CN110981905B - Phosphorus-bromine-containing cardanol-based photosensitive resin, preparation method and application thereof - Google Patents
Phosphorus-bromine-containing cardanol-based photosensitive resin, preparation method and application thereof Download PDFInfo
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- CN110981905B CN110981905B CN201911170022.1A CN201911170022A CN110981905B CN 110981905 B CN110981905 B CN 110981905B CN 201911170022 A CN201911170022 A CN 201911170022A CN 110981905 B CN110981905 B CN 110981905B
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- cardanol
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- phosphorus
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- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 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 58
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 58
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 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 55
- HOHPOKYCMNKQJS-UHFFFAOYSA-N [P].[Br] Chemical compound [P].[Br] HOHPOKYCMNKQJS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000576 coating method Methods 0.000 claims abstract description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 29
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 28
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001723 curing Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims abstract description 21
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 trihydroxyethyl Chemical group 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000010452 phosphate Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 244000226021 Anacardium occidentale Species 0.000 claims abstract description 12
- 235000020226 cashew nut Nutrition 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 5
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 7
- 239000011574 phosphorus Substances 0.000 abstract description 7
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003063 flame retardant Substances 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 2
- 229960001701 chloroform Drugs 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 10
- 229910052794 bromium Inorganic materials 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000005337 ground glass Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a phosphorus-bromine cardanol-based photosensitive resin, and a preparation method of the photosensitive resin comprises the following steps: firstly, dissolving hydroxyethyl cashew shell oil ether and triethylamine in trichloromethane, dropwise adding phosphorus oxychloride at 0-30 ℃ for reaction, then heating for continuous reaction, carrying out suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing and drying to obtain a trihydroxyethyl cardanol phosphate ether oligomer; and reacting the obtained trihydroxyethyl cardanol phosphate oligomer, acrylic acid and N-bromosuccinimide at room temperature for 7d, adding diethyl ether, deionized water and a potassium iodide solution to obtain a mixture, neutralizing the pH value of the solution to 7, separating, washing and drying to obtain the phosphorus-bromine cardanol-based photosensitive resin. The coating prepared from the photosensitive resin containing phosphorus cardanol groups has greatly improved mechanical properties, good flame retardant property and light curing crosslinking reaction due to the double bond contained on the long-chain side group.
Description
Technical Field
The invention relates to the technical field of ultraviolet light curing, in particular to a method for preparing bio-based photosensitive resin by reacting hydroxyethyl cashew nut shell oil ether with phosphorus oxychloride and then adding acrylic acid and N-bromosuccinimide and an ultraviolet light curing coating prepared from the resin.
Background
The cardanol is used as a main component in Cashew Nut Shell Liquid (CNSL for short) which is one of agricultural byproducts with the largest global yield, the source is rich, the price is low, most of the Cashew Nut Shell Liquid sold in the market is a product after hot pressing decarboxylation treatment, and the content of the cardanol reaches about 90 percent. The cardanol is a light yellow oily liquid at normal temperature, has four different structural components of saturated, monoene, diene and triene, and all of the components have long unsaturated side chains with 15 carbons, and the average degree of unsaturation is about 2. Cardanol derivatives, such as hydroxyethyl cashew nut shell oil ether (HCE), have high activity, are easy to modify in chemical industry, have good hydrophobicity and chemical resistance, and play an important role in replacing petroleum-based products.
Phosphorus oxychloride, an industrial chemical raw material, is prepared by adding phosphorus trichloride into a reactor and introducing chlorine gas into the reactor through a chlorination hydrolysis method, and is a colorless and transparent fuming liquid. Different functional groups can be grafted through nucleophilic substitution and other reactions to have different structures, so that the material has diversity of physical and chemical properties.
Ultraviolet (UV) curing technology belongs to the class of radiation curing technology, and is a new curing technology. The method is a chemical process that liquid resin with photochemical reaction activity is excited by using energy radiated by ultraviolet light, rapidly generates and participates in photopolymerization, and then is mutually crosslinked into a three-dimensional network to be converted into a solid substance. Since the advent of the UV curing technology, the UV curing technology has been developed in the field of coatings, and is continuously developed and matured in the aspects of technology, raw materials and the like.
Considering the ecological and economic problems of the new generation of coating industry, improving the specific gravity of natural materials in polymer synthesis is a better choice, and the bio-based photocureable coating based on renewable resources increasingly becomes a research hotspot in the coating field due to the characteristics of green environmental protection and high cost performance. Due to the limited variety of biological raw materials, the structural characteristics of the biological raw materials and the like, the bio-based UV curing resin at the present stage has more problems, such as poor mechanical properties of a coating, difficulty in meeting the requirements of high bio-based content and excellent comprehensive properties, and the like, and the polymer materials have the common problem of flammability, so that more intensive research is needed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a phosphorus-bromine cardanol-based photosensitive resin, which comprises the following steps:
(1) dissolving hydroxyethyl cashew nut shell oil ether and triethylamine in chloroform, dropwise adding phosphorus oxychloride at 0-30 ℃ for reacting for 1-5 h, then heating to 40-60 ℃, continuing to react for 3-6 h, performing suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing and drying to obtain a trihydroxyethyl cardanol phosphate oligomer;
(2) and (2) reacting the trihydroxyethyl cardanol phosphate oligomer, acrylic acid and N-bromosuccinimide at room temperature, adding diethyl ether, deionized water and a potassium iodide solution to obtain a mixture, neutralizing the pH value of the solution to 7, and separating, washing and drying to obtain the phosphorus-bromine cardanol-based photosensitive resin.
In one embodiment, the phosphorus oxychloride is added dropwise in the step (1) at 25 ℃ for reaction for 3 hours, and then the temperature is increased to 50 ℃ for further reaction for 6 hours.
In one embodiment, the molar ratio of triethylamine, phosphorus oxychloride and hydroxyethyl cashew nut shell oil ether in the step (1) is 2-4: 1: 1-10.
In one embodiment, the amount of chloroform in step (1) is 0.1-1 times of the mass of hydroxyethyl cardanol shell oil ether.
In one embodiment, the molar ratio of the double bond in the trihydroxyethyl cardanol phosphate oligomer, the acrylic acid and the N-bromosuccinimide in the step (2) is 1: 15-40: 1-10.
Another object of the present invention is to provide a photosensitive resin containing a phosphorus-bromine cardanol group, which is prepared by any one of the above methods.
In one embodiment, the photosensitive resin having a phosphorous-bromine cardanol group has a structure as shown below:
Another object of the present invention is to provide a use of a photosensitive resin containing a phosphorus-bromine cardanol group, comprising: mixing the photosensitive resin containing the phosphorus-bromine cardanol group, the active diluent and the photoinitiator, coating the mixture on a base material with the thickness of 30-120 mu m, and exposing the mixture to 1000mJ/cm2～2000mJ/cm2Curing under the ultraviolet light of energy to prepare the ultraviolet curing coating material.
In one embodiment, the weight ratio of the photosensitive resin containing phosphorus-bromine cardanol group, the reactive diluent and the photoinitiator is 7-10: 1-3: 0.1-0.5.
In one embodiment, the photoinitiator is selected from one or more of photoinitiator 819, photoinitiator 1173, photoinitiator 184, photoinitiator 907, TPO, ITX, TBPB, DCP.
The active diluent is one or more of ethylene glycol diacrylate, propylene glycol diacrylate, N-butyl acrylate, isooctyl acrylate, isodecyl acrylate, lauryl acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, vinyl acetate, N-vinyl pyrrolidone and tripropylene glycol diacrylate.
The base material is one of a wood plate, a tinplate, a steel plate and a glass plate.
The beneficial technical effects of the invention are as follows:
4. according to the invention, hydroxyethyl cashew nut shell oil ether is adopted as a raw material for synthesizing the photosensitive resin containing phosphorus-bromine cardanol group, and the alcoholic hydroxyl group of the hydroxyethyl cashew nut shell oil ether can be used for carrying out affinity substitution reaction with phosphorus oxychloride under mild conditions, so that the controllability is strong, and the operation is simple.
5. According to the phosphorus-bromine-containing cardanol-based photosensitive resin prepared by the invention, a rigid benzene ring structure and a long carbon chain are introduced by using hydroxyethyl cashew nut shell oil ether, so that the resin has excellent mechanical strength and flexibility, and the mechanical property is greatly improved; the long carbon chain contains double bonds, so that addition polymerization reaction can occur, and further bromine is introduced, and the resin has better flame retardant property due to the synergistic action of phosphorus and bromine;
6. the phosphorus-bromine cardanol-based photosensitive resin prepared by the invention contains double bonds, can be applied to ultraviolet curing crosslinking, increases the variety of ultraviolet curing materials, widens the application field and improves the application value.
Drawings
Fig. 1 is a schematic diagram of a reaction mechanism of synthesizing the photosensitive resin containing phosphorus-bromine cardanol group in example 1.
FIG. 2 is a combustion test chart of a phosphorus-bromine cardanol-based photosensitive resin APT-HCE, wherein A is horizontally combusted and B is vertically combusted.
Detailed Description
In order to better explain the present invention, the present invention is further explained in detail with reference to specific examples below.
Example 1:
fig. 1 is a schematic diagram of the synthesis of a photosensitive resin containing phosphorus-bromine cardanol group.
Preparing a photosensitive resin containing phosphorus-bromine cardanol group:
(1) 137.180g (0.4mol) of Hydroxyethyl Cardanol Ether (HCE) and 40.480g of triethylamine (0.4mol) (TEA) were weighed out separately and added to a three-necked flask, and 15.000g of chloroform was taken and dissolved by ultrasonic agitation. After the stirring and the thermometer are assembled, the mixture is put into a water bath kettle, 18.500g (0.12mol) of phosphorus oxychloride is weighed and dissolved in 20ml of chloroform in a constant pressure dropping funnel, the dropping is completed within 0.5h at 25 ℃, after the reaction is carried out for 3h, the temperature is raised to 50 ℃, and the reaction is continued for 6 h. Performing suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing, drying, and drying in a vacuum oven for 24h to obtain a trihydroxyethyl cardanol ether phosphate oligomer (PT-HCE);
(2) 15g (containing 0.06mol of double bond) of the trihydroxyethylcardanol phosphate oligomer were dissolved in 142.560g (1.98mol) of acrylic acid in a three-necked flask equipped with a mechanical stirring device under argon, and 32.400g (0.18mol) of N-bromosuccinimide were added to obtain a pale yellow mixture. Then plugging the three-mouth bottle by using a ground glass plug, wrapping the bottleneck of the three-mouth bottle by using tinfoil, and reacting for 7d at room temperature; after the reaction is finished, adding 250mL of diethyl ether, 250mL of deionized water and 500mL of potassium iodide solution with the mass fraction of 10% to obtain a mixture, washing twice with 1000mL of sodium thiosulfate solution with the mass fraction of 5%, and neutralizing excessive acrylic acid with sodium hydroxide solution with the mass fraction of 10% until the pH value of the solution is 7; the organic phase was separated, washed twice with 250mL of water, and MgSO4Drying, and finally drying in a vacuum oven at normal temperature for 24h to obtain the phosphorus-bromine cardanol-based photosensitive resin (APT-HCE).
Preparing a phosphorus-bromine cardanol-based photosensitive resin ultraviolet curing coating material:
mixing 1.400g of the above phosphorus-containing-bromine cardanol-based photosensitive resin APT-HCE, 0.600g of tripropylene glycol diacrylate (TPGDA) and 0.020g of photoinitiator 1173, coating the mixture on a steel plate to obtain a coating with a thickness of 100 μm, and exposing the coated steel plate to light at 1600mJ/cm2Curing under an ultraviolet lamp with energy to prepare the cured coating material.
The burning test of the photosensitive resin APT-HCE containing phosphorus-bromine cardanol group in the example 1 is determined according to the GB/T2567-2008 method, and the results are shown in the table 1:
TABLE 1 APT-HCE spline vs. national Standard
As can be seen from Table 1, the phosphorus-bromine cardanol-based photosensitive resin APT-HCE prepared by the invention reaches V-0 grade compared with the national standard; meanwhile, as shown in fig. 2, the horizontal combustion and vertical combustion tests of the A and B of the phosphorus-bromine cardanol-based photosensitive resin APT-HCE show that the APT-HCE is self-extinguished after 2S and does not drip, which indicates that the photosensitive resin APT-HCE is strong in self-extinguishment, poor in flammability and excellent in flame retardant property.
Example 2:
preparing a photosensitive resin containing phosphorus-bromine cardanol group:
(1) 206.700g (0.6mol) of Hydroxyethyl Cardanol Ether (HCE) and 40.480g (0.4mol) of Triethylamine (TEA) were weighed into a three-necked flask, and 15.000g of chloroform was added and dissolved by ultrasonic agitation. After the stirring and the thermometer are assembled, the mixture is put into a water bath kettle, 18.500g (0.12mol) of phosphorus oxychloride is weighed and dissolved in 20ml of chloroform in a constant pressure dropping funnel, the dropping is completed within 0.5h at 25 ℃, after the reaction is carried out for 3h, the temperature is raised to 50 ℃, and the reaction is continued for 6 h. Performing suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing, drying, and drying in a vacuum oven for 24h to obtain a trihydroxyethyl cardanol ether phosphate oligomer (PT-HCE);
(2) 15g (containing 0.06mol of double bond) of the trihydroxyethylcardanol phosphate oligomer were dissolved in 142.560g (1.98mol) of acrylic acid in a three-necked flask equipped with a mechanical stirring device under argon, and 32.400g (0.18mol) of N-bromosuccinimide were added to obtain a pale yellow mixture. Then plugging the three-mouth bottle by using a ground glass plug, wrapping the bottleneck of the three-mouth bottle by using tinfoil, and reacting for 7d at room temperature; after the reaction is finished, adding 250mL of diethyl ether, 250mL of deionized water and 500mL of potassium iodide solution with the mass fraction of 10% to obtain a mixture, washing twice with 1000mL of sodium thiosulfate solution with the mass fraction of 5%, and neutralizing excessive acrylic acid with sodium hydroxide solution with the mass fraction of 10% until the pH value of the solution is 7; the organic phase was separated, washed twice with 250mL of water, dried over MgSO4, and finally dried in a vacuum oven at normal temperature for 24h to obtain the phosphorus-bromine cardanol-based photosensitive resin (APT-HCE).
Preparing a phosphorus-bromine cardanol-based photosensitive resin ultraviolet curing coating material:
mixing 1.4g of the bio-based APT-HCE resin, 0.6g of tripropylene glycol diacrylate (TPGDA) and 0.02g of photoinitiator 1173, coating the mixture on a steel plate to obtain a coating with a thickness of 100 μm, and exposing the coated steel plate to light at 1600mJ/cm2Curing under an ultraviolet lamp with energy to prepare the cured coating material.
Example 3:
preparing a photosensitive resin containing phosphorus-bromine cardanol group:
(1) 275.600g (0.8mol) of Hydroxyethyl Cardanol Ether (HCE) and 40.480g (0.4mol) of Triethylamine (TEA) were weighed into a three-necked flask, and 15.000g of chloroform was added and dissolved by ultrasonic agitation. After the stirring and the thermometer are assembled, the mixture is put into a water bath kettle, 18.500g (0.12mol) of phosphorus oxychloride is weighed and dissolved in 20ml of chloroform in a constant pressure dropping funnel, the dropping is completed within 0.5h at 25 ℃, after the reaction is carried out for 3h, the temperature is raised to 50 ℃, and the reaction is continued for 6 h. Performing suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing, drying, and drying in a vacuum oven for 24h to obtain a trihydroxyethyl cardanol ether phosphate oligomer (PT-HCE);
(2) 15g (containing 0.06mol of double bond) of the trihydroxyethylcardanol phosphate oligomer were dissolved in 142.560g (1.98mol) of acrylic acid in a three-necked flask equipped with a mechanical stirring device under argon, and 32.400g (0.18mol) of N-bromosuccinimide were added to obtain a pale yellow mixture. Then plugging the three-mouth bottle by using a ground glass plug, wrapping the bottleneck of the three-mouth bottle by using tinfoil, and reacting for 7d at room temperature; after the reaction is finished, adding 250mL of diethyl ether, 250mL of deionized water and 500mL of potassium iodide solution with the mass fraction of 10% to obtain a mixture, washing twice with 1000mL of sodium thiosulfate solution with the mass fraction of 5%, and neutralizing excessive acrylic acid with sodium hydroxide solution with the mass fraction of 10% until the pH value of the solution is 7; the organic phase was separated, washed twice with 250mL of water, dried over MgSO4, and finally dried in a vacuum oven at normal temperature for 24h to obtain the phosphorus-bromine cardanol-based photosensitive resin (APT-HCE).
Preparing a phosphorus-bromine cardanol-based photosensitive resin ultraviolet curing coating material:
mixing 1.4g of the bio-based APT-HCE resin, 0.6g of tripropylene glycol diacrylate (TPGDA) and 0.02g of photoinitiator 1173, coating the mixture on a steel plate to obtain a coating with a thickness of 100 μm, and exposing the coated steel plate to light at 1600mJ/cm2Curing under an ultraviolet lamp with energy to prepare the cured coating material.
The performance test of the phosphorus-bromine cardanol-based photosensitive resin ultraviolet curing coating material obtained in the examples 1-3 is performed according to GB1743-89, GB/T1730-2007, GB6739-86, GB9286-88, GB/T6287.4-2000 and GB/T30791-2014, and the results are shown in Table 2:
TABLE 2 Performance test results of P-bromo cardanol-based photosensitive resin coating materials
As can be seen from table 2, the phosphorus-bromine cardanol-based photosensitive resin ultraviolet curing coating material prepared by the invention has better glossiness, impact strength, pencil hardness, pendulum rod hardness, cross-cut adhesion and T-bend, which indicates that the phosphorus-bromine cardanol-based photosensitive resin-containing ultraviolet curing coating material has excellent mechanical strength and hardness and simultaneously has flexibility.
Comparative example 1:
preparing a phosphorus-containing cardanol-based photosensitive resin:
(1) 137.180g of Hydroxyethyl Cardanol Ether (HCE) and 40.480g of Triethylamine (TEA) were weighed into a three-necked flask, and 10ml of chloroform was added and dissolved by ultrasonic agitation. After the stirring and the thermometer are assembled, the mixture is put into a water bath kettle, 18.500g of phosphorus oxychloride is weighed and dissolved in 30.000g of chloroform in a constant pressure dropping funnel, the dropping is completed within 0.5h at 25 ℃, after the reaction is carried out for 3h, the temperature is raised to 50 ℃, and the reaction is continued for 6 h. Performing suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing, drying, and drying in a vacuum oven for 24h to obtain a trihydroxyethyl cardanol ether phosphate oligomer (PT-HCE);
(2) weighing 15g of synthesized oligomer in a three-neck flask, assembling a stirring rod and a thermometer, putting the oligomer into an oil bath pot, raising the temperature to 50 ℃, dropwise adding a quantitative mixture of formic acid and hydrogen peroxide by using a constant-pressure dropping funnel after the oligomer is stabilized, slowly dropwise adding the mixture within 1h, controlling the temperature to be 50 ℃ during the period to be stabilized, reacting for 3h after the dropwise adding is finished, wherein the molar ratio of the double bond content in the oligomer to the formic acid is 1:0.4, the corresponding formic acid content is 2.208g, and the hydrogen peroxide is 16.320 g. And (4) carrying out post-treatment to obtain the epoxy resin.
Adding 15g (epoxy content is 0.027mol) of the obtained epoxy resin, 0.15g (1.0 wt.%) of chromium (III) 2-ethylhexanoate, 0.015g (0.1 wt.%) of Hydroquinone (HQ) and 4.2g of Toluene (TL) into a three-neck flask, assembling a stirring device, a thermometer and the like, putting the three-neck flask into an oil bath pot, heating to 95 ℃ for stabilization, adding 1.500g of Acrylic Acid (AA) into a constant-pressure funnel, slowly and uniformly dropping into the three-neck flask for 0.5-1 h, heating to 100 ℃, and reacting for 8h to obtain the trihydroxyethyl cardanol ether epoxy acrylate resin (AEPT-HCE).
The preparation of the phosphorus-containing cardanol-based photosensitive resin ultraviolet curing coating material comprises the following steps:
mixing 1.400g of trihydroxyethyl cardanol ether phosphate epoxy acrylate resin AEPT-HCE, 0.600g of tripropylene glycol diacrylate (TPGDA) and 0.020g of photoinitiator 1173, coating on a steel plate to obtain a coating with a thickness of 100 μm, and exposing to 1600mJ/cm2Curing under an ultraviolet lamp with energy to prepare the cured coating material.
Comparative example 2:
preparing photosensitive resin containing bromine cardanol group:
is first divided intoSeparately, 15g of Hydroxyethyl Cardanol Ether (HCE) was dissolved in 142.560g of acrylic acid, and 32.400g N-bromosuccinimide was added to obtain a pale yellow mixture. Then plugging the three-mouth bottle by using a ground glass plug, wrapping the bottleneck of the three-mouth bottle by using tinfoil, and reacting for 7d at room temperature; after the reaction is finished, adding 250mL of diethyl ether, 250mL of deionized water and 500mL of potassium iodide solution with the mass fraction of 10% to obtain a mixture, washing twice with 1000mL of sodium thiosulfate solution with the mass fraction of 5%, and neutralizing excessive acrylic acid with sodium hydroxide solution with the mass fraction of 10% until the pH value of the solution is 7; the organic phase was separated, washed twice with 250mL of water, and MgSO4Drying, and finally drying in a vacuum oven at normal temperature for 24h to obtain the photosensitive resin (AP-HCE) containing the bromine cardanol group.
Preparing a photosensitive resin ultraviolet curing coating material containing bromine cardanol groups:
mixing 1.400g g photosensitive resin AP-HCE containing bromine cardanol group, 0.600g tripropylene glycol diacrylate (TPGDA) and 0.020g photoinitiator 1173, coating on a steel plate with a coating thickness of 100 μm, and exposing to 1600mJ/cm2Curing under an ultraviolet lamp with energy to prepare the cured coating material.
The performance test results of the ultraviolet curing coating materials obtained in the examples 1 to 3 and the comparative examples 1 to 2 are shown in table 3, and the critical oxygen index is determined according to the method GB/T2406.1-2008.
Table 3 table of results of testing combustion performance of uv-curable coating material
The above critical oxygen index shows that the phosphorus-bromine-containing photosensitive resin coating material prepared by the invention has better flame retardant property than the phosphorus-only or bromine-only photosensitive resin coating material, and the flame retardant property of the prepared coating material tends to rise with the increase of the phosphorus-bromine-containing cardanol-based photosensitive resin, which shows that the synergistic action of phosphorus and bromine greatly improves the flame retardant property of the photosensitive resin coating material.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the photosensitive resin containing the phosphorus-bromine cardanol group is characterized by comprising the following steps:
(1) dissolving hydroxyethyl cashew nut shell oil ether and triethylamine in chloroform, dropwise adding phosphorus oxychloride at 0-30 ℃ for reacting for 1-5 h, then heating to 40-60 ℃, continuing to react for 3-6 h, performing suction filtration to remove solid residues, adding acetonitrile to obtain a mixture, separating, washing and drying to obtain a trihydroxyethyl cardanol phosphate oligomer;
(2) reacting the trihydroxyethyl cardanol phosphate oligomer, acrylic acid and N-bromosuccinimide at room temperature, adding diethyl ether, deionized water and a potassium iodide solution to obtain a mixture, neutralizing the pH value of the solution to 7, separating, washing and drying to obtain the phosphorus-bromine cardanol-based photosensitive resin;
wherein the molar ratio of the triethylamine, the phosphorus oxychloride and the hydroxyethyl cashew nut shell oil ether in the step (1) is 2-4: 1-10;
in the step (2), the molar ratio of double bonds, acrylic acid and N-bromosuccinimide in the trihydroxyethyl cardanol phosphate oligomer is 1: 15-40: 1-10.
2. The method for preparing photosensitive resin containing phosphorus-bromine cardanol according to claim 1, wherein in step (1), phosphorus oxychloride is added dropwise at 25 ℃ for reaction for 3 hours, and then the temperature is raised to 50 ℃ for further reaction for 6 hours.
3. The method for preparing photosensitive resin containing phosphorus-bromine cardanol according to claim 1, wherein the amount of chloroform in step (1) is 0.1-1 times the mass of hydroxyethyl cardanol shell oil ether.
4. A phosphorus-bromine-containing cardanol-based photosensitive resin characterized by being prepared by the method of any one of claims 1 to 3.
5. The photosensitive resin of claim 4, wherein the photosensitive resin has a structure as shown below:
The photosensitive resin containing phosphorus-bromine cardanol group contains 4 structures of the R1 at the same time.
6. The application of the photosensitive resin containing phosphorus-bromine cardanol as claimed in claim 5, characterized in that the photosensitive resin containing phosphorus-bromine cardanol, the photoinitiator and the active diluent are mixed, coated on a substrate with a thickness of 30-120 μm, and then exposed to 1000mJ/cm2～2000mJ/cm2Curing under the ultraviolet light of energy to prepare the ultraviolet curing coating material.
7. The application of the photosensitive resin containing phosphorus-bromine cardanol according to claim 6, wherein the mass ratio of the photosensitive resin containing phosphorus-bromine cardanol, the reactive diluent and the photoinitiator is 7-10: 1-3: 0.1-0.5.
8. The use of the photosensitive resin containing p-bromo cardanol according to claim 7, wherein said photoinitiator is one or more of photoinitiator 819, photoinitiator 1173, photoinitiator 184, photoinitiator 907, TPO, ITX, TBPB, DCP.
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| CN1403465A (en) * | 2001-08-24 | 2003-03-19 | 中国科学院化学研究所 | Phosphorous alicyclic epoxy compound and its prepn |
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| CN1403465A (en) * | 2001-08-24 | 2003-03-19 | 中国科学院化学研究所 | Phosphorous alicyclic epoxy compound and its prepn |
| WO2015104007A2 (en) * | 2014-01-13 | 2015-07-16 | 西安坚瑞安全应急设备有限责任公司 | Fire extinguishing composition comprising alcohol phenol compound and derivative thereof |
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