyl amine type epoxy resin of the cured epoxy resin composition described above is selected from the list comprising Tris(2,3-epoxypropyl) isocyanurate, 4,4'-Methylenebis(N,N- diglycidylaniline), bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-Diglycidyl-4- glycidyloxyaniline and a combination thereof.
- a further embodiment of the present invention provides a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula I
- Ri and R3 are independently selected from the list comprising epoxides, -XR 4 , -alkyl(Ci-C 4 )-COO-R 5 , -COOR 6 and -Y-NH 2 ,
- X is selected from O, -NH, -S-,
- Y is selected from the list comprising hydrogen, alkyl (C1-C10), cycloalkyl, aryl and aralkyl,
- R 4 , R 5 and R6 are independently selected from the list comprising hydrogen, alkyl (Ci-C 4 ), aryl and diol,
- R2 is selected from the list comprising hydrogen, alkyl (Ci-C 4 ), cycloalkyl, aryl and aralkyl,
- epoxide relates to is cyclic ether with three ring atoms.
- epoxides feature the epoxy prefix, such as in the compound 1 ,2-epoxycycloheptane, which can also be called cycloheptene epoxide, or simply cycloheptene oxide.
- alkyl (Ci-C 4 ) as used herein relates to a linear or branched aliphatic chains, which have from 1 to 4 carbon atoms, for example, methyl, ethyl, n- propyl, i-propyl, n-butyl, tert-butyl and sec-butyl.
- the alkyl group has between 1 and 3 atoms, more preferably between 1 and 2 atoms, more preferably is methyl.
- alkyl (C1-C10) as used herein relates to a linear or branched aliphatic chains, which have from 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl and sec-butyl.
- the alkyl group has between 1 and 6 atoms.
- the term "aryl” relates to an aromatic carbocyclic chain, which has from 6 to 18 carbon atoms, and can be a single or multiple ring, in this last case with separated and/or condensed rings.
- the aryl group is a phenyl.
- Non-limiting examples of aryl os are phenyl, naphthyl and indenyl groups.
- the aryl group is a phenyl, wherein the phenyl group may contain 1 or more substituents such as alkyl, hydroxyl, nitro and amine groups.
- the term "diol” as used herein relates to a chemical compound containing two hydroxyl groups (— OH groups), which can be geminal, this means, the diol has two hydroxyl groups bonded to the same atom or vicinal (glycols), wherein the two hydroxyl groups occupy vicinal positions, that is, they are attached to adjacent atoms.
- An example of a diol group is -CH 2 -CHOH-CH 2 OH.
- cycloalkyl relates to a stable monocyclic or bicyclic radical of 3 to 10 members that is saturated or partially saturated, and which only consists of carbon and hydrogen atoms, such as cyclopentyl, cyclohexyl or adamantyl
- aralkyl relates, in the present invention, to an aliphatic chain wherein at least one of the hydrogen has been substituted by an aryl group, with the previous senses but without being limited to, a benzyl or phenethyl group.
- Ri and R3 are -OH and R 2 is a phenyl group.
- Ri is an -OH
- R 2 is a phenyl group
- R3 is a alkyl(Ci-C 4 )-COO-R 5 and R 5 is a hydrogen.
- Ri and R3 are -OH and R 2 is a methyl group.
- Ri and R3 are -OH and R 2 is hydrogen. These reactive phosphorous compounds provide flame retardancy and consequently fire retardancy to the cured epoxy resin compositions. Furthermore, they enhance the mechanical properties of the cured epoxy resin compositions.
- the compound of formula I is the compound of formula II.
- the compound of formula I is the compound of formula III.
- Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula IV havin n values between 0 and 10.
- Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula V having n between 0 and 10.
- Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula VI having n values between 0 and 10.
- Another preferred embodiment refers to a epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula VII havingn values between 0 and 5.
- Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula VII having n values between 0 and 5.
- a further embodiment of the present invention provides a cured epoxy resin composition, wherein the flame retardant phosphorous compound is in a weight percent between 0.5 and 5% based on the total weight of the cured composition. More preferably is in a weight percent between 0.5 and 4% based on the total weight of the cured composition.
- Another preferred embodiment relates to a cured epoxy resin composition, wherein the hardener of the epoxy resin matrix comprises an aryl group. This aryl group has been defined above. More preferably, the hardener is selected from the list comprising aminophenyl sulfone (DDS), diaminodiphenylmethane (DDM) and a combination thereof.
- DDS aminophenyl sulfone
- DDM diaminodiphenylmethane
- the term "hardener” as used herein refers to compounds that serve as crossi inkers of the epoxy resins so that the mechanical properties as well as high temperature and chemical resistance are improved.
- the hardener of the epoxy resin composition described above is in a weight percent between 10 and 40% based on the total weight of the cured composition.
- a further embodiment of the present invention relates to the cured epoxy resin composition described previously, which further comprises a nanofiller. More preferably, the nanofiller is selected from the list comprising nanoclay, carbon nanotubes and nanofibers, nanodiamonds, nano zirconium phosphate, graphite, and a combination thereof.
- nanofiller relates to a doping agent distributed in the matrix of an epoxy resin composition, whose individual elements have at least one of their dimensions in the nanoscale.
- nanofillers include nanoclays, carbon nanotubes and nanofibres, nanodiamonds, nano zirconium phosphate and graphite.
- the second aspect of the present invention refers to a process for obtaining the cured epoxy resin composition described previously that comprises following steps:
- step (a) adding at least one flame retardant phosphorous compound to the mixture of step (a),
- step (b) transferring the mixture obtained in step (b) into a mold
- step (c) curing the mixture inside a mold of step (c) at least once at a temperature value between 120 and 220°C.
- the invention relates to the above mentioned process, wherein the curing step (d) is carried out in one step at a temperature of 180°C and maintaining said temperature for 2 hours.
- the invention refers to the process described previously, wherein the curing step (d) is carried out in three steps at temperatures values between 120°C and 220 a c and maintaining said temperature for between 30 and 150 minutes.
- step (d) is carried out by following continuously the next three steps: i) curing the mixture obtained in step (c) at a temperature of 150 °C and maintaining the temperature for 1 hour,
- a further embodiment of the present invention relates to the above mentioned process described previously, wherein flame retardant phosphorous compound of step (b) is further combined with a nanofiller. More preferably, the nanofiller is selected from the list comprising nanoclay, carbon nanotubes and nanofibers, nanodiamonds, nano zirconium phosphate, graphite, and a combination thereof.
- a third aspect of the present invention relates to the use of the cured epoxy resin composition described before as adhesive.
- a fourth aspect of the present invention relates to an article comprising the above mentioned cured epoxy resin composition.
- a fifth aspect of the present invention refers to an article coated by the cured epoxy resin composition described above.
- a sixth aspect of the invention relates to a fiber reinforced composite article comprising the previously described cured epoxy resin composition.
- the fiber reinforced composite article is a laminate or a prepreg.
- Pre-preg as used here is a term for "pre-impregnated" composite fibres where a material, such as epoxy is already present. Usually the pre-preg takes the form of a weave or is unidirectional.
- the epoxy resin is only partially cured to allow easy handling and requires cold storage to prevent complete curing until complete polymerization is done, most commonly by heat.
- a seventh aspect of the invention refers to the above mentioned article which is an electric or electronic circuit component or a structural element for transportation and building.
- transportation refers to aircrafts, ships, rails, cars, bicycles and the like.
- building relates to any structural element forming any kind of building. Furthermore, the term refers to any element taking part of the indoor decoration of a building.
- An eighth aspect of the invention relates to an electric or electronic circuit component having an insulating coating of the cured epoxy resin composition described previously.
- a ninth aspect of the invention is a compound of formula II, which is obtained by reaction of phenylphosphonic acid with glycidol at temperatures between 30 and 70°C.
- a tenth aspect of the invention is a compound of formula III, which is obtained by reaction of 2-carboxyethyl(phenyl)phosphonic acid with glycidol
- An eleveth aspect of the invention is a compound of formula IV, which is obtained by reaction of phenylphosphonic acid with ethylene glycol diglycidyl ether at temperatures between 30 and 70°C.
- a twelfth aspect of the present invention is a compound of formula V, which is obtained by reaction of phenylphosphonic acid with diglycidyl ether at temperatures between 30 and 70°C.
- a thirteenth aspect of the present invention is a compound of formula VI, which is obtained by reaction of 2-carboxyethyl(phenyl)phosphinic acid with diglycidyl ether at temperatures between 30 and 70°C.
- a fourteenth aspect of the present invention refers to a compound of formula VII, which is obtained by reaction of phenylphosphomic acid with phenylene diisocyanate at temperatures between 30 and 70 °C.
- a fifteenth aspect of the present invention relates to a compound of formula VIII, which is obtained by reaction of phosphorous acid with tolyene diisocyanate at temperatures between 30 and 70 °C.
- a sixteenth aspect of the invention relates to the use of a compound selected from the list comprising the compound of formula II
- a curable epoxy resin composition was made by mixing:
- the limiting oxygen index is the minimum concentration of oxygen (expressed as a percentage) that will support combustion of a polymer. It was measured by passing a mixture of oxygen and nitrogen over a burning specimen, and reducing the oxygen level until a critical level was reached. LOI values for the composites were determined by standardized tests, according to the ASTM D2863 (samples of dimensions 130 * 6.5 * 3.2 mm 3 ).
- UL 94 is a plastics flammability standard released by Underwriters Laboratories of the USA. The standard classifies plastics according to how they burn in various orientations and thicknesses. From lowest (least flame-retardant) to highest (most flame-retardant), the classifications are: HB: slow burning on a horizontal specimen; burning rate ⁇ 76 mm/min for thickness ⁇ 3 mm and burning stops before 100 mm
- ⁇ V1 burning stops within 30 seconds on a vertical specimen; drips of particles allowed as long as they are not inflamed.
- V0 burning stops within 10 seconds on a vertical specimen; drips of particles allowed as long as they are not inflamed.
- CCT Cone Calorimeter Test
- the cone calorimeter test is the most significant bench scale instrument to study the fire behavior of small specimen of various materials, following the procedures in ISO 5660 (without the use of the "frame and grid") using an FTT cone calorimeter.
- Square specimens (100x100 ⁇ 3 mm 3 ) were irradiated at a heat flux of 50 kW/m 2 .
- This method is able to investigate some important parameters in a fire, like heat release rate (HRR), peak of heat release rate (p- HRR), total heat release (THR), total smoke production (TSP), among others.
- the glass-liquid transition (or glass transition for short) is the reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle state into a molten or rubber-like state.
- all Tg have been measured by dynamic mechanical analysis (DMA).
- Example 9 A curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- Example 11 A curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- Example 13 A curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- Curing process 70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 40 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 7.4 g of 2- carboxyethyl(phenyl)phosphinic acid was added as a flame retardant. The mixture was stirred at 120°C until 2-carboxyethyl(phenyl)phosphinic acid had completely dissolved, and then the mixture was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
- a curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- a curable epoxy resin composition was made by mixing:
- Example 20 A curable epoxy resin composition was made by mixing:
- Curing process 50 g of high purity bisphenol A diglycidylether (D.E.R. 332), 50 g of 4, 4'- methylenebis(N,N-digylcidylaniline), and 48 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 16 g of the flame retardant compound of formula V described in Example 4, that is, the product of phenylphosphonic acid and phenylene diisocyanate was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was obtained, and then the solution was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
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Abstract
The present invention discloses a novel halogen free flame retardant epoxy resin composition with excellent mechanical properties, thermal resistance, fire retardancy, low smoke release and good processability. Its flame retardancy derives from the flame retardant halogen free phosphorous ingredient. Furthermore, the invention refers to the process of obtaining said epoxy resin composition. Moreover, the present invention relates to the use of the halogen free flame/fire retardant epoxy resin composition as adhesive. In addition, the present invention relates to articles comprising halogen free flame/fire retardant epoxy resin composition and their uses as an electric or electronic circuit component or a structural element for transportation and building.
Description
A HALOGEN FREE FLAME RETARDANT EPOXY RESIN COMPOSITION
The invention relates to a halogen free flame/fire retardant epoxy resin composition with excellent mechanical properties, thermal resistance, low smoke release and good processability.
The invention also refers to the process of obtaining said epoxy resin composition. Moreover, the present invention relates to the use of the halogen free flame/fire retardant epoxy resin composition as adhesive.
Furthermore, the present invention relates to articles comprising halogen free flame/fire retardant epoxy resin composition and their uses as an electric or electronic circuit component or a structural element for transportation and building.
BACKGROUND ART Epoxy resins are widely-used matrix resins due to their superior thermal, chemical-resistance, electrical-resistance and mechanical properties. However, the flammability of epoxy resins greatly restricts their applications. As the awareness of fire security increased, improving the flame retardancy has been the key challenge for epoxy resins research.
Although adding halogenated flame retardants to epoxy resins matrices, such as tetrabromobisphenol A (TBBPA), is quite effective method for improving the flame retardancy of epoxy resins with electrical and electronic applications, they produce a poisonous and corrosive smoke and may generate super-toxic halogenated dibenzodioxins and dibenzofurans during combustion, which is forbidden in the new environmental legislations Registration, Evaluation, Authorisation and Restriction of Chemical substances (REACH), Waste
Electrical and Electronic Equipment Directive (WEEE) and Restriction of Hazardous Substances (RoHS).
Since the implementation of environmental directives banning or limiting the use of halogenated compounds, the development of flame retardants based on epoxy resins has focused on more environmentally friendly alternatives. In recent years, a broad range of new halogen free flame retardants have been developed. Flame retardants can either be physically mixed with the base material (additive flame retardants) or chemically bonded to it (reactive flame retardants). New additive non-halogen flame retardants formulations are, for example, ammonium polyphosphate (APP), triphenyl phosphate (TPP), dimethyl methylphosphonate (DMMP), tricresyl phosphate (TCP), cresyldiphenyl phosphate (CDP), resorcinol bis(diphenyl phosphate) (RDP) and bisphenol A bis(diphenyl phosphate) (BDP), which are described in the corresponding patents US5945467, US5919844, US4918122, US5932637, US6348523, US6713163 and EP1359174. Here, the flame retardancy of epoxy resins has been improved in some extent; however, this effect sacrifices application performances such as water resistance, mechanical resistance and transparency due to the high percentage addition and the poor chemical compatibility with the polymer structure.
The main disadvantage of the additive flame retardant has been overcome by a great number of the reactive type formulations. For example, organophosphoruses compounds are commonly incorporated to epoxy resins due to its thermal and hydrolytic stability [US6353080 and US6403690]. Moreover, other phosphorus element-containing compounds are described as difunctional or trifunctional phosphine oxide crosslinkers, that is, as effective curing agents [US0065869]. Reactive flame retardants as 9, 10-Dihydro-9-oxa- 10-phosphaphenanthrene 10-oxide (DOPO) and their derivatives are also examples to mention [US4280951]. A plastics flammability standard released
UL 94-VO rating of approximately 3 mm, was reached incorporating about 12 wt% DOPO in the DGEBA/DDS system [D. Sunand Y. Yao, Polymer Degradation and Stability, 96, 1720-1724 (201 1 )]. However a decrease of the Glass Transition Temperature (Tg) is also observed herein. Main disadvantages of the reactive flame retardants relate to decreases of mechanical performances, thermal resistance, and processability of the epoxy resins composition containing them. Moreover, the flame retardant efficiency is low and the combustion produces a big amount of smoke. For the reasons stated above, it is needed to develop new halogen free flame retardant epoxy resin composition with excellent thermal resistance, superior mechanical properties and low smoke release.
SUMMARY OF THE INVENTION
The present invention discloses a novel halogen free flame retardant epoxy resin composition with excellent mechanical properties, thermal resistance, fire retardancy, low smoke release and good processability. Its flame retardancy derives from the flame retardant halogen free phosphorous ingredient.
The invention also refers to the process of obtaining said epoxy resin composition.
Moreover, the present invention relates to the use of the halogen free flame/fire retardant epoxy resin composition as adhesive.
Furthermore, the present invention relates to articles comprising halogen free flame/fire retardant epoxy resin composition and their uses as an electric or electronic circuit component or a structural element for transportation and building.
Therefore, a first aspect of the present invention relates to a halogen free cured epoxy resin composition that comprises the following components:
• at least one epoxy resin matrix selected from the list comprising a glycidyl ether/ester type epoxy resin, a glycidyl amine type epoxy resin and a combination thereof, wherein the glycidyl amine type epoxy resin has at least one of the following molecular group,
• at least one flame retardant phosphorous compound, wherein the flame retardant compound is in a weight percent between 0.5 and 15% based on the weight of the cured composition,
• and at least a hardener of the epoxy resin matrix in a stoichiometric amount based on the weight of the cured composition, which comprises an amine group, an anhydride group, an aryl group, a sulfhydryl group or a combination thereof.
Thus a preferred embodiment of the present invention provides a cured epoxy resin composition, wherein the glycidyl ether/ester type epoxy resin is selected from the list consisting of
Bisphenol A epoxy resin
II
>-CHr-CH-CHr+-0- ■O-CH2-CH-CH2
H OH H
Bisphenol F epoxy resin
Bisphenol S epoxy resin
and Novolac epoxy resin,
wherein n is a value between 0 and 10. More preferably, the glycidyl ether/ester type epoxy resins have n values between 1 a 5.
In another preferred embodiment, the glycidyl amine type epoxy resin of the cured epoxy resin composition described above, is selected from the list comprising Tris(2,3-epoxypropyl) isocyanurate, 4,4'-Methylenebis(N,N- diglycidylaniline), bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-Diglycidyl-4- glycidyloxyaniline and a combination thereof.
A further embodiment of the present invention provides a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula I
wherein
Ri and R3 are independently selected from the list comprising epoxides, -XR4, -alkyl(Ci-C4)-COO-R5, -COOR6 and -Y-NH2,
X is selected from O, -NH, -S-,
Y is selected from the list comprising hydrogen, alkyl (C1-C10), cycloalkyl, aryl and aralkyl,
R4, R5 and R6 are independently selected from the list comprising hydrogen, alkyl (Ci-C4), aryl and diol,
and R2 is selected from the list comprising hydrogen, alkyl (Ci-C4), cycloalkyl, aryl and aralkyl,
In the present invention, the term "epoxide" relates to is cyclic ether with three ring atoms. As a functional group, epoxides feature the epoxy prefix, such as in the compound 1 ,2-epoxycycloheptane, which can also be called cycloheptene epoxide, or simply cycloheptene oxide.
The term "alkyl (Ci-C4)" as used herein relates to a linear or branched aliphatic chains, which have from 1 to 4 carbon atoms, for example, methyl, ethyl, n- propyl, i-propyl, n-butyl, tert-butyl and sec-butyl. Preferably the alkyl group has between 1 and 3 atoms, more preferably between 1 and 2 atoms, more preferably is methyl. The term "alkyl (C1-C10)" as used herein relates to a linear or branched aliphatic chains, which have from 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, tert-butyl and sec-butyl. Preferably the alkyl group has between 1 and 6 atoms. In the present invention, the term "aryl" relates to an aromatic carbocyclic chain, which has from 6 to 18 carbon atoms, and can be a single or multiple ring, in this last case with separated and/or condensed rings. In the present invention, preferably the aryl group is a phenyl. Non-limiting examples of aryl grupos are phenyl, naphthyl and indenyl groups. Preferably the aryl group is a phenyl, wherein the phenyl group may contain 1 or more substituents such as alkyl, hydroxyl, nitro and amine groups.
The term "diol" as used herein relates to a chemical compound containing two hydroxyl groups (— OH groups), which can be geminal, this means, the diol has two hydroxyl groups bonded to the same atom or vicinal (glycols), wherein the two hydroxyl groups occupy vicinal positions, that is, they are attached to adjacent atoms. An example of a diol group is -CH2-CHOH-CH2OH.
The term "cycloalkyl" relates to a stable monocyclic or bicyclic radical of 3 to 10 members that is saturated or partially saturated, and which only consists of carbon and hydrogen atoms, such as cyclopentyl, cyclohexyl or adamantyl
The term "aralkyl" relates, in the present invention, to an aliphatic chain wherein at least one of the hydrogen has been substituted by an aryl group, with the previous senses but without being limited to, a benzyl or phenethyl group. In a more preferred embodiment, Ri and R3 are -OH and R2 is a phenyl group.
In another more preferred embodiment, Ri is an -OH, R2 is a phenyl group, R3 is a alkyl(Ci-C4)-COO-R5 and R5 is a hydrogen. In another more preferred embodiment, Ri and R3 are -OH and R2 is a methyl group.
In another more preferred embodiment, Ri and R3 are -OH and R2 is hydrogen. These reactive phosphorous compounds provide flame retardancy and consequently fire retardancy to the cured epoxy resin compositions. Furthermore, they enhance the mechanical properties of the cured epoxy resin compositions. In another more preferred embodiment, the compound of formula I is the compound of formula II.
Another preferred embodiment, the compound of formula I is the compound of formula III.
Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula IV havin n values between 0 and 10.
[IV]
Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula V having n between 0 and 10.
[V]
Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula VI having n values between 0 and 10.
[VI]
Another preferred embodiment refers to a epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula VII havingn values between 0 and 5.
[VII]
Another preferred embodiment refers to a cured epoxy resin composition, wherein the flame retardant phosphors compound is a compound of formula VII having n values between 0 and 5.
[VIII]
A further embodiment of the present invention provides a cured epoxy resin composition, wherein the flame retardant phosphorous compound is in a weight percent between 0.5 and 5% based on the total weight of the cured composition. More preferably is in a weight percent between 0.5 and 4% based on the total weight of the cured composition. Another preferred embodiment relates to a cured epoxy resin composition, wherein the hardener of the epoxy resin matrix comprises an aryl group. This aryl group has been defined above. More preferably, the hardener is selected from the list comprising aminophenyl sulfone (DDS), diaminodiphenylmethane (DDM) and a combination thereof.
In the present invention, the term "hardener" as used herein refers to compounds that serve as crossi inkers of the epoxy resins so that the mechanical properties as well as high temperature and chemical resistance are improved.
In another preferred embodiment, the hardener of the epoxy resin composition described above is in a weight percent between 10 and 40% based on the total weight of the cured composition. A further embodiment of the present invention relates to the cured epoxy resin composition described previously, which further comprises a nanofiller. More preferably, the nanofiller is selected from the list comprising nanoclay, carbon nanotubes and nanofibers, nanodiamonds, nano zirconium phosphate, graphite, and a combination thereof.
In the present invention, the term "nanofiller" relates to a doping agent distributed in the matrix of an epoxy resin composition, whose individual elements have at least one of their dimensions in the nanoscale. Examples of nanofillers include nanoclays, carbon nanotubes and nanofibres, nanodiamonds, nano zirconium phosphate and graphite.
Moreover, the second aspect of the present invention refers to a process for obtaining the cured epoxy resin composition described previously that comprises following steps:
a) mixing at least one epoxy resin matrix and at least a hardener at a temperature value between 60 and 150°C,
b) adding at least one flame retardant phosphorous compound to the mixture of step (a),
c) transferring the mixture obtained in step (b) into a mold, and
d) curing the mixture inside a mold of step (c) at least once at a temperature value between 120 and 220°C.
In a preferred embodiment, the invention relates to the above mentioned process, wherein the curing step (d) is carried out in one step at a temperature of 180°C and maintaining said temperature for 2 hours.
In another preferred embodiment, the invention refers to the process described previously, wherein the curing step (d) is carried out in three steps at temperatures values between 120°C and 220ac and maintaining said temperature for between 30 and 150 minutes.
Another preferred embodiment refers to the above mentioned process, wherein the curing step (d) is carried out by following continuously the next three steps: i) curing the mixture obtained in step (c) at a temperature of 150 °C and maintaining the temperature for 1 hour,
ii) curing the mixture obtained in (ii) at a temperature of 180 °C and maintaining the temperature for 2 hours, and
iii) curing the mixture obtained in (iii) at a temperature of 200°C and maintaining the temperature for 1 hour. A further embodiment of the present invention relates to the the above mentioned process described previously, wherein flame retardant phosphorous compound of step (b) is further combined with a nanofiller. More preferably, the nanofiller is selected from the list comprising nanoclay, carbon nanotubes and nanofibers, nanodiamonds, nano zirconium phosphate, graphite, and a combination thereof.
A third aspect of the present invention relates to the use of the cured epoxy resin composition described before as adhesive. A fourth aspect of the present invention relates to an article comprising the above mentioned cured epoxy resin composition.
A fifth aspect of the present invention refers to an article coated by the cured epoxy resin composition described above.
A sixth aspect of the invention relates to a fiber reinforced composite article comprising the previously described cured epoxy resin composition.
In a preferred embodiment, the fiber reinforced composite article is a laminate or a prepreg. Pre-preg as used here is a term for "pre-impregnated" composite fibres where a material, such as epoxy is already present. Usually the pre-preg takes the form of a weave or is unidirectional. The epoxy resin is only partially cured to allow easy handling and requires cold storage to prevent complete curing until complete polymerization is done, most commonly by heat.
A seventh aspect of the invention refers to the above mentioned article which is an electric or electronic circuit component or a structural element for transportation and building. In the present invention the term "transportation" refers to aircrafts, ships, rails, cars, bicycles and the like.
The term "building" relates to any structural element forming any kind of building. Furthermore, the term refers to any element taking part of the indoor decoration of a building.
An eighth aspect of the invention relates to an electric or electronic circuit component having an insulating coating of the cured epoxy resin composition described previously.
A ninth aspect of the invention is a compound of formula II, which is obtained by reaction of phenylphosphonic acid with glycidol at temperatures between 30 and 70°C.
A tenth aspect of the invention is a compound of formula III, which is obtained by reaction of 2-carboxyethyl(phenyl)phosphonic acid with glycidol
at temperatures between 30 and 70°C.
An eleveth aspect of the invention is a compound of formula IV, which is obtained by reaction of phenylphosphonic acid with ethylene glycol diglycidyl ether at temperatures between 30 and 70°C.
[IV]
A twelfth aspect of the present invention is a compound of formula V, which is obtained by reaction of phenylphosphonic acid with diglycidyl ether at temperatures between 30 and 70°C.
[V]
A thirteenth aspect of the present invention is a compound of formula VI, which is obtained by reaction of 2-carboxyethyl(phenyl)phosphinic acid with diglycidyl ether at temperatures between 30 and 70°C.
[VI]
A fourteenth aspect of the present invention refers to a compound of formula VII, which is obtained by reaction of phenylphosphomic acid with phenylene diisocyanate at temperatures between 30 and 70 °C.
-N=C=0
A fifteenth aspect of the present invention relates to a compound of formula VIII, which is obtained by reaction of phosphorous acid with tolyene diisocyanate at temperatures between 30 and 70 °C.
[VIM]
A sixteenth aspect of the invention relates to the use of a compound selected from the list comprising the compound of formula II
the compound of formula
[VII] and the compound of formula VIII
[VIII],
as flame retardants.
The compounds of formulas II, III, IV, V, VI, VII and VIII described previously as flame retardants. These compounds can be also considered as flame retardants diluents, as shown in the examples, they reduce the viscosity of the epoxy resin compositions to values below 30 mPa-s. Common values of viscosities are 30- 70 mPa-s when other phosphorous flame retardants are used.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skilled in the art to which this invention belongs. Methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. Throughout the description and claims the word "comprise" and its variations are not intended to exclude other technical features, additives, components, or steps. Additional objects, advantages and features of the invention will become apparent to those skilled in the art upon examination of the description or may
be learned by practice of the invention. The following examples are provided by way of illustration and are not intended to be limiting of the present invention.
EXAMPLES
Example 1 : Synthesis of the compound of formula II.
[II]
Into a 1 L flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping funnel, 142.3 g (0.9 mol) of phenylphosphonic acid and 300 ml of acetone were put to obtain a solution. Then, 133.4 g (1 .8 mol) of glycidol was dropped into the acetone solution of phenylphosphonic acid over 30 min. After the dropping, the reaction was further performed at 50°C for another 6 hours to complete the reaction. After the reaction ended, the flask was connected to a vacuum system to remove acetone leaving 273 g of a colorless, transparent liquid product at a yield of 99%.
Example 2 Synthesis of the compound of formula III
Into a 1 L flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping funnel, 192.7 g (0.9 mol) of 2-carboxyethyl(phenyl)phosphinic acid and 300 ml of ethanol were put to obtain a solution. Then, 133.4 g (1 .8 mol) of glycidol was dropped into the ethanol solution of 2- carboxyethyl(phenyl)phosphinic acid over 30 min. After the dropping, the
reaction was further performed at 50oC for another 8 hours to complete the reaction. After the reaction ended, the flask was connected to a vacuum system to remove ethanol leaving 319.6 g of a colorless, transparent liquid product at a yield of 98%.
Example 3 Synthesis of the compound of formula IV
Example 4 Synthesis of the compound of formula V
Into a 1 L flask equipped with a reflux condenser, a thermometer, a stirrer, a dropping funnel, 192.7 g (0.9 mol) of 2-carboxyethyl(phenyl)phosphinic acid and 300 ml of ethanol were put to obtain a solution. Then, 1 17.1 g (0.9 mol) of diglycidyl ether was dropped into the ethanol solution of 2- carboxyethyl(phenyl)phosphinic acid over 30 min. After the dropping, the reaction was further performed at 50°C for another 6 hours to complete the reaction. After the reaction ended, the flask was connected to a vacuum system to remove acetone leaving 303.5 g of a colorless, transparent liquid product at a yield of 98%.
Example 6 Synthesis of the compound of formula VII
Example 7 Synthesis of the compound of formula VIII
A curable epoxy resin composition was made by mixing:
100 parts by weight of 4,4'-Methylenebis(N,N-diglycidylaniline);
59 parts of 4-aminophenyl sulfone;
8 parts of the flame retardant compound of formula II described in example 1 , that is, the product of phenylphosphonic acid and glycidol (4.8wt% based on the total weight of the cured product) Curing process:
100 g of 4,4'-Methylenebis(N,N-diglycidylaniline) and 59 g of 4-aminophenyl sulfone was mixed at 80°C by removal of air bubbles and moisture under vacuum. 8 g of the flame retardant compound of formula II described in example 1 , that is, the product of phenylphosphonic acid and glycidol was added as a flame retardant. The mixture was cured at 180°C for 2 hours.
LOI: Limited Oxygen Index
The limiting oxygen index (LOI) is the minimum concentration of oxygen (expressed as a percentage) that will support combustion of a polymer. It was measured by passing a mixture of oxygen and nitrogen over a burning specimen, and reducing the oxygen level until a critical level was reached. LOI values for the composites were determined by standardized tests, according to the ASTM D2863 (samples of dimensions 130 * 6.5 * 3.2 mm3).
UL 94 is a plastics flammability standard released by Underwriters Laboratories of the USA. The standard classifies plastics according to how they burn in various orientations and thicknesses. From lowest (least flame-retardant) to highest (most flame-retardant), the classifications are:
HB: slow burning on a horizontal specimen; burning rate < 76 mm/min for thickness < 3 mm and burning stops before 100 mm
V2 burning stops within 30 seconds on a vertical specimen; drips of flaming particles are allowed.
· V1 : burning stops within 30 seconds on a vertical specimen; drips of particles allowed as long as they are not inflamed.
V0: burning stops within 10 seconds on a vertical specimen; drips of particles allowed as long as they are not inflamed.
5VB: burning stops within 60 seconds on a vertical specimen; no drips allowed; plaque specimens may develop a hole.
5VA: burning stops within 60 seconds on a vertical specimen; no drips allowed; plaque specimens may not develop a hole
Cone Calorimeter Test (CCT): p-HRR: peak Heat Release Rate, THR: Total Heat Release and TSP: Total Smoke Production.
The cone calorimeter test (CCT) is the most significant bench scale instrument to study the fire behavior of small specimen of various materials, following the procedures in ISO 5660 (without the use of the "frame and grid") using an FTT cone calorimeter. Square specimens (100x100^3 mm3) were irradiated at a heat flux of 50 kW/m2. This method is able to investigate some important parameters in a fire, like heat release rate (HRR), peak of heat release rate (p- HRR), total heat release (THR), total smoke production (TSP), among others.
Tg (Glass transition temperature)
The glass-liquid transition (or glass transition for short) is the reversible transition in amorphous materials (or in amorphous regions within semicrystalline materials) from a hard and relatively brittle state into a molten or rubber-like state. In this invention all Tg have been measured by dynamic mechanical analysis (DMA).
Example 9:
A curable epoxy resin composition was made by mixing:
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332), a transparent super-cooled liquid which has an epoxide equivalent weight of 171 - 175 and is commercially available from the DOW Chemical Company;
30 parts of tris(2,3-epoxypropyl) isocyanurate;
43 parts of 4-aminophenyl sulfone;
1 .5 parts of phenylphonic acid (1wt% based on the total weight of the cured product) Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 43 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 1 .5 g of phenylphosphonic acid was added as a flame retardant. The mixture was stirred at 120°C until phenylphosphonic acid had completely dissolved, and then the mixture was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 10
A curable epoxy resin composition was made by mixing:
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
30 parts of tris(2,3-epoxypropyl) isocyanurate;
42 parts of 4-aminophenyl sulfone;
2.9 parts of phenylphonic acid (2wt% based on the total weight of the cured product)
Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 42 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 2.9 g of phenylphosphonic acid was added as a flame retardant. The mixture was stirred at 120°C until phenylphosphonic acid had completely dissolved, and then the mixture was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 11 A curable epoxy resin composition was made by mixing:
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
30 parts of tris(2,3-epoxypropyl) isocyanurate;
40 parts of 4-aminophenyl sulfone;
5.8 parts of phenylphonic acid (4wt% based on the total weight of the cured product)
Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 40 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 5.8 g of phenylphosphonic acid was added as a flame retardant. The mixture was stirred at 120°C until phenylphosphonic acid had completely dissolved, and then the
mixture was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
A curable epoxy resin composition was made by mixing:
75 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
25 parts of tris(2,3-epoxypropyl) isocyanurate;
38 parts of 4-aminophenyl sulfone;
7.2 parts of phenylphonic acid (5wt% based on the total weight of the cured product)
Curing process:
75 g of high purity bisphenol A diglycidylether (D.E.R. 332), 25 g of tris(2,3- epoxypropyl) isocyanurate, and 38 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 7.2 g of phenylphosphonic acid was added as a flame retardant. The mixture was stirred at 120°C until phenylphosphonic acid had completely dissolved, and then the mixture was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
30 parts of tris(2,3-epoxypropyl) isocyanurate;
44 parts of 4-aminophenyl sulfone;
16 parts of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol (10wt% based on the total weight of the cured product) Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 44 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 16 g of the product of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was obtained, and then the solution was transferred in to mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 14
A curable epoxy resin composition was made by mixing:
80 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
20 parts of tris(2,3-epoxypropyl) isocyanurate;
42 parts of 4-aminophenyl sulfone;
20 parts of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol (12wt% based on the total weight of the cured product) Curing process:
80 g of high purity bisphenol A diglycidylether (D.E.R. 332), 20 g of tris(2,3- epoxypropyl) isocyanurate, and 42 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 20 g of of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was obtained, and then the solution was transferred in to mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 15
A curable epoxy resin composition was made by mixing:
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
30 parts of tris(2,3-epoxypropyl) isocyanurate;
40 parts of 4-aminophenyl sulfone;
7.4 parts of 2-carboxyethyl(phenyl)phosphinic acid (5wt% based on the total weight of the cured product)
Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 40 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 7.4 g of 2- carboxyethyl(phenyl)phosphinic acid was added as a flame retardant. The mixture was stirred at 120°C until 2-carboxyethyl(phenyl)phosphinic acid had completely dissolved, and then the mixture was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 16
A curable epoxy resin composition was made by mixing:
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
30 parts of tris(2,3-epoxypropyl) isocyanurate;
44 parts of 4-aminophenyl sulfone;
16 parts of the flame retardant compound of formula III described in Example 2, that is, the product of 2-carboxyethyl(phenyl)phosphinic acid and glycidol (10wt% based on the total weight of the cured product)
Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 44 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 16 g of the flame retardant compound of formula III described in Example 2, that is, the product of 2-carboxyethyl(phenyl)phosphinic acid and glycidol was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was
obtained, and then the solution was transferred in to mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 17
A curable epoxy resin composition was made by mixing:
50 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
50 parts of 4,4'-methylenebis(N,N-diglycidylaniline);
48 parts of 4-aminophenyl sulfone;
16.5 parts of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol (10wt% based on the total weight of the cured product)
Curing process:
50 g of high purity bisphenol A diglycidylether (D.E.R. 332), 50 g of 4,4'- methylenebis(N,N-digylcidylaniline), and 48 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 16.5 g of the flame retardant compound of formula II described in Example 1 , that is, product of phenylphosphonic acid and glycidol was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was obtained, and then the solution was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Viscosity LOI UL94 p-HRR THR TSP Tg
(mPa-s at 80°C) (%) (3.2±0.3 mm) (kW/m2) (MJ/m2) (m2) (°C)
<30 33.7 VO 463 58 17 229
Example 18
A curable epoxy resin composition was made by mixing:
50 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
50 parts of N,N-diglycidyl-4-glycidyloxyaniline;
50 parts of 4-aminophenyl sulfone;
16 parts of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol (10wt% based on the total weight of the cured product)
Curing process:
50 g of high purity bisphenol A diglycidylether (D.E.R. 332), 50 g of N,N- digylcidyl-4-glycidyloxyaniline, and 50 g of 4-aminophenyl sulfone was mixed at 120oC by removal of air bubbles and moisture under vacuum. 16 g of the flame retardant compound of formula II described in Example 1 , that is, the product of phenylphosphonic acid and glycidol was added as a flame retardant. The mixture was stirred at 120oC until a homogeneous solution was obtained, and then the solution was transferred into mold and cured at 150oC for 1 hour, 180oC for 2 hours, and finally postcured at 200oC for 1 hour.
Example 19
A curable epoxy resin composition was made by mixing:
70 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
30 parts of tris(2,3-epoxypropyl) isocyanurate;
44 parts of 4-aminophenyl sulfone;
16 parts of the flame retardant compound of formula V described in Example 4, that is, the product of phenylphosphonic acid and phenylene diisocyanate (10wt% based on the total weight of the cured product)
Curing process:
70 g of high purity bisphenol A diglycidylether (D.E.R. 332), 30 g of tris(2,3- epoxypropyl) isocyanurate, and 44 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 16 g of the flame retardant compound of formula V described in Example 4, that is, the product of phenylphosphonic acid and phenylene dissocyanate was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was obtained, and then the solution was transferred in to mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Example 20 A curable epoxy resin composition was made by mixing:
50 parts by weight of high purity bisphenol A diglycidylether (D.E.R. 332);
50 parts of 4,4'-methylenebis(N,N-diglycidylaniline);
48 parts of 4-aminophenyl sulfone;
16 parts of the flame retardant compound of formula V described in Example 4, that is, the product of phenylphosphonic acid and phenylene diisocyanate (10wt% based on the total weight of the cured product)
Curing process:
50 g of high purity bisphenol A diglycidylether (D.E.R. 332), 50 g of 4, 4'- methylenebis(N,N-digylcidylaniline), and 48 g of 4-aminophenyl sulfone was mixed at 120°C by removal of air bubbles and moisture under vacuum. 16 g of the flame retardant compound of formula V described in Example 4, that is, the product of phenylphosphonic acid and phenylene diisocyanate was added as a flame retardant. The mixture was stirred at 120°C until a homogeneous solution was obtained, and then the solution was transferred into mold and cured at 150°C for 1 hour, 180°C for 2 hours, and finally postcured at 200°C for 1 hour.
Viscosity LOI UL94 p-HRR THR TSP Tg
(mPa-s at 80°C) (%) (3.2±0.3 mm) (kW/m2) (MJ/m2) (m2) (°C)
<30 29.7 VO 563 69 23 208
Claims
1 . A halogen free cured epoxy resin composition that comprises the following components:
• at least one epoxy resin matrix selected from the list comprising a glycidyl ether/ester type epoxy resin, a glycidyl amine type epoxy resin and a combination thereof, wherein the glycidyl amine type epoxy resin has at least one of the following molecular group
• at least one flame retardant phosphorous compound, wherein the flame retardant compound is in a weight percent between 0.5 and 15% based on the weight of the cured composition,
• and at least a hardener of the epoxy resin matrix in a stoichiometric based on the weight of the cured composition, which comprises an amine group, an anhydride group, an aryl group, a sulfhydryl group or a combination thereof.
2. The cured epoxy resin composition, according to claim 1 , wherein the glycidyl ether/ester type epoxy resin is selected from the list consisting of
Bisphenol A epoxy resin
H
-0-CH2-CfI-C¾-H> O-CH2-CH-CH2
H OH H
Bisphenol F epoxy resin
Bisphenol S epoxy resin
and Novolac epoxy resin. wherein n is a value between 0 and 10.
3. The cured epoxy resin composition, according to claim 2, wherein the glycidyl ether/ester type epoxy resins have n values between 1 a 5.
4. The cured epoxy resin composition, according to any one of claims 1 to 3, wherein the glycidyl amine type epoxy resin is selected from the list comprising Tris(2,3-epoxypropyl) isocyanurate, 4,4'-Methylenebis(N,N-diglycidylaniline), bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-Diglycidyl-4-glycidyloxyaniline and a combination thereof.
5. The cured epoxy resin composition, according to any one of claims 1 to 4, wherein the flame retardant phosphors compound is a compound of formula I
R2 p o wherein
Ri and R3 are independently selected from the list comprising epoxides, -XR4, -alkyl(Ci-C4)-COO-R5, -COOR6 and -Y-NH2 X is selected from O, -NH, -S-,
Y is selected from the list comprising hydrogen, alkyl (C1-C10), cycloalkyl, aryl and aralkyl,
R4, R5 and R6 are independently selected from the list comprising hydrogen, alkyl (Ci-C4), aryl and diol,
and R2 is selected from the list comprising hydrogen, alkyl (Ci-C4), cycloalkyl, aryl and aralkyl.
6. The cured epoxy resin composition, according to claim 5, wherein Ri and R3 are -OH and R2 is a phenyl group.
7. The cured epoxy resin composition, according to claim 5, wherein Ri is an - OH, R2 is a phenyl group, R3 is a alkyl(Ci-C4)-COO-R5 and R5 is a hydrogen.
8. The cured epoxy resin composition, according to claim 5, wherein Ri and R3 are -OH and R2 is a methyl group.
9. The cured epoxy resin composition, according to claim 5, wherein Ri and R3 are -OH and R2 is hydrogen.
10. The cured epoxy resin composition, according to any one of claims 1 to 5, wherein the compound of formula I is the compound of formula II
[II]
1 1 . The cured epoxy resin composition, according to any one of claims 1 to 5, wherein the compound of formula I is the compound of formula III
12. The cured epoxy resin composition, according to any one of claims 1 to 4, wherein the flame retardant phosphors compound is a compound of formula IV having n values between 0 and 10.
[IV]
13. The cured epoxy resin composition, according to any one of claims 1 to 4, wherein the flame retardant phosphors compound is a compound of formula Vhaving n values between 0 and 10.
[V]
14. The cured epoxy resin composition, according to any one of claims 1 to 4, wherein the flame retardant phosphors compound is a compound of formula VI h ving n values between 0 and 10.
[VI] 15. The cured epoxy resin composition, according to any one of claims 1 to 4, wherein the flame retardant phosphors compound is a compound of formula VII having n values between 0 and 5.
16. The cured epoxy resin composition, according to any one of claims 1 to 4, wherein the flame retardant phosphors compound is a compound of formula VII having n values between 0 and 5,
[VIII] 17. The cured epoxy resin composition, according to any one of claims 1 to 16, wherein the flame retardant phosphorous compound is in a weight percent between 0.5 and 5% based on the total weight of the cured composition.
18. The cured epoxy resin composition, according to claim 17, wherein the flame retardant phosphorous compound is in a weight percent between 0.5 and
4% based on the total weight of the cured composition.
19. The cured epoxy resin composition, according to any one of claims 1 to 18, wherein the hardener of the epoxy resin matrix comprises an aryl group.
20. The cured epoxy resin composition, according to claim 19, wherein the hardener is selected from the list comprising aminophenyl sulfone (DDS), diaminodiphenylmethane (DDM) and a combination thereof.
21 . The cured epoxy resin composition, according to any one of claims 1 to 20, wherein the hardener is in a weight percent between 10 and 40% based on the total weight of the cured composition.
22. The cured epoxy resin composition, according to any one of claims 1 to 21 , which further comprises a nanofiller.
23. The cured epoxy resin composition, according to claim 22, wherein the nanofiller is selected from the list comprising nanoclay, carbon nanotubes and nanofibers, nanodiamonds, nano zirconium phosphate, graphite, and a combination thereof.
24. A process for obtaining the cured epoxy resin composition according to any one of claims 1 to 23 that comprises following steps:
a) mixing at least one epoxy resin matrix and at least a hardener at a temperature value between 60 and 150°C,
b) adding at least one flame retardant phosphorous compound to the mixture of step (a),
c) transferring the mixture obtained in step (b) into a mold, and
d) curing the mixture inside a mold of step (c) at least once at a temperature value between 120 and 220°C.
25. The process, according to claim 24, wherein the curing step (d) is carried out in one step at a temperature of 180°C and maintaining said temperature for 2 hours.
26. The process, according to claim 24, wherein the curing step (d) is carried out in three-steps at temperatures values between 120°C and 220°C and maintaining said temperature for between 30 and 150 minutes.
27. The process, according to the preceding claim 26, wherein the curing step (d) is carried out by following continuously the next three steps:
i) curing the mixture obtained in step (c) at a temperature of 150 °C and maintaining the temperature for 1 hour,
ii) curing the mixture obtained in (ii) at a temperature of 180 °C and maintaining the temperature for 2 hours, and
iii) curing the mixture obtained in (iii) at a temperature of 200°C and maintaining the temperature for 1 hour.
28. The process, according to any one of claims 24 to 27, wherein flame retardant phosphorous compound of step (b) is further combined with a nanofiller.
29. The process, according to claim 28, wherein the nanofiller is selected from the list comprising nanoclay, carbon nanotubes and nanofibers, nanodiamonds, nano zirconium phosphate, graphite, and a combination thereof.
30. Use of the cured epoxy resin composition, according to any one of claims 1 to 23, as adhesive.
31 . An article comprising the cured epoxy resin composition according to any one of claims 1 to 23.
32. An article coated by the cured epoxy resin composition according to any one of claims 1 to 23.
33. A fiber reinforced composite article comprising the cured epoxy resin composition according to any one of claims 1 to 23.
34. The fiber reinforced composite article, according to claim 33, which is a laminate or a prepreg.
35. An article according to any of claims 31 to 33, wherein the article is an electric or electronic circuit component or a structural element for transportation and building.
36. An electric or electronic circuit component having an insulating coating of the cured epoxy resin composition according to any one of claims 1 to 23.
37. A compound of formula II
38. A compound of formula
39. A com ound of formula IV
[V]
41 . A compound of formula VI
43. A compound of formula VIII
[VIM]
44. Use of a compound selected from the list comprising the compound of formula II
the com ound of formula IV
the compound of formula V
[V],
the compound of formula VI
[VII] and the compound of formula VIII
[VIII], as flame retardants.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2013/063658 WO2014206487A1 (en) | 2013-06-28 | 2013-06-28 | A halogen free flame retardant epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2013/063658 WO2014206487A1 (en) | 2013-06-28 | 2013-06-28 | A halogen free flame retardant epoxy resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014206487A1 true WO2014206487A1 (en) | 2014-12-31 |
Family
ID=48745933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2013/063658 WO2014206487A1 (en) | 2013-06-28 | 2013-06-28 | A halogen free flame retardant epoxy resin composition |
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| Country | Link |
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| WO (1) | WO2014206487A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105505108A (en) * | 2015-11-27 | 2016-04-20 | 沈阳顺风新城建筑材料有限公司 | Waterborne fireproof coating and preparation method thereof |
| EP3037426A1 (en) * | 2013-08-22 | 2016-06-29 | Adeka Corporation | Phosphorus-containing compound, and curable epoxy resin composition containing same |
| WO2024046794A1 (en) | 2022-09-02 | 2024-03-07 | Clariant International Ltd | Phosphinate flame retardant and process for manufacture thereof |
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| EP3037426A1 (en) * | 2013-08-22 | 2016-06-29 | Adeka Corporation | Phosphorus-containing compound, and curable epoxy resin composition containing same |
| EP3037426A4 (en) * | 2013-08-22 | 2017-05-03 | Adeka Corporation | Phosphorus-containing compound, and curable epoxy resin composition containing same |
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| WO2024046794A1 (en) | 2022-09-02 | 2024-03-07 | Clariant International Ltd | Phosphinate flame retardant and process for manufacture thereof |
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