CN117736238A - Preparation method and application of phosphorus/boron synergistic cardanol-based flame retardant - Google Patents
Preparation method and application of phosphorus/boron synergistic cardanol-based flame retardant Download PDFInfo
- Publication number
- CN117736238A CN117736238A CN202311459587.8A CN202311459587A CN117736238A CN 117736238 A CN117736238 A CN 117736238A CN 202311459587 A CN202311459587 A CN 202311459587A CN 117736238 A CN117736238 A CN 117736238A
- Authority
- CN
- China
- Prior art keywords
- cardanol
- phosphorus
- flame retardant
- acid
- based 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
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 140
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 140
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 140
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 140
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 140
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 107
- 239000011574 phosphorus Substances 0.000 title claims abstract description 107
- 239000003063 flame retardant Substances 0.000 title claims abstract description 106
- 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 102
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 54
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 42
- 239000003822 epoxy resin Substances 0.000 claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 239000004327 boric acid Substances 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 hydrogen compound Chemical class 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- VWBYXJRDIQCSLW-UHFFFAOYSA-N O=[P](c1ccccc1)c1ccccc1 Chemical compound O=[P](c1ccccc1)c1ccccc1 VWBYXJRDIQCSLW-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 7
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-UHFFFAOYSA-N 0.000 claims description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 5
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- ZMUANTVDGHVAHS-UHFFFAOYSA-N OBOB(O)C1=CC=CC=C1 Chemical compound OBOB(O)C1=CC=CC=C1 ZMUANTVDGHVAHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- YVCYOVLYYZRNJC-UHFFFAOYSA-N (2-methoxyphenoxy)boronic acid Chemical compound COC1=CC=CC=C1OB(O)O YVCYOVLYYZRNJC-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- XIPRTRJDLZVSHO-UHFFFAOYSA-N aminooxy(phenoxy)borinic acid Chemical compound NOB(O)OC1=CC=CC=C1 XIPRTRJDLZVSHO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 claims 1
- HTGQCLJTWPSFNL-UHFFFAOYSA-N (2-methylphenoxy)boronic acid Chemical compound CC1=CC=CC=C1OB(O)O HTGQCLJTWPSFNL-UHFFFAOYSA-N 0.000 claims 1
- JEIZEIQZFFUKCV-UHFFFAOYSA-N (3-methylthiophen-2-yl)oxyboronic acid Chemical compound CC=1C=CSC=1OB(O)O JEIZEIQZFFUKCV-UHFFFAOYSA-N 0.000 claims 1
- ZZCMLQKQCWGLCJ-UHFFFAOYSA-N 2-boronooxybenzoic acid Chemical compound OB(O)OC1=CC=CC=C1C(O)=O ZZCMLQKQCWGLCJ-UHFFFAOYSA-N 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- YDMRDHQUQIVWBE-UHFFFAOYSA-N (2-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1O YDMRDHQUQIVWBE-UHFFFAOYSA-N 0.000 description 2
- MOOOGTOEKZWEJA-UHFFFAOYSA-N (3-methylthiophen-2-yl)boronic acid Chemical compound CC=1C=CSC=1B(O)O MOOOGTOEKZWEJA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ILOJFJBXXANEQW-UHFFFAOYSA-N aminooxy(phenyl)borinic acid Chemical compound NOB(O)C1=CC=CC=C1 ILOJFJBXXANEQW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 2
- KNPNGMXRGITFLE-UHFFFAOYSA-N methylperoxy(phenyl)borinic acid Chemical compound COOB(O)C1=CC=CC=C1 KNPNGMXRGITFLE-UHFFFAOYSA-N 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 244000226021 Anacardium occidentale Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- FMNFAXVBAQEWCV-UHFFFAOYSA-N aminooxyboronic acid Chemical compound NOB(O)O FMNFAXVBAQEWCV-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000020226 cashew nut Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention relates to a preparation method and application of a phosphorus/boron synergistic cardanol-based flame retardant, wherein the method comprises the steps of dropwise adding peroxy acid into cardanol under the protection of nitrogen at the temperature of below 10 ℃ to obtain epoxidized cardanol; step A2, heating the mixed solution of the phosphorus-containing hydrogen compound and the epoxidized cardanol to 80 ℃ to obtain phosphorus-containing cardanol; and step A3, respectively preparing a phosphorus-containing cardanol/organic solvent solution and a boric acid-containing compound/organic solvent solution to obtain the phosphorus/boron-containing synergistic cardanol-based flame retardant. According to the preparation method and the application of the phosphorus/boron synergistic cardanol-based flame retardant, the cardanol, the phosphorus-containing hydrogen compound and the boric acid-containing compound are adopted as raw materials to prepare the phosphorus/boron synergistic cardanol-based flame retardant which is liquid at room temperature, and the preparation process is environment-friendly and pollution-free. The liquid flame retardant has good compatibility with the epoxy resin matrix, is easy to disperse, can be directly used, can play the roles of flame retardance, reinforcement and toughening, and can also keep the transparency of the epoxy resin.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method and application of a phosphorus/boron synergistic cardanol-based flame retardant.
Background
The epoxy resin is a thermosetting material with a three-dimensional network structure formed by reacting monomers containing two or more epoxy groups with curing agents (such as polyamine, anhydride, polyacid, polyphenol, polythiol, polyimidazole and the like) under certain conditions. The adhesive has excellent cohesiveness, light transmittance, electrical insulation, chemical corrosion resistance and mechanical property, and has very wide application in the fields of aerospace, electronic and electric appliances, transportation, wind power generation and the like. Currently, bisphenol a type epoxy resins are the most widely used industrially. It is highly flammable, and when burning, it releases a lot of heat and toxic smoke, severely limiting its range of use and jeopardizing human life safety. Therefore, the improvement of the flame retardant property of the epoxy resin to reduce the fire hazard is of great significance.
Flame retardants are of many kinds and are classified as elemental flame retardants of halogen, phosphorus, nitrogen, silicon, boron and the like. Although the halogen flame retardant has good compatibility with a polymer matrix and high flame retardant efficiency, the halogen flame retardant can release toxic gases and generate cancerogenic substances in the degradation process, and the application of the halogen flame retardant is greatly limited. The development and application of halogen-free, low-toxicity flame retardants is the main focus of development in the flame retardant field. The phosphorus flame retardant has various types, can not only capture combustion chain free radicals in gas phase to inhibit combustion, but also form a heat-resistant carbon layer in solid phase to play a role in blocking, has the characteristics of low toxicity and high flame retardance, and is a flame retardant system capable of most replacing halogen-containing flame retardants. The nitrogen flame retardant mainly plays a dilution effect by decomposing and releasing nonflammable gas at high temperature. The phosphorus and nitrogen flame retardant are commonly used cooperatively to form the intumescent flame retardant, and the porous foam carbon layer is formed on the surface of the polymer, so that the flame retardant has the effects of heat insulation, oxygen isolation, smoke suppression and melt drip prevention, and has a good flame retardant effect. However, phosphorus/nitrogen compounded intumescent flame retardant systems often reduce the transparency of the polymer matrix and deteriorate its mechanical properties. The silicon and boron flame retardant is decomposed at high temperature to generate glassy silicon dioxide or diboron trioxide, has physical barrier effect, is nontoxic and good in smoke suppression performance, has small influence on the transparency and mechanics of a matrix, and has low flame retardant efficiency when being singly used. Thus, the synergistic use of different flame retardant elements is one of the most effective methods to increase flame retardant efficiency and maintain other physical and mechanical properties of the polymer matrix.
Cardanol is a renewable natural polyphenol compound obtained by decarboxylation of cashew nut shell oil at high temperature, and is oily liquid at room temperature. The benzene ring structure of cardanol makes it have high temperature resistant performance, while unsaturated long chain in benzene ring meta position has the chemical property of olefin, and provides excellent toughness, hydrophobicity and self-drying property. And when flame retardant elements such as phosphorus, nitrogen, boron and the like are introduced into the cardanol molecular chain, excellent flame retardant properties can be also imparted thereto. Chinese patent patents 111808252A, 114907399A and 111825821B respectively disclose a preparation method of a cardanol-based nitrogen-phosphorus-containing synergistic flame retardant or curing agent, but formaldehyde is used in the preparation process, so that the harm to operators is great. Patent 109251471A discloses a tricdanol phosphate toughening modifier and a preparation method and application thereof, 104610571A discloses a cardanol phosphate flame retardant plasticizer and a preparation method thereof, and the two patents adopt phosphoryl chloride as a raw material, wherein the phosphoryl chloride is easy to volatilize and generates strong acid when meeting water, and has high toxicity and corrosiveness and high requirements on reaction equipment and operator equipment. The biomass raw material is widely used because of the irreplaceable renewable and low toxicity characteristics, so that the environmental protection of the cardanol-based flame retardant in the synthesis and application processes is very necessary.
Disclosure of Invention
The invention provides a preparation method and application of a phosphorus/boron synergistic cardanol-based flame retardant, which adopts cardanol, a phosphorus-containing hydrogen compound and a boric acid-containing compound as raw materials to prepare the phosphorus/boron synergistic cardanol-based flame retardant which is liquid at room temperature, and the preparation process is environment-friendly and pollution-free. The liquid flame retardant has good compatibility with an epoxy resin matrix, is easy to disperse, can be directly used, can simultaneously play the roles of flame retardance, reinforcement and toughening, can also maintain the transparency of the epoxy resin, and has high application potential.
According to one aspect of the invention, a preparation method of a phosphorus/boron synergistic cardanol-based flame retardant is provided, wherein the cardanol-based flame retardant has a chemical structure shown in the following formula:
wherein R' is any one of the following structures:
r is any one of the following structures:
R＝-H,-NH 2 ,-OH,-COOH,-CH 3 ,-OCH 3 ,-SCH 3 and n=0 to 3, x=0 to 1.
The invention also provides a preparation method of the phosphorus/boron synergistic cardanol-based flame retardant, which comprises the following steps:
step A1, dropwise adding peroxy acid into cardanol at a speed of 1-5 drops/s under the protection of nitrogen at the temperature of below 10 ℃, keeping low-temperature reaction for 1-3 hours, then heating to 40-60 ℃, continuously stirring and reacting for 3-12 hours to obtain a reaction solution, and extracting the reaction solution by ethyl acetate to obtain the epoxidized cardanol;
step A2, heating the mixed solution of the phosphorus-containing compound and the epoxidized cardanol obtained in the step A1 to 80 ℃, adding a triphenylphosphine catalyst after the phosphorus-containing compound is completely melted, heating the mixed solution to 160 ℃ from 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 4-12 h, cooling the mixed solution to room temperature, adding ethyl acetate, and precipitating excessive phosphorus-containing compound to obtain phosphorus-containing cardanol;
and step A3, preparing a phosphorus-containing cardanol/organic solvent solution and a boric acid-containing compound/organic solvent solution respectively, dripping pyridine into the phosphorus-containing cardanol/organic solvent solution to adjust the pH value to 8-10, adding the boric acid-containing compound/organic solution, stirring and heating to 60-120 ℃, and carrying out reflux reaction for 6-24 hours to obtain the phosphorus/boron-containing synergistic cardanol-based flame retardant.
Preferably, the peroxy acid in the step A1 is an oxidizing agent based on the above scheme.
On the basis of the scheme, preferably, the oxidant is any one of hydrogen peroxide, peroxybenzoic acid, peroxym-chlorobenzoic acid and peroxytrifluoroacetic acid, and the molar ratio of the peroxyacid to cardanol is 1-5: 1, a step of; when the peroxyacid is hydrogen peroxide, formic acid or acetic acid needs to be added, and the molar ratio of the formic acid to the acetic acid is 1:1.
based on the above scheme, preferably, the molar ratio of the phosphorus-containing hydrogen compound to the cyclized cardanol in the step A2 is 1-6: 1, wherein triphenylphosphine accounts for 1-5% of the mass of the cyclized cardanol; the phosphorus-containing hydrogen compound is any one of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diphenyl phosphite and diphenyl phosphorus oxide.
Based on the above scheme, preferably, the concentration of the phosphorus-containing cardanol/organic solvent solution in the step A3 is 0.01-2 mol/L, the concentration of the boric acid-containing compound/organic solvent solution is 0.01-2 mol/L, and the molar ratio of the phosphorus-containing cardanol to the boric acid-containing compound is 2-6: 1.
on the basis of the above scheme, preferably, the boric acid-containing compound in the step A3 is any one of aminophenylboronic acid, hydroxyphenylboronic acid, carboxylic phenylboronic acid, methylphenylboronic acid, methoxyphenylboronic acid alcohol, methylthiophenylboronic acid and phenyldiboronic acid, and the organic solvent required for the reaction is any one of methanol, ethanol and tetrahydrofuran.
On the basis of the above scheme, preferably, the organic solvent used in the step A3 is any one of methanol, ethanol and tetrahydrofuran.
Based on the above scheme, preferably, the molar ratio of the phosphorus-containing cardanol to the boric acid-containing compound in the step A3 is 2-6: 1.
based on the above scheme, preferably, the concentration of the phosphorus-containing cardanol/organic solvent solution in the step A3 is 0.01-2 mol/L, and the concentration of the boric acid-containing compound/organic solvent solution is 0.01-2 mol/L.
The invention also provides a phosphorus/boron synergistic cardanol-based flame retardant which is obtained by any one of the preparation methods.
Based on the scheme, the obtained phosphorus/boron synergistic cardanol-based flame retardant is preferably applied to the preparation of epoxy resin.
Based on the scheme, preferably, the mass ratio of the flame retardant to the epoxy resin is (2-8): (92-98).
The invention also provides application of the phosphorus/boron synergistic cardanol-based flame retardant, and the obtained phosphorus/boron synergistic cardanol-based flame retardant is applied to preparation of epoxy resin.
Compared with the prior art, the invention has the beneficial effects that:
1) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention is orange oily liquid at room temperature, has good compatibility with an epoxy resin matrix, can be directly added for use, does not need a volatile organic solvent as a dispersion medium, and is safe in construction, energy-saving and environment-friendly.
2) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention contains rich phosphorus and boron flame retardant elements, and has high flame retardant efficiency; in addition, the hydroxyl in the molecular chain of the flame retardant can participate in the curing reaction of the epoxy resin to be fixed in the epoxy resin crosslinked network structure, so that the flame retardant is not easy to migrate and separate out and has lasting flame retardant property.
3) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention contains a large number of rigid structures such as benzene rings, phosphate (phosphaphenanthrene), borate and the like, and can provide enhanced and heat-resistant properties; on the other hand, the flexible alkyl long chain is contained, so that the toughness of the epoxy resin matrix can be improved; on the other hand, the epoxy resin has good dispersibility and small dosage, and can maintain the transparency of the epoxy resin.
4) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention takes the renewable resource cardanol as a raw material, has the advantages of low cost, rich sources and the like, meets the requirement of sustainable development, widens the application range of cardanol, and improves the additional value of rural residual agricultural products.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Attached at
In the figure:
FIG. 1 is a flow chart of a preparation method of a phosphorus/boron synergistic cardanol-based flame retardant of the present invention;
FIG. 2 is a reaction diagram of the preparation of the phosphorus/boron synergistic cardanol-based flame retardant of the present invention.
Detailed Description
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
It should be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
For the sake of simplicity of the drawing, the parts relevant to the present invention are shown only schematically in the figures, which do not represent the actual structure thereof as a product. Additionally, in order to simplify the drawing for ease of understanding, components having the same structure or function in some of the drawings are shown schematically with only one of them, or only one of them is labeled. Herein, "a" means not only "only this one" but also "more than one" case.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
In the embodiment shown in the drawings, indications of orientation (such as up, down, left, right, front and rear) are used to explain the structure and movement of the various components of the invention are not absolute but relative. These descriptions are appropriate when the components are in the positions shown in the drawings. If the description of the location of these components changes, then the indication of these directions changes accordingly.
In addition, in the description of the present application, the terms "first," "second," and the like are used merely to distinguish between descriptions and are not to be construed as indicating or implying relative importance.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will explain the specific embodiments of the present invention with reference to the accompanying drawings. It is evident that the drawings in the following description are only examples of the invention, from which other drawings and other embodiments can be obtained by a person skilled in the art without inventive effort.
Referring to fig. 1, and referring to fig. 2, the invention provides a preparation method of a phosphorus/boron synergistic cardanol-based flame retardant, which comprises the following specific steps:
and step A1, dropwise adding peroxy acid into cardanol at a speed of 1-5 drops/s under the protection of nitrogen at a low temperature (T <10 ℃) and after the dropwise adding, stirring, keeping the low temperature for reaction for 1-3 hours, heating to 40-60 ℃, continuing to stir and react for 3-12 hours, and completely oxidizing unsaturated double bonds into epoxy rings. Extracting the reaction liquid by ethyl acetate, reserving an organic phase, adding anhydrous sodium sulfate for removing water, filtering to remove sodium sulfate, and distilling under reduced pressure to remove ethyl acetate, wherein the product is the epoxidized cardanol;
and step A2, heating the mixed solution of the phosphorus-containing compound and the epoxidized cardanol to 80 ℃, adding triphenylphosphine as a catalyst after the phosphorus-containing compound is completely melted, gradually heating and refluxing for 4-12 hours at 80-160 ℃ under the protection of nitrogen, and grafting the phosphorus-containing flame retardant to a cardanol molecular chain through the ring opening reaction of a phosphorus hydrogen bond and an epoxy ring. Cooling the reaction liquid to room temperature, adding ethyl acetate to precipitate excessive phosphorus-containing hydrogen compounds, removing impurities by suction filtration, and distilling under reduced pressure to remove the ethyl acetate, wherein the product is phosphorus-containing cardanol;
and step A3, preparing phosphorus-containing cardanol/organic solvent solutions and boric acid-containing compound/organic solvent solutions respectively. And (3) dropwise adding pyridine into the phosphorus-containing cardanol/organic solvent solution, adjusting the pH value to be 8-10, adding the boric acid-containing compound/organic solvent solution, stirring and heating to 60-120 ℃, carrying out reflux reaction for 6-24 h, and obtaining the cardanol-based flame retardant containing phosphate (or phosphaphenanthrene) and borate simultaneously through esterification reaction. The reaction solution is subjected to suction filtration, washing, reduced pressure distillation to remove the solvent, and drying treatment is carried out, and the final product is orange oily liquid.
Wherein, the peroxyacid in the step A1 is any one of hydrogen peroxide, peroxybenzoic acid, peroxym-chlorobenzoic acid and peroxytrifluoroacetic acid. When hydrogen peroxide is selected, formic acid or acetic acid needs to be added, and the molar ratio of the formic acid to the acetic acid is 1:1.
in the step A1, the molar ratio of the peroxyacid to the cardanol is 1-5: 1.
in the step A2, the phosphorus-containing compound is any one of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diphenyl phosphite and diphenyl phosphorus oxide, preferably DOPO.
In the step A2, the mol ratio of the phosphorus-containing hydrogen compound to the epoxidized cardanol is 1-6: 1.
in the step A3, triphenylphosphine accounts for 1-5% of the mass of the epoxidized cardanol.
The boric acid compound in the step A3 is any one of amino phenylboronic acid, hydroxy phenylboronic acid, carboxylic phenylboronic acid, methyl phenylboronic acid, methoxy phenylboronic acid alcohol, methylthiophenylboronic acid and phenyldiboronic acid, preferably phenyldiboronic acid.
The organic solvent used in the step A3 is any one or a mixture of methanol, ethanol and tetrahydrofuran, preferably tetrahydrofuran.
In the step A3, the mol ratio of the phosphorus-containing cardanol to the boric acid-containing compound is 2-6: 1.
in the step A3, pyridine is used as a pH value regulator, and the pH value is 8-10.
In the step A3, the concentration of the phosphorus-containing cardanol/organic solvent solution is 0.01-2 mol/L, and the concentration of the boric acid-containing compound/organic solvent solution is 0.01-2 mol/L.
The application of the phosphorus/boron synergistic cardanol-based flame retardant in epoxy resin comprises the following specific steps: the liquid flame retardant is directly added into an epoxy resin monomer, heated to 60-120 ℃ and stirred for 20-50 min, so that the flame retardant is uniformly dispersed in the epoxy resin monomer; adding the curing agent, continuously stirring for 10-60 min to enable the curing agent to be completely melted and uniformly dispersed, pouring the mixture into a preheated mold while the mixture is hot, curing the mixture for 2-8 h at 80-200 ℃, cooling and demolding the mixture to obtain the cured epoxy resin system.
In order to illustrate the technical effects of the present application, the following will be described with specific examples and comparative examples:
example 1
Preparation of phosphorus/boron synergistic cardanol-based flame retardant
1) Dropwise adding m-chlorobenzoic acid peroxide into cardanol at a speed of 1 drop/s at a temperature lower than 5 ℃ under the protection of nitrogen, wherein the m-chlorobenzoic acid peroxide: the molar ratio of cardanol is 1:1, after the dripping is finished, keeping the low-temperature reaction for 3 hours, heating to 60 ℃, continuing to stir and react for 10 hours, extracting by ethyl acetate, retaining an organic phase, adding anhydrous sodium sulfate to remove water, filtering to remove sodium sulfate salt, and distilling under reduced pressure to remove ethyl acetate, wherein the product is the epoxidized cardanol;
step A2, heating a mixed solution of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and epoxidized cardanol to 80 ℃, wherein the molar ratio of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to the epoxidized cardanol is 3:1. after DOPO is completely melted, triphenylphosphine (Ph) is added 3 P) catalyst (cardanol mass 1%) and reflux reaction at 100 deg.C, 120 deg.C, 140 deg.C and 160 deg.C under nitrogen protection for 2 hr. After the reaction solution is cooled to room temperature, adding ethyl acetate to precipitate excessive DOPO, removing impurities by suction filtration, and distilling under reduced pressure to remove the ethyl acetate, wherein the product is phosphorus-containing cardanol;
step A3, after adjusting the ph=8 of the phosphorus-containing cardanol/tetrahydrofuran solution (0.05 mol/L) with pyridine, adding 1, 4-phenyldiboronic acid/tetrahydrofuran solution (0.025 mol/L), wherein the molar ratio of phosphorus-containing cardanol to 1, 4-phenyldiboronic acid is 6:1. and heating the reaction solution to 110 ℃, carrying out reflux reaction for 24 hours, and carrying out suction filtration, washing and reduced pressure distillation to remove the solvent to obtain the cardanol-based flame retardant 1 with the synergistic effect of phosphorus and boron.
Example 2
Preparation of phosphorus/boron synergistic cardanol-based flame retardant
1) Dropwise adding 30% hydrogen peroxide and 80% formic acid into cardanol at a speed of 2 drops/s at a temperature lower than <5 ℃ under the protection of nitrogen, wherein the hydrogen peroxide: formic acid: the molar ratio of cardanol is 2:2:1, after the dripping is finished, keeping the low-temperature reaction for 2 hours, heating to 40 ℃, continuing to stir and react for 8 hours, extracting by ethyl acetate, retaining an organic phase, adding anhydrous sodium sulfate to remove water, filtering to remove sodium sulfate salt, and distilling under reduced pressure to remove ethyl acetate, wherein the product is the epoxidized cardanol;
2) Adding diphenyl phosphite into the mixed solution of the epoxidation cardanol, and heating to 80 ℃ (the molar ratio of the diphenyl phosphite to the mixed solution is 3: 1) After diphenyl phosphite is completely melted, triphenylphosphine catalyst (1.5% of cardanol mass) is added, and reflux reaction is carried out at 100 ℃ and 120 ℃ and 140 ℃ under the protection of nitrogen, wherein each reflux reaction is carried out at 160 ℃ for 2.5h. Cooling the reaction liquid to room temperature, adding ethyl acetate to precipitate excessive diphenyl phosphite, filtering out precipitate, and distilling under reduced pressure to remove the ethyl acetate, wherein the product is phosphorus-containing cardanol;
3) After adjusting the ph=9 of the phosphorus-containing cardanol/tetrahydrofuran solution (0.1 mol/L) with pyridine, an aminophenylboric acid/tetrahydrofuran solution (0.05 mol/L) was added, wherein the molar ratio of phosphorus-containing cardanol to aminoboric acid was 3:1. and heating the reaction solution to 90 ℃, carrying out reflux reaction for 18 hours, and carrying out suction filtration and reduced pressure distillation to remove the solvent to obtain the cardanol-based flame retardant 2 with the synergistic effect of phosphorus and boron.
Example 3
Preparation of phosphorus/boron synergistic cardanol-based flame retardant
1) At a temperature below <5 ℃ and under nitrogen protection, peroxytrifluoroacetic acid was added dropwise to cardanol at a rate of 1 drop/s (peroxytrifluoroacetic acid: the molar ratio of cardanol is 1: 1) After the dripping is finished, keeping the low temperature for 2 hours, heating to 40 ℃, continuing to stir and react for 3 hours, extracting by ethyl acetate, retaining an organic phase, adding anhydrous sodium sulfate to remove water, filtering to remove sodium sulfate salt, and distilling under reduced pressure to remove ethyl acetate, wherein the product is the epoxidized cardanol;
2) The mixed solution of diphenyl phosphorus oxide and epoxidized cardanol is heated to 80 ℃ (the molar ratio of the diphenyl phosphorus oxide to the epoxidized cardanol is 4: 1) After diphenyl phosphorus oxide is completely melted, adding triphenylphosphine catalyst (cardanol mass 2%), and carrying out reflux reaction at 100 ℃,120 ℃,140 ℃ and 160 ℃ under the protection of nitrogen gas for 2h. Cooling the reaction liquid to room temperature, adding ethyl acetate to precipitate excessive diphenyl phosphorus oxide, filtering out precipitate, and distilling under reduced pressure to remove ethyl acetate, wherein the product is phosphorus-containing cardanol;
3) After adjusting the ph=9 of the phosphorus-containing cardanol/methanol solution (0.06 mol/L) with pyridine, methoxyphenylboric acid/methanol solution (0.03 mol/L) was added, wherein the molar ratio of the phosphorus-containing cardanol to the methoxyphenylboric acid was 3:1. and heating the reaction solution to 110 ℃, carrying out reflux reaction for 14 hours, and carrying out suction filtration and reduced pressure distillation to remove the solvent to obtain the cardanol-based flame retardant 3 with the synergistic effect of phosphorus and boron.
Example 4
Preparation of phosphorus/boron synergistic cardanol-based flame retardant
1) Dropwise adding peroxybenzoic acid into cardanol at a speed of 1 drop/s at a temperature below <5 ℃ under the protection of nitrogen, wherein the peroxybenzoic acid: the molar ratio of cardanol is 1:1, after the dripping is finished, keeping the low temperature for 2 hours, heating to 50 ℃, continuously stirring and reacting for 4 hours, extracting by ethyl acetate, retaining an organic phase, adding anhydrous sodium sulfate for removing water, filtering to remove sodium sulfate salt, and distilling under reduced pressure to remove ethyl acetate, wherein the product is the epoxidized cardanol;
2) The mixture of DOPO and epoxidized cardanol was heated to 80 ℃ (both molar ratio 4: 1) After DOPO is completely melted, triphenylphosphine is added as a catalyst (3% of the mass of cardanol), and reflux reaction is carried out for 3 hours under the protection of nitrogen at 100 ℃,120 ℃,140 ℃ and 160 ℃ in a gradual heating mode. Cooling the reaction liquid to room temperature, adding ethyl acetate to precipitate excessive DOPO, filtering out precipitate, and distilling under reduced pressure to remove ethyl acetate, wherein the product is phosphorus-containing cardanol;
3) After adjusting the ph=10 of the phosphorus-containing cardanol/ethanol solution (0.1 mol/L) with pyridine, 1, 4-phenyldiboronic acid/ethanol solution (0.05 mol/L) was added, wherein the molar ratio of phosphorus-containing cardanol to 1, 4-phenyldiboronic acid was 6:1. and heating the reaction solution to 110 ℃, carrying out reflux reaction for 12 hours, and then carrying out suction filtration and reduced pressure distillation to remove the solvent to obtain the cardanol-based flame retardant 4 with the synergistic effect of phosphorus and boron.
Application example 1
1g of the flame retardant in preparation method example 1 is weighed, added into 34.3g of epoxy resin E51, heated to 80 ℃ and stirred for 10min, added with 14.7g of diaminodiphenyl methane curing agent, continuously stirred for 20min until the curing agent is completely melted, poured into a preheated mold while the curing agent is hot, respectively cured for 2h at 100 ℃ and 140 ℃, cooled and demoulded, thus obtaining the cured epoxy resin system 1.
Application example 2
Weighing 2g of the flame retardant in preparation method example 1, adding 33.6g of epoxy resin E51, heating to 80 ℃, stirring for 10min, adding 14.4g of diaminodiphenyl methane curing agent, continuously stirring for 20min until the curing agent is completely melted, pouring into a preheated mold while the curing agent is hot, respectively curing at 100 ℃ and 140 ℃ for 2h, cooling and demolding to obtain a cured epoxy resin system 2.
Application example 3
3g of the flame retardant in preparation method example 1 is weighed, added into 32.9g of epoxy resin E51, heated to 80 ℃ and stirred for 15min, added with 14.1g of diaminodiphenyl methane curing agent, continuously stirred for 20min until the curing agent is completely melted, poured into a preheated mold while the curing agent is hot, respectively cured for 2h at 100 ℃ and 140 ℃, cooled and demoulded, thus obtaining a cured epoxy resin system 3.
Application example 4
Weighing 4g of the flame retardant in preparation method example 1, adding 32.2g of epoxy resin E51, heating to 80 ℃, stirring for 20min, adding 13.8g of diaminodiphenyl methane curing agent, continuously stirring for 20min until the curing agent is completely melted, pouring into a preheated mold while the curing agent is hot, respectively curing at 100 ℃ and 140 ℃ for 2h, cooling and demolding to obtain a cured epoxy resin system 4.
Comparative example
Heating 35g of epoxy E51 to 80 ℃, stirring for 10min, adding 15g of diaminodiphenyl methane curing agent, continuously stirring for 20min until the curing agent is completely melted, pouring the mixture into a preheated mold while the mixture is hot, respectively curing the mixture at 100 ℃ and 140 ℃ for 2h, cooling and demolding the mixture to obtain a cured pure epoxy resin system.
Performance test results table of epoxy resin prepared from cardanol-based flame retardant 1 containing different contents of phosphorus/boron synergism
The table shows that with the increase of the adding amount of the phosphorus/boron synergistic cardanol-based flame retardant 1, the tensile strength of the prepared epoxy resin sample is highest when the flame retardant content is 6%, and is improved by 31.7% compared with the pure epoxy resin; impact strength increases with increasing flame retardant content, and at 8% content, 121.0% is improved over pure epoxy resin; the oxygen index can reach more than 30% when the content of the flame retardant is 2%, and the oxygen index is increased along with the increase of the consumption of the flame retardant; UL94 vertical burn rating can reach V-0 rating at 4% flame retardant content; transparency decreases with increasing amounts of flame retardant.
Compared with the prior art, the invention has the beneficial effects that:
1) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention is orange oily liquid at room temperature, has good compatibility with an epoxy resin matrix, can be directly added for use, does not need a volatile organic solvent as a dispersion medium, is safe in construction, saves energy and protects environment.
2) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention contains rich phosphorus and boron flame retardant elements, and has high flame retardant efficiency; in addition, the hydroxyl in the molecular chain of the flame retardant can participate in the curing reaction of the epoxy resin to be fixed in the epoxy resin crosslinked network structure, so that the flame retardant is not easy to migrate and separate out and has lasting flame retardant property.
3) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention contains a large number of rigid structures such as benzene rings, phosphaphenanthrene, borate and the like, and can provide enhanced and heat-resistant properties; on the other hand, the flexible alkyl long chain is contained, so that the toughness of the epoxy resin matrix can be improved; on the other hand, the epoxy resin has good dispersibility and small dosage, and can maintain the transparency of the epoxy resin.
4) The phosphorus/boron-containing synergistic cardanol-based flame retardant provided by the invention takes the renewable resource cardanol as a raw material, has the advantages of low cost, rich sources and the like, meets the requirement of sustainable development, widens the application range of cardanol, and improves the additional value of rural residual agricultural products.
Finally, the methods of the present application are only preferred embodiments and are not intended to limit the scope of the invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the phosphorus/boron synergistic cardanol-based flame retardant is characterized in that the chemical structure of the cardanol-based flame retardant is shown as the following formula:
wherein R' is any one of the following structures:
r is any one of the following structures:
R＝-H,-NH 2 ,-OH,-COOH,-CH 3 ,-OCH 3 ,-SCH 3 and n=0 to 3, x=0 to 1.
2. The preparation method of the phosphorus/boron synergistic cardanol-based flame retardant is characterized by comprising the following steps of:
step A1, dropwise adding peroxy acid into cardanol at a speed of 1-5 drops/s under the protection of nitrogen at the temperature of below 10 ℃, keeping low-temperature reaction for 1-3 hours, then heating to 40-60 ℃, continuously stirring and reacting for 3-12 hours to obtain a reaction solution, and extracting the reaction solution by ethyl acetate to obtain the epoxidized cardanol;
step A2, heating the mixed solution of the phosphorus-containing compound and the epoxidized cardanol obtained in the step A1 to 80 ℃, adding a triphenylphosphine catalyst after the phosphorus-containing compound is completely melted, heating the mixed solution to 160 ℃ from 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 4-12 h, cooling the mixed solution to room temperature, adding ethyl acetate, and precipitating excessive phosphorus-containing compound to obtain phosphorus-containing cardanol;
and step A3, preparing a phosphorus-containing cardanol/organic solvent solution and a boric acid-containing compound/organic solvent solution respectively, dripping pyridine into the phosphorus-containing cardanol/organic solvent solution to adjust the pH value to 8-10, adding the boric acid-containing compound/organic solution, stirring and heating to 60-120 ℃, and carrying out reflux reaction for 6-24 hours to obtain the phosphorus/boron-containing synergistic cardanol-based flame retardant.
3. The method for preparing a phosphorus/boron synergistic cardanol-based flame retardant of claim 2, wherein the peroxyacid in step A1 is an oxidizing agent.
4. The method for preparing the phosphorus/boron synergistic cardanol-based flame retardant of claim 3, wherein the oxidant is any one of hydrogen peroxide, peroxybenzoic acid, peroxym-chlorobenzoic acid and peroxytrifluoroacetic acid, and the molar ratio of the peroxyacid to cardanol is 1-5: 1, a step of; when the peroxyacid is hydrogen peroxide, formic acid or acetic acid needs to be added, and the molar ratio of the formic acid to the acetic acid is 1:1.
5. the method for preparing the phosphorus/boron synergistic cardanol-based flame retardant of claim 2, wherein the molar ratio of the phosphorus-containing compound to the cyclized cardanol in the step A2 is 1-6: 1, wherein triphenylphosphine accounts for 1-5% of the mass of the cyclized cardanol; the phosphorus-containing hydrogen compound is any one of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diphenyl phosphite and diphenyl phosphorus oxide.
6. The method for preparing a phosphorus/boron synergistic cardanol-based flame retardant of claim 2, wherein the concentration of the solution of cardanol/organic solvent containing phosphorus in step A3 is 0.01-2 mol/L, the concentration of the solution of cardanol/organic solvent containing boric acid is 0.01-2 mol/L, and the molar ratio of cardanol/boric acid compound containing phosphorus is 2-6: 1.
7. the method for preparing a phosphorus/boron synergistic cardanol-based flame retardant of claim 2, wherein the boric acid-containing compound in step A3 is any one of aminophenylboric acid, hydroxyphenylboric acid, carboxyphenylboric acid, methylphenylboric acid, methoxyphenylboric acid alcohol, methylthiophenylboric acid and phenyldiboronic acid, and the organic solvent required for the reaction is any one of methanol, ethanol and tetrahydrofuran.
8. A phosphorus/boron synergistic cardanol-based flame retardant obtainable by the process of any one of claims 2 to 7.
9. The use of a phosphorus/boron synergistic cardanol-based flame retardant as defined in claim 8 in the preparation of epoxy resins.
10. The use of a phosphorus/boron synergistic cardanol based flame retardant of claim 9, wherein the mass ratio of flame retardant to epoxy resin is (2-8): (92-98).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311459587.8A CN117736238A (en) | 2023-11-03 | 2023-11-03 | Preparation method and application of phosphorus/boron synergistic cardanol-based flame retardant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311459587.8A CN117736238A (en) | 2023-11-03 | 2023-11-03 | Preparation method and application of phosphorus/boron synergistic cardanol-based flame retardant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117736238A true CN117736238A (en) | 2024-03-22 |
Family
ID=90251596
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311459587.8A Pending CN117736238A (en) | 2023-11-03 | 2023-11-03 | Preparation method and application of phosphorus/boron synergistic cardanol-based flame retardant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117736238A (en) |
-
2023
- 2023-11-03 CN CN202311459587.8A patent/CN117736238A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Preparation, thermal properties, and flame retardance of epoxy–silica hybrid resins | |
| Wang et al. | Phosphorus‐containing epoxy resin for an electronic application | |
| CN112300538B (en) | Preparation method of novel inorganic-organic hybrid flame-retardant epoxy resin material | |
| CN107337694A (en) | A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate | |
| TW201125873A (en) | Hydroxyphenyl phosphine oxide mixtures and their use as flame retardants for epoxy resins | |
| CN109897219A (en) | A kind of reactive flame retardant and its preparation method and application | |
| TW593527B (en) | Halogen-free, phosphorus-free flame-retardant advanced epoxy resin and an epoxy composition containing the same | |
| CN111635618A (en) | Phosphazene-based organic metal complex flame-retardant epoxy resin and preparation method thereof | |
| CN111732607A (en) | Carboxylic acid compound containing phosphorus, nitrogen and boron, preparation method thereof, and preparation method and application of flame-retardant epoxy resin | |
| CN111662421A (en) | Intrinsic flame-retardant cardanol-based phenolic epoxy resin and preparation method thereof | |
| CN113234228B (en) | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof | |
| CN113429770A (en) | Preparation method of efficient flame-retardant modified unsaturated polyester resin | |
| CN112250712A (en) | DOPO-containing bisphthalonitrile flame retardant and preparation method and application method thereof | |
| CN109897167A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN109897224A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN117736238A (en) | Preparation method and application of phosphorus/boron synergistic cardanol-based flame retardant | |
| CN108485193B (en) | Flame-retardant epoxy resin composition for electronic packaging material and preparation method thereof | |
| CN107501526B (en) | DOPO type epoxy resin curing agent and preparation method thereof | |
| CN109897164A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN109897220A (en) | A kind of reactive flame retardant and its preparation method and application | |
| CN114634654A (en) | Efficient halogen-free phosphorus and nitrogen intumescent flame retardant and preparation method thereof | |
| CN109575076B (en) | Preparation of phosphorus-containing bismaleimide and application of phosphorus-containing bismaleimide in flame-retardant epoxy resin | |
| CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
| CN112430381B (en) | Preparation method of intrinsic organic-inorganic smoke-suppression flame-retardant epoxy resin composite material | |
| CN109206594A (en) | A kind of Intrinsical halogen-free flameproof epoxy glue and preparation method thereof |
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 |