CN117603262A - 一种磷系阻燃剂及其制备方法与应用 - Google Patents
一种磷系阻燃剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN117603262A CN117603262A CN202311404573.6A CN202311404573A CN117603262A CN 117603262 A CN117603262 A CN 117603262A CN 202311404573 A CN202311404573 A CN 202311404573A CN 117603262 A CN117603262 A CN 117603262A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphorus
- solution
- reaction
- phosphorus flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 claims abstract description 145
- 239000003063 flame retardant Substances 0.000 title claims abstract description 145
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 54
- 239000011574 phosphorus Substances 0.000 title claims abstract description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- -1 alkyl phosphate Chemical compound 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000002367 halogens Chemical class 0.000 claims abstract description 4
- 239000010452 phosphate Substances 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 57
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000003365 glass fiber Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910001853 inorganic hydroxide Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229920013638 modified polyphenyl ether Polymers 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920001470 polyketone Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012266 salt solution Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 18
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 13
- 239000011889 copper foil Substances 0.000 description 13
- 239000004952 Polyamide Substances 0.000 description 12
- 229920002647 polyamide Polymers 0.000 description 12
- 238000009472 formulation Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000011342 resin composition Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- PVKCVCDTYNNNOG-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrobromide Chemical compound [Br-].NC1=NC(N)=[NH+]C(N)=N1 PVKCVCDTYNNNOG-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 241000208818 Helianthus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical group OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- JOQAMSDLZYQHMX-UHFFFAOYSA-L disodium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Na+].[Na+].[O-]P([O-])(=O)C1=CC=CC=C1 JOQAMSDLZYQHMX-UHFFFAOYSA-L 0.000 description 1
- HBPTWDLRHFZEER-UHFFFAOYSA-L disodium;methyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [Na+].[Na+].CP([O-])([O-])=O HBPTWDLRHFZEER-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 1
- HHJJPFYGIRKQOM-UHFFFAOYSA-N sodium;oxido-oxo-phenylphosphanium Chemical compound [Na+].[O-][P+](=O)C1=CC=CC=C1 HHJJPFYGIRKQOM-UHFFFAOYSA-N 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 235000012773 waffles Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 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
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4025—Esters of poly(thio)phosphonic acids
- C07F9/4053—Esters of poly(thio)phosphonic acids containing substituents selected from B, Si, P (other than -PO3H2 groups in free or esterified form), or a metal
-
- 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
- C08K5/5333—Esters of phosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开一种磷系阻燃剂及其制备方法与应用,属于阻燃剂合成及应用领域。该磷系阻燃剂的制备方法包括以下步骤:(1)将烷基磷酸盐、烷基次磷酸盐中的至少一种溶解于水中,得到溶液一;将金属可溶性盐溶解于水中,得到溶液二;(2)将溶液二滴加到溶液一中,进行搅拌反应,得到反应液;(3)将反应液过滤或浓缩,然后烘干、粉碎,得到磷系阻燃剂。本发明所制得的磷系阻燃剂,具有阻燃效果好,热稳定性高,优异的抗析出性能等。本发明通过将烷基磷酸可溶性盐溶液、烷基次磷酸可溶性盐溶液与2~8价金属的非卤素可溶性盐溶液反应,并控制反应条件,得到新型的有机磷化物阻燃剂,制备方法具有工艺简单、环保、成本低、实用性强等优点。
Description
技术领域
本发明涉及阻燃剂合成及应用领域,具体地说是涉及一种磷系阻燃剂,该磷系阻燃剂的制备方法,以及该磷系阻燃剂在制备阻燃剂组合物等方面的应用。
背景技术
二乙基次膦酸铝(ADP)是一种应用范围广,阻燃效果较好的无卤磷系阻燃剂,可以广泛应用于聚酰胺、聚酯、热塑性弹性体环氧等领域。但是它也存在一定的缺点,比如热稳定性略差,成碳性不足,需与其他MPP、MCA等磷氮阻燃剂协效复配使用。特别是玻纤增强高温尼龙中,由于加工温度高,体系粘度大,使得螺杆附近温度比设定温度高很多,此种情况下ADP和MCA易分解不能满足要求。而在聚酯、PA6、PA66中,使用MPP与ADP复配时,MPP容易析出,影响下游的应用场景,如在注塑成型时,容易析出腐蚀模具,降低模具使用寿命。针对这些问题有些研究人员做了研究,比如对ADP和MPP进行表面改性,选择其他协效体系等方式,但只能稍有改善,仍然不能较好解决。
发明内容
基于上述技术问题,本发明提出一种磷系阻燃剂,其具有阻燃效果好,热稳定性高,优异的抗析出性能等;本发明还提出一种磷系阻燃剂的制备方法,及其在阻燃组合物中的应用。
本发明所采用的技术解决方案是:
一种磷系阻燃剂,其是具有以下结构式的化合物:
式中,R为甲基或苯基,R1、R2分别为氢、C1~C7的饱和脂肪族结构或C6~C13的至少含有一个芳环结构的有机链段;a为1~4,取整数,且a+1=m;M为金属。
上述磷系阻燃剂,更加优选a为2,m为3。
优选的,所述R1、R2分别为氢、甲基、乙基或苯基;所述金属为镁、钙、铁、铝、锌、锡、锰、镍、钛、锗、钡、锶、铈、锆、镧、钕或镨。更加优选为镁、钙、铝、锌中的一种。
如上所述磷系阻燃剂的制备方法,包括以下步骤:
(1)将烷基磷酸盐、烷基次磷酸盐中的至少一种溶解于水中,得到溶液一;将金属可溶性盐溶解于水中,得到溶液二;
(2)将溶液二滴加到溶液一中,进行搅拌反应,得到反应液;
(3)将反应液过滤或浓缩,然后烘干、粉碎,得到磷系阻燃剂。
优选的,步骤(1)中:所述金属可溶性盐选自硫酸盐或其水合物、硝酸盐或其水合物。具体可为硫酸铝或其水合物、硫酸锌或其水合物、硫酸镁或其水合物、硫酸锰或其水合物、硫酸钛或其水合物、硫酸铈或其水合物、硫酸高铈、硫酸锆、硫酸铁、硫酸亚锡、硝酸钙、硝酸镁、硝酸铁、硝酸铈、硝酸高铈、硝酸锆、硝酸钛、硝酸钡、硝酸镍、硝酸锶、硝酸锡、醋酸钡、硝酸镧或其水合物、硝酸钕或其水合物、硫酸钕或其水合物等具有有限水溶性的无机或有机二到四价金属盐及金属盐水合物。
优选的,步骤(2)中:控制溶液一中酸根与溶液二中金属离子的摩尔比为1∶(0.1~10);控制反应温度为50℃~100℃,反应时间为60min~240min。
优选的,步骤(3)中:在80℃~200℃的烘箱中烘干,粉碎得到磷系阻燃剂的粒径为0.001μm~60μm。
一种磷系阻燃剂组合物,其采用如上所述的磷系阻燃剂。
优选的,该磷系阻燃剂组合物还包含高分子聚合物;所述高分子聚合物为聚酰胺树脂、环氧树脂、改性聚苯醚树脂、聚酯树脂、聚烯烃、热塑性弹性体、POK聚酮树脂、丙烯酸/EVA乳液中的至少一种或多种的混合物。
更加优选,聚酰胺树脂为PA6、PA66、高温尼龙中的至少一种;环氧树脂优选为缩水甘油醚类、缩水甘油酯类、缩水甘油胺类、线型脂肪族类、含磷环氧树脂、聚苯醚改性环氧树脂以及脂肪族类环氧树脂中的一种或多种共混而成的树脂材料;改性聚苯醚树脂优选为含磷酚醛树脂、末端乙烯基的聚苯醚树脂的一种或两种的混合物。
上述磷系阻燃剂组合物可通过双螺杆、密炼机,搅拌浸渍等常用的加工方式加工而成。
优选的,该磷系阻燃剂组合物还包含阻燃协效剂、增韧剂、填料、增强材料、固化剂、溶剂和加工助剂;
所述阻燃协效剂为磷氮系阻燃剂、硼系阻燃剂、硅系阻燃剂、卤系阻燃剂、无机氢氧化物或金属化合物所述增韧剂为二异氰酸酯、氢化苯乙烯-丁二烯-二乙烯基苯共聚物中的一种或两种以上的混合物;所述填料为二氧化硅、氢氧化镁、云母粉、高岭土、滑石粉、碳酸钙和氢氧化物中的一种或两种以上的组合;所述增强材料为玻璃纤维、玄武岩纤维、玻璃纤维布、电子级玻璃纤维布、芳纶纤维中的一种或两种以上的混合物;所述固化剂为胺类固化剂、酸酐类固化剂、酚醛类固化剂中的一种或两种以上的混合物;所述溶剂为甲苯、丙酮、丁酮、二甲基甲酰胺、丙二醇甲醚、丙二醇甲醚醋酸酯或环己酮。
更加优选的,阻燃协效剂为聚膦腈、DOPO衍生物、二苯基氧化膦衍生物、焦磷酸哌嗪、有机改性MPP、MCA、硼酸锌、有机硅树脂、三(2,3-二溴丙基)异三聚氰酸酯、氢溴酸三聚氰胺、氢氧化铝、氢氧化镁、氧化锌、硼酸锌中的至少一种或多种的混合物。所述咪唑类固化剂包含2-甲基咪唑、2-乙基-4-甲基咪唑中的一种或二者的混合物。
上述加工助剂包含硅烷偶联剂、抗氧剂等。
上述磷系阻燃剂组合物能够在碳纤维复合材料、电子覆铜板及封装、汽车部件、涂料乳液、航空航天、电子电器领域中应用。
本发明的有益技术效果是:
(1)本发明通过将烷基磷酸可溶性盐溶液、烷基次磷酸可溶性盐溶液与2~8价金属的非卤素可溶性盐溶液反应,并控制反应条件,得到新型的有机磷化物阻燃剂。该工艺简单,环保,制备阻燃剂的成本低,具有较强的实用性,并且原料成本低易得,具有更强的环保性。
(2)本发明有机磷化物阻燃剂相比于ADP等目前常用有机膦酸盐阻燃剂,将不同氧化态的含磷结构引入到一个阻燃剂分子结构中,可以充分发挥不同氧化态的磷之间的阻燃协同效应,从而在聚酰胺、环氧树脂等高分子材料中具有更高的阻燃效率。引入的甲基膦酸和苯基膦酸结构可以与金属盐形成更高分子量的阻燃剂,从而具有更优异的抗析出性能。并且该结构中引入了甲基和苯基等不同的有机基团,可以制备出具有更高磷含量,较高的分解温度和更高相容性阻燃剂。
附图说明
图1为本发明所制得阻燃剂1的红外表征谱图;
图2为本发明实施例合成的阻燃剂与市场上的ADP阻燃剂的TGA数据图。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
阻燃剂的制备实施例如下:
实施例a
将1mol/L的苯基膦酸钠溶液1L,加入1mol/L的二乙基次膦酸钠溶液4L中,混合均匀后,再向其中滴加1L 1mol/L的硫酸铝溶液,2小时内滴加结束。滴加结束后搅拌反应3小时,整个过程保持90-100℃恒温(滴加和搅拌反应都维持在该温度),得到反应液。将反应液经过洗涤、过滤、干燥、粉碎过筛得到磷系阻燃剂,收率为97%。该磷系阻燃剂称为阻燃剂1。
上述干燥过程在80℃~200℃的烘箱中烘干。所得磷系阻燃剂的粒径为0.001μm~30μm。
红外测试显示合成阻燃剂1,如图2所示。其分子式如下:
实施例b
将1mol/L的甲基膦酸钠溶液1L,加入到1mol/L的苯基次膦酸钠溶液4L中,混合均匀后,向其中滴加1L 1mol/L的硫酸铝溶液,2小时内滴加结束,滴加结束后搅拌3小时,整个过程保持90-100℃恒温,得到反应液。将反应液经过洗涤、过滤、干燥、粉碎过筛得到磷系阻燃剂,收率为98%。磷系阻燃剂的粒径为0.001μm~30μm。该磷系阻燃剂称为阻燃剂2。
阻燃剂2的分子式如下:
将本发明实施例合成的阻燃剂与市场上的ADP阻燃剂的TGA数据进行对比,如图2所示,可见阻燃剂1与阻燃剂2初始分解温度以及最大分解速率温度都比ADP要高,阻燃剂1与阻燃剂2残炭率也更高,相比于ADP而言,更适于在尼龙等中应用。
采用以上实施例制得的磷系阻燃剂可进一步制备磷系阻燃剂组合物。其中,所用到的原料来源如下:
聚酰胺PA-66,EP159,华峰集团有限公司;玻璃纤维,ECS10-3.0-T435N,泰山玻璃纤维有限公司;二乙基次磷酸铝(ADP)、MCA,青岛欧普瑞新材料有限公司;双酚A环氧树脂、DCPD苯酚酚醛环氧树脂,济南圣泉;聚苯醚S202A,旭化成;六苯氧基环三膦腈(HPCTP),东营道一生物医药科技有限公司;电子纤维布(7628玻璃纤维布)购自南亚塑胶;固化剂双氰胺、2-甲基咪唑,山鑫葵高分子新材料有限公司;溶剂丙酮等常规助剂市售。
性能评价方式及实行标准:
力学性能,按照GB/T1843测试冲击强度、GB/T1040测试拉伸强度,垂直燃烧测试按照GB/T2408-2008方法测试;氧指数(LOI)测试按照GB/T2406.1-2008方法测试;玻璃转化温度(Tg),DMA仪器测;介电常数(Dk)、介电损耗(Df),(10GHz)AET微波诱电分析仪测。
磷系阻燃剂组合物的制备实施例如下:
制备非增强聚酰胺体系
步骤一:将PA-66与阻燃剂放在80℃真空烘箱中干燥4小时,随后混合均匀后用双螺杆挤出机挤出造粒,并将制得PA-66阻燃颗粒放置于80℃真空烘箱中干燥4小时,备用。
步骤二:将完全干燥的PA-66阻燃颗粒使用注塑机注塑出阻燃条(1.6mm)、哑铃条测试样板,并在25℃、50%湿度下放置24小时后测试阻燃性能、力学性能。
30wt%玻纤增强聚酰胺体系
除了增加30wt%玻纤外,测试步骤与非增强聚酰胺体系一致。
实施例1
按照上述非增强聚酰胺体系制样并测试,阻燃剂以及PA66具体配比数据及性能测试如表1所示。
实施例2
除了改变阻燃剂以及PA66的用量比例外,实施过程与实施例1一致,具体配比数据及性能测试如表1所示。
实施例3
除了增加30wt%玻纤(玻璃纤维)外,测试步骤与非增强聚酰胺体系一致,阻燃剂、无碱玻纤以及PA66具体配比数据及性能测试如表1所示。
实施例4
除了改变阻燃剂以及PA66的比例外,实施过程与实施例3一致,具体配比数据及性能测试如表1所示。
对比例1
除了将阻燃剂替换成二乙基次膦酸铝外,实施过程与实施例1一致,具体配比数据及性能测试如表1所示。
对比例2
除了将阻燃剂替换成二乙基次膦酸铝外,实施过程与实施例3一致,具体配比数据及性能测试如表1所示。
表1示出实施例1-4与对比例1-2成分数据表及物理性能测试结果。
表1
通过表1可以看出,使用本发明的阻燃剂应用在PA体系中,无论是增强体系还是非增强体系,都能够在较低的阻燃剂使用量条件下使得阻燃PA复合材料达到UL94-V0@1.6mm的阻燃等级。相比于本发明阻燃剂,ADP则需要更多添加量才能满足UL94-V0@1.6mm阻燃要求,特别是30wt%玻纤增强PA-66体系需要添加量达到23wt%才行。可见,本发明阻燃剂可以大幅度降低阻燃剂添加用量,并能够提高阻燃聚酰胺的物理性能。
实施例5
按照增强聚酰胺体系制样并测试,阻燃剂以及PBT具体配比数据及性能测试如表2所示。
实施例6
按照非增强聚酰胺体系制样并测试,阻燃剂以及PP具体配比数据及性能测试如表2所示。
实施例7
按照非增强聚酰胺体系制样并测试,阻燃剂以及PP具体配比数据及性能测试如表2所示。
表2示出实施例5-7的成分数据及性能测试结果。
表2
通过表2可以看出,使用本发明阻燃剂可以应用在PBT、ABS、以及PP体系中,尤其是在PBT以及PP中具有优异的阻燃效果,在PBT中添加18%即可以达到V-0级,在PP中与焦磷酸哌嗪体系协效使用,添加1%可以降低3%的焦磷酸哌嗪的添加量。
阻燃环氧树脂体系
称取100质量份的环氧树脂,然后按配方加入阻燃剂,在150℃混合3-5min,呈流动状态后,趁热按配方加入固化剂,在150℃再搅拌5min搅拌均匀置于真空干燥箱中除去气泡后,趁热倒入标准模具中后于120℃固化2h,180℃固化2h,脱模后得到阻燃环氧树脂材料。
实施例8
称取100质量份的双酚A环氧树脂,然后按配方加入阻燃剂1,在150℃混合3-5min,呈流动状态后,趁热加入固化剂DDS、2-甲基咪唑,在150℃再搅拌5min置于真空干燥箱中除去气泡后,趁热倒入标准模具中后于120℃固化2h,180℃固化2h,脱模后得到阻燃环氧树脂材料,具体配比数据及性能测试如表3所示。
实施例9
除了改变环氧树脂、阻燃剂、固化剂外,实施过程与实施例8一致,具体配比数据及性能测试如表3所示。
实施例10
除了改变环氧树脂、阻燃剂、固化剂外,实施过程与实施例8一致,具体配比数据及性能测试如表3所示。
对比例3
除了改变环氧树脂、阻燃剂、固化剂外,实施过程与实施例8一致,具体配比数据及性能测试如表3所示。
对比例4
除了改变环氧树脂、阻燃剂、固化剂外,实施过程与实施例8一致,具体配比数据及性能测试如表3所示。
表3示出环氧树脂成分数据表及物理性能测试结果。
表3
通过表3可以看出,纯环氧树脂在未加阻燃剂时,氧指数只有23.4%,UL94@3mm无等级,对比常用的HPCTP阻燃剂需要添加18份才可以达到V0级,相比较只需加入本发明阻燃剂10份时就可以达到V-0级,并且氧指数达到31.5%,明显优于常用的阻燃体系。更换不同类型的环氧树脂以及固化剂时也可以得到相似的阻燃效果。另外,添加相同量的阻燃剂1也比HPCTP有更高的Tg。
阻燃环氧树脂胶液的制备、树脂组合物的固化及基板的制备:
将环氧树脂配成固含量为50-70%的溶液,然后按配方加入固化剂双氰胺、2-甲基咪唑混合5-10min,得到环氧树脂组合物的溶液即树脂清漆,浓度50-60%。以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布,再进行155℃、2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔,依铜箔、四片半固化片、铜箔的顺序进行迭合,再于真空条件下经由150℃、2h和180℃、2h压合形成铜箔基板,分别将上述含铜箔基板及铜箔蚀刻后,不含铜箔的基板做物性测定。
实施例11
将双酚A环氧树脂配成固含量为50-70%的丙酮溶液,然后按配方加入阻燃剂1,固化剂双氰胺,2-甲基咪唑混合5-10min,得到环氧树脂组合物的丙酮溶液即树脂清漆,浓度50-60%。以含浸或涂覆等方式使树脂组合物附着于玻璃纤维布,再进行155℃、2min加热烘烤成半固化态而得半固化片。取四张上述制得的半固化片及两张铜箔,依铜箔、四片半固化片、铜箔的顺序进行迭合,再于真空条件下经由150℃、2h和180℃、2h压合形成铜箔基板。
实施例12
除了改变环氧树脂、聚苯醚、阻燃剂外,实施过程与实施例11一致,具体配比数据及性能测试如表4所示。
实施例13
除了改变环氧树脂、阻燃剂外,实施过程与实施例11一致,具体配比数据及性能测试如表4所示。
对比例5
除了改变环氧树脂、阻燃剂外,实施过程与实施例11一致,具体配比数据及性能测试如表4所示。
表4示出环氧树脂层压板成分数据表及物理性能测试结果。
表4
本发明将阻燃剂与树脂组合物应用到覆铜板基板中,在环氧体系或者环氧聚苯醚复合体系中都具有良好的综合性能。添加10份时环氧树脂基板可以达到V-0级,同时对介电性能无不良影响;尤其是加入到DCPD酚醛环氧体系中以及环氧聚苯醚复合体系中时具有更优的介电性能。
Claims (10)
1.一种磷系阻燃剂,其特征在于是具有以下结构式的化合物:
式中,R为甲基或苯基,R1、R2分别为氢、C1~C7的饱和脂肪族结构或C6~C13的至少含有一个芳环结构的有机链段;a为1~4,取整数,且a+1=m;M为金属。
2.根据权利要求1所述的一种磷系阻燃剂,其特征在于:所述R1、R2分别为氢、甲基、乙基或苯基;所述金属为镁、钙、铁、铝、锌、锡、锰、镍、钛、锗、钡、锶、铈、锆、镧、钕或镨。
3.如权利要求1所述磷系阻燃剂的制备方法,其特征在于包括以下步骤:
(1)将烷基磷酸盐、烷基次磷酸盐中的至少一种溶解于水中,得到溶液一;将金属可溶性盐溶解于水中,得到溶液二;
(2)将溶液二滴加到溶液一中,进行搅拌反应,得到反应液;
(3)将反应液过滤或浓缩,然后烘干、粉碎,得到磷系阻燃剂。
4.根据权利要求3所述的磷系阻燃剂的制备方法,其特征在于,步骤(1)中:所述金属可溶性盐选自硫酸盐或其水合物、硝酸盐或其水合物。
5.根据权利要求3所述的磷系阻燃剂的制备方法,其特征在于,步骤(2)中:控制溶液一中酸根与溶液二中金属离子的摩尔比为1∶(0.1~10);控制反应温度为50℃~100℃,反应时间为60min~240min。
6.根据权利要求3所述的磷系阻燃剂的制备方法,其特征在于,步骤(3)中:在80℃~200℃的烘箱中烘干,粉碎得到磷系阻燃剂的粒径为0.001μm~60μm。
7.一种磷系阻燃剂组合物,其特征在于:采用如权利要求1所述的磷系阻燃剂。
8.如权利要求7所述一种磷系阻燃剂组合物,其特征在于:该磷系阻燃剂组合物还包含高分子聚合物;所述高分子聚合物为聚酰胺树脂、环氧树脂、改性聚苯醚树脂、聚酯树脂、聚烯烃、热塑性弹性体、POK聚酮树脂、丙烯酸/EVA乳液中的至少一种或多种的混合物。
9.如权利要求7所述一种磷系阻燃剂组合物,其特征在于:该磷系阻燃剂组合物还包含阻燃协效剂、增韧剂、填料、增强材料、固化剂、溶剂和加工助剂;
所述阻燃协效剂为磷氮系阻燃剂、硼系阻燃剂、硅系阻燃剂、卤系阻燃剂、无机氢氧化物或金属化合物所述增韧剂为二异氰酸酯、氢化苯乙烯-丁二烯-二乙烯基苯共聚物中的一种或两种以上的混合物;所述填料为二氧化硅、氢氧化镁、云母粉、高岭土、滑石粉、碳酸钙和氢氧化物中的一种或两种以上的组合;所述增强材料为玻璃纤维、玄武岩纤维、玻璃纤维布、电子级玻璃纤维布、芳纶纤维中的一种或两种以上的混合物;所述固化剂为胺类固化剂、酸酐类固化剂、酚醛类固化剂中的一种或两种以上的混合物;所述溶剂为甲苯、丙酮、丁酮、二甲基甲酰胺、丙二醇甲醚、丙二醇甲醚醋酸酯或环己酮。
10.如权利要求7所述一种磷系阻燃剂组合物,其特征在于:该磷系阻燃剂组合物能够在碳纤维复合材料、电子覆铜板及封装、汽车部件、涂料乳液、航空航天、电子电器领域中应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311404573.6A CN117603262A (zh) | 2023-10-26 | 2023-10-26 | 一种磷系阻燃剂及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311404573.6A CN117603262A (zh) | 2023-10-26 | 2023-10-26 | 一种磷系阻燃剂及其制备方法与应用 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117603262A true CN117603262A (zh) | 2024-02-27 |
Family
ID=89946985
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311404573.6A Pending CN117603262A (zh) | 2023-10-26 | 2023-10-26 | 一种磷系阻燃剂及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117603262A (zh) |
-
2023
- 2023-10-26 CN CN202311404573.6A patent/CN117603262A/zh active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104177809A (zh) | 低介电的无卤素树脂组合物及其应用 | |
CN103709717A (zh) | 乙烯苄基醚化-dopo化合物树脂组合物及制备和应用 | |
CN101928380B (zh) | 制备阻燃性多聚环氧化合物的方法 | |
EP3114170A1 (en) | Epoxy compositions | |
WO2005118604A1 (en) | Phosphorus-containing compounds useful for making halogen-free, ignition-resistant polymers | |
KR20020095190A (ko) | 난연성 에폭시수지 조성물, 그 성형물 및 전자부품 | |
KR101849833B1 (ko) | 에폭시 수지 조성물 및 상기 조성물을 사용하여 제작된 프리프레그 및 동박적층판 | |
JP2013216884A (ja) | 熱硬化性樹脂組成物、プリプレグ及び積層板 | |
CN105440645A (zh) | 含磷阻燃剂的低介电树脂组合物及其制备方法和应用 | |
CN110760163B (zh) | 一种无卤阻燃环氧树脂组合物及其应用 | |
JP5767250B2 (ja) | リン含有化合物を有する組成物 | |
EP2334691A1 (en) | Phosphorus-containing compounds and polymeric compositions comprising same | |
TWI548690B (zh) | 用於電用層板、高密度互連件以及互連基板應用之高性能熱固性樹脂 | |
Bao et al. | Synthesis of a novel flame retardant with phosphaphenanthrene and phosphazene double functional groups and flame retardancy of poly (lactic acid) composites | |
CN105801814A (zh) | 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板 | |
KR20130120212A (ko) | 에폭시몰딩컴파운드용 자기소화성 에폭시 수지 및 그 제법, 에폭시몰딩컴파운드용 에폭시 수지 조성물 | |
CN117603262A (zh) | 一种磷系阻燃剂及其制备方法与应用 | |
CN116004008A (zh) | 树脂组合物及其应用 | |
JP5024605B2 (ja) | 硬化性樹脂組成物、その硬化物、新規フェノール樹脂及びその製造方法 | |
JP2015224313A (ja) | 繊維強化樹脂材料、樹脂成形品および繊維強化樹脂材料の製造方法 | |
CN110831921A (zh) | 活性酯化合物和固化性组合物 | |
CN114106514B (zh) | 一种环氧树脂组合物、包含其的预浸料以及层压板和印制电路板 | |
JP2008195897A (ja) | プリプレグ及び積層板 | |
JP2006045546A (ja) | 熱硬化性樹脂組成物、ホウ酸変性トリアジン構造含有ノボラック樹脂、およびその製造方法 | |
JP2000129090A (ja) | 難燃性樹脂組成物、並びにこれを用いた半導体封止材料および積層板 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |