CN102827332A - Ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester and preparation method thereof - Google Patents
Ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester and preparation method thereof Download PDFInfo
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- CN102827332A CN102827332A CN2012103090392A CN201210309039A CN102827332A CN 102827332 A CN102827332 A CN 102827332A CN 2012103090392 A CN2012103090392 A CN 2012103090392A CN 201210309039 A CN201210309039 A CN 201210309039A CN 102827332 A CN102827332 A CN 102827332A
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- unsaturated polyester
- retardant
- percent
- flame
- anhydride
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- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 94
- 239000003063 flame retardant Substances 0.000 title claims abstract description 72
- 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 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 phosphaphenanthrene anhydride Chemical class 0.000 claims abstract description 26
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 17
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical group C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 8
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000001530 fumaric acid Substances 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 8
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 8
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 4
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical group C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 claims description 4
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 claims description 4
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 4
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 244000028419 Styrax benzoin Species 0.000 claims description 4
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 4
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 4
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 4
- 229960002130 benzoin Drugs 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 235000019382 gum benzoic Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- VVBVBVJDNZYTHD-UHFFFAOYSA-N ClC1=CC=CC=2S(C3=CC=CC=C3SC12)=O Chemical compound ClC1=CC=CC=2S(C3=CC=CC=C3SC12)=O VVBVBVJDNZYTHD-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 2
- BEUGBYXJXMVRFO-UHFFFAOYSA-N [4-(dimethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=CC=C1 BEUGBYXJXMVRFO-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 22
- 239000004327 boric acid Substances 0.000 abstract description 22
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UGLYZYWXVZIHEC-UHFFFAOYSA-N [4,4-bis(methylamino)cyclohexa-1,5-dien-1-yl]-phenylmethanone Chemical compound C1=CC(NC)(NC)CC=C1C(=O)C1=CC=CC=C1 UGLYZYWXVZIHEC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- LNYYKKTXWBNIOO-UHFFFAOYSA-N 3-oxabicyclo[3.3.1]nona-1(9),5,7-triene-2,4-dione Chemical compound C1=CC(C(=O)OC2=O)=CC2=C1 LNYYKKTXWBNIOO-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VBQRUYIOTHNGOP-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound C1=CC=C2P(=O)OC3=CC=CC=C3C2=C1 VBQRUYIOTHNGOP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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Abstract
The invention discloses an ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester and preparation method thereof. A raw material formula comprises the following raw materials in percentage by mass: 49.5-65 percent of a phosphorus-boron flame-retardant unsaturated polyester prepolymer, 50-30 percent of an active diluent, 0.4-4.5 percent of a photoinitiator and 0.1-0.5 percent of a polymerization inhibitor, wherein the phosphorus-boron flame-retardant unsaturated polyester prepolymer is prepared by reacting dibasic alcohol, unsaturated dibasic anhydride and/or unsaturated dicarboxylic acid, a phosphaphenanthrene anhydride derivative and boric acid at the temperature of 150-205 DEG C. The volatilization loss rate in the curing process of unsaturated polyester is less than 1 percent, the appearance is transparent before curing and after curing, and vertical combustion passes through a grade UL94 V-0; and the ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester has the advantages of low volatilization loss, freeness from halogen, flame retardance, transparence and the like.
Description
Technical Field
The invention relates to halogen-free flame-retardant unsaturated polyester resin, in particular to ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester and a preparation method thereof. The unsaturated polyester has transparent appearance and moderate viscosity, and can be used as printing ink, electronic packaging, adhesive, printing plates and the like.
Background
Unsaturated Polyester (UPR) is a thermosetting resin with large yield, is usually cured by heating, and has high saturated vapor pressure (853 Pa at 25 ℃), strong volatility, strong smell,The irritating styrene diluent has unpleasant smell during paint dipping and baking, which not only wastes seriously, but also has great harm to operators and the surrounding environment. Ultraviolet (UV) curing has the advantages of high curing speed, energy conservation, high production efficiency, good coating performance and the like, and compared with thermal curing, the emission of volatile organic compounds is greatly reduced, so that the UV curing coating is widely applied to coatings, printing ink, electronic packaging, adhesives, printing plates and electronic industry. However, the existing ultraviolet light cured UPR is not implemented with flame retardant technology and is easy to burn, for example, Chinese patent ZL200410051590.7 discloses an allyl ether modified unsaturated polyester which is characterized in that a molecular chain contains an unsaturated carbon-carbon double bond and also contains allyloxy, and has the performances of photocuring and air (oxygen) curing, but the patent only endows the unsaturated polyester with the photooxidative curing performance, and the obtained unsaturated polyester is not flame retardant. With the enhancement of environmental awareness, flame retardance, particularly halogen-free flame retardance, becomes one of the necessary conditions for various materials. The transparency of UPR is affected by additive flame-retardant UPR technologies such as Melamine (MA), Red Phosphorus (RP), ammonium polyphosphate (APP), expanded graphite, layered silicate nanoclay and the like, and the problems can be avoided to a certain extent by reactive flame retardance. Chinese patent CN200810218735.6 discloses a reactive phosphorus-containing unsaturated polyester, represented by formula C2-6Dihydric alcohol, C3-8Saturated dibasic acid or anhydride, C4Unsaturated dibasic acid or anhydride and bifunctional reactive phosphorus-containing flame retardant are synthesized into unsaturated polyester oligomer, styrene is used as a cross-linking agent, the prepared unsaturated polyester is transparent after cross-linking and curing, the limiting oxygen index can be improved from 19% to 29%, UL94V-0 level can be achieved through vertical combustion, and the reactive phosphorus-containing unsaturated polyester is non-ultraviolet light curing. In a word, the unsaturated polyester prepared by the prior art can not simultaneously take account of the properties of ultraviolet curing, halogen-free flame retardance, transparency and the like.
Disclosure of Invention
The invention provides an ultraviolet light curing transparent halogen-free flame-retardant unsaturated polyester, aiming at solving the problems of volatilization loss and halogen-free flame retardance of the existing unsaturated polyester resin;
the invention also aims to provide a preparation method of the ultraviolet curing transparent halogen-free flame-retardant unsaturated polyester.
In order to achieve the purpose, the invention adopts the following technical scheme:
an ultraviolet light cured transparent halogen-free flame retardant unsaturated polyester: the raw material formula comprises the following components in percentage by mass: 49.5 to 65 percent of phosphorus-boron flame-retardant unsaturated polyester prepolymer, 50 to 30 percent of reactive diluent, 0.4 to 4.5 percent of photoinitiator and 0.1 to 0.5 percent of polymerization inhibitor;
the structural general formula of the phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
in the general formula, R is
R' is-CH ═ CH-,
r' is
-CH2CH2OCH2CH2-、-CH2CH2-、
Or
x, y and z are relative fractions of three structural units in sequence, wherein x is 0.55-0.75, y is 0.1-0.2, z is 0.15-0.25, and x + y + z is 1;
the reactive diluent is one or more of a monofunctional reactive diluent, a difunctional reactive diluent and a multifunctional reactive diluent; the monofunctional reactive diluent is hydroxyethyl acrylate, isooctyl acrylate or isobornyl acrylate; the difunctional reactive diluent is triethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol (200) diacrylate, neopentyl glycol diacrylate or propoxylated neopentyl glycol diacrylate; the multifunctional reactive diluent is trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate or pentaerythritol triacrylate.
The photoinitiator is benzoin butyl ether, benzophenone, benzoin dimethyl ether (Irgacure 651), 4-dimethylamino benzophenone (Michman ketone), 2-Isopropyl Thioxanthone (ITX), chlorothianthrone (2-CTX), 2-hydroxy-methyl phenyl propane-1-ketone (1173), 1-hydroxy cyclohexyl benzophenone (Irgacure184), 2-phenyl-2-N-dimethylamino 1- (-4-morpholinyl phenyl) -butanone (Irgacure369), ferric salt (Irgacure 261) or acyl phosphorous oxide (BAPO).
The polymerization inhibitor is hydroquinone, p-tert-butyl catechol, methyl hydroquinone, p-benzoquinone, p-hydroxyanisole, 2-butyl hydroquinone or 2, 5-di-tert-butyl hydroquinone.
The preparation method of the ultraviolet curing transparent halogen-free flame-retardant unsaturated polyester comprises the following steps:
(1) adding dihydric alcohol and three monomers into a container, heating to 150-160 ℃, keeping the temperature for 1-3 hours, then heating to 180-205 ℃ for reaction, and controlling the temperature of a distillation outlet to be lower than 100 ℃; the three monomers are first unsaturated dicarboxylic anhydride and/or unsaturated dicarboxylic acid; a second class of monomeric phosphaphenanthrene anhydride derivatives; a third type of monomeric boronic acid; the total mole number of the dihydric alcohol is 1-1.5 times of the total mole number of the three types of monomers; the first type monomer, the second type monomer and the third type monomer respectively account for 55-75 percent, 10-20 percent and 15-25 percent of the total mole number of the three types of monomers; the unsaturated dicarboxylic anhydride is maleic anhydride and/or fumaric anhydride, and the unsaturated dicarboxylic acid is maleic acid and/or fumaric acid; the phosphaphenanthrene anhydride derivative is an addition product of maleic anhydride or itaconic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
(2) and when the reaction is carried out until the acid value is lower than 40mg KOH/g, reducing the temperature to 100-120 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer, adding an active diluent, cooling to room temperature, adding a polymerization inhibitor and a photoinitiator, and stirring at room temperature for 30-60 minutes to obtain the ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester.
The dihydric alcohol in the step (1) is preferably one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol and 1, 4-butanediol.
The structural formula of the addition product of maleic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in the specification
The structural formula of the addition product of itaconic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in the specification
Compared with the prior art, the invention has the following beneficial effects:
(1) the unsaturated polyester can be cured by ultraviolet light, the volatilization loss rate in the curing process is lower than 1 percent, and the appearance is transparent before and after curing.
(2) According to the unsaturated polyester disclosed by the invention, phosphorus and boron flame-retardant elements are introduced into the molecular chain of the unsaturated polyester prepolymer, when the total content of phosphorus and boron is about 1.5%, the limited oxygen index of a cured product can be increased from 19% to 31%, and the vertical combustion passes UL94V-O level.
(3) Compared with unsaturated polyester which is only flame-retardant by phosphorus, the unsaturated polyester has the advantages of enhanced oxidation resistance and improved heat resistance.
Drawings
FIG. 1 shows the addition product of itaconic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in each example1H-NMR spectrum.
FIG. 2 shows the addition product of maleic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in each example1H-NMR spectrum.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the examples.
Example 1
Adding 1.2mol of 1, 3-propylene glycol, 0.55mol of maleic anhydride, 0.2mol of an addition product of maleic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and 0.25mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 100 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding hydroxyethyl acrylate, cooling to room temperature, adding hydroquinone and benzoin butyl ether, and stirring at room temperature for 30 minutes to obtain ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the mass usage of each substance is 49.5 parts of phosphorus boron flame-retardant unsaturated polyester prepolymer, 50 parts of hydroxyethyl acrylate, 0.1 part of hydroquinone and 0.4 part of benzoin butyl ether. The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein R is
R 'is-CH ═ CH-, R' is- (CH)2)3X is calculated according to the mole fraction of the added phosphaphenanthrene maleic anhydride derivative in the three monomers of phosphaphenanthrene maleic anhydride derivative, maleic anhydride and boric acid, y is calculated according to the mole fraction of the added maleic anhydride in the three monomers, z is calculated according to the mole fraction of the added boric acid in the three monomers, x is 0.2, y is 0.55 and z is 0.25.
Example 2
Adding 0.5mol of ethylene glycol, 0.6mol of 1, 2-propylene glycol, 0.55mol of maleic anhydride, 0.15mol of maleic acid, 0.15mol of addition product of itaconic anhydride and DOPO and 0.15mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for about 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value once every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 120 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding hydroxyethyl acrylate and triethylene glycol diacrylate, cooling to room temperature, adding p-tert-butyl catechol and benzoin dimethyl ether (Irgacure 651), and stirring at room temperature for 60 minutes to obtain ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the mass amounts of the components are 50.7 parts of phosphorus boron flame-retardant unsaturated polyester prepolymer, 32 parts of hydroxyethyl acrylate, 13 parts of triethylene glycol diacrylate, 0.3 part of tert-butyl catechol and 4 parts of benzoin dimethyl ether (Irgacure 651). The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein R is
R' is-CH ═ CH-, R "is
x is calculated according to the mole fraction of the added phosphaphenanthrene itaconic anhydride derivative in four monomers of the phosphaphenanthrene itaconic anhydride derivative, maleic anhydride, maleic acid and boric acid, y is calculated according to the mole fraction of the added maleic anhydride and maleic acid in the four monomers, z is calculated according to the mole fraction of the added boric acid in the four monomers, x is 0.15, y is 0.7 and z is 0.15.
Example 3
Adding 0.65mol of diethylene glycol, 0.6mol of 1, 3-propylene glycol, 0.4mol of maleic anhydride, 0.2mol of fumaric anhydride, 0.2mol of addition product of itaconic anhydride and DOPO and 0.2mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for about 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 110 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding hydroxyethyl acrylate, propoxylated neopentyl glycol diacrylate and trimethylolpropane triacrylate, cooling to room temperature, adding methyl hydroquinone and 4, 4-dimethylamino benzophenone (mikimonone), and stirring at room temperature for 40 minutes to obtain the ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the amounts of each substance by mass were 65 parts of phosphorus-boron flame-retardant unsaturated polyester prepolymer, 15 parts of hydroxyethyl acrylate, 10 parts of propoxylated neopentyl glycol diacrylate, 5 parts of trimethylolpropane triacrylate, 0.5 part of methylhydroquinone and 4.5 parts of 4, 4-dimethylaminobenzophenone (michelson). The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein,
r 'is-CH ═ CH-, R' is- (CH)2)3-and-CH2CH2OCH2CH2X is calculated according to the mole fraction of the added phosphaphenanthrene itaconic anhydride derivative in the four monomers of phosphaphenanthrene itaconic anhydride derivative, maleic anhydride, fumaric anhydride and boric acid, y is calculated according to the mole fraction of the added maleic anhydride and fumaric anhydride in the four monomers, z is calculated according to the mole fraction of the added boric acid in the four monomers, x is 0.2, y is 0.6 and z is 0.2.
Example 4
Adding 1.2mol of 1, 4-butanediol, 0.62mol of fumaric anhydride, 0.18mol of addition product of itaconic anhydride and DOPO and 0.2mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for about 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value once every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 105 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding hydroxyethyl acrylate, triethylene glycol diacrylate and propoxylated trimethylolpropane triacrylate, cooling to room temperature, adding p-benzoquinone and 2-Isopropyl Thioxanthone (ITX), and stirring at room temperature for 45 minutes to obtain ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the mass dosage is 55 parts of phosphorus-boron flame-retardant unsaturated polyester prepolymer, 20 parts of hydroxyethyl acrylate, 10 parts of triethylene glycol diacrylate, 12.8 parts of propoxylated trimethylolpropane triacrylate, 0.2 part of p-benzoquinone and 2 parts of 2-Isopropyl Thioxanthone (ITX). The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein R is
R 'is-CH ═ CH-, R' is- (CH)2)4X is calculated according to the mole fraction of the added phosphaphenanthrene itaconic anhydride derivative in the three monomers of phosphaphenanthrene itaconic anhydride derivative, fumaric anhydride and boric acid, y is calculated according to the mole fraction of the added fumaric anhydride in the three monomers, z is calculated according to the mole fraction of the added boric acid in the three monomers, x is 0.18, y is 0.62 and z is 0.2.
Example 5
Adding 0.95mol of diethylene glycol, 0.55mol of ethylene glycol, 0.35mol of fumaric anhydride, 0.3mol of fumaric acid, 0.2mol of addition product of itaconic anhydride and DOPO and 0.15mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for about 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value once every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 120 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding isooctyl acrylate, ethylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, cooling to room temperature, adding p-hydroxyanisole and chlorothioxanthone (2-CTX), and stirring at room temperature for 30 minutes to obtain ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the mass dosage is 60 parts of phosphorus-boron flame-retardant unsaturated polyester prepolymer, 30 parts of isooctyl acrylate, 3.6 parts of ethylene glycol diacrylate, 3.6 parts of ethoxylated trimethylolpropane triacrylate, 0.3 part of p-hydroxyanisole and 2.5 parts of chlorothianthrone (2-CTX). The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein R is
R' is- (CH)2)2-and-CH2CH2OCH2CH2-, R' is-CH ═ CH-, x is in terms of mole fraction of the added phosphaphenanthrene itaconic anhydride derivative in the four monomers phosphaphenanthrene itaconic anhydride derivative, fumaric anhydride, fumaric acid and boric acid, y is in terms of mole fraction of the added fumaric anhydride and fumaric acid in the four monomers, z is in terms of mole fraction of the added boric acid in the four monomers, x is 0.2, y is 0.65, and z is 0.15.
Example 6
Adding 0.2mol of diethylene glycol, 0.4mol of 1, 2-propylene glycol, 0.4mol of 1, 3-propylene glycol, 0.45mol of maleic anhydride, 0.2mol of fumaric acid, 0.12mol of an addition product of maleic anhydride and DOPO and 0.23mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for about 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value once every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 110 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding hydroxyethyl acrylate and polyethylene glycol (200) diacrylate, cooling to room temperature, adding 2-butylhydroquinone and 2-hydroxy-methyl phenyl propane-1-ketone (1173), and stirring at room temperature for 55 minutes to obtain ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the mass amount is 56.6 parts of phosphorus boron flame-retardant unsaturated polyester prepolymer, 20 parts of hydroxyethyl acrylate, 20 parts of polyethylene glycol (200) diacrylate, 0.4 part of 2-butylhydroquinone and 3 parts of 2-hydroxy-methyl phenyl propane-1-ketone (1173). The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein R isR 'is-CH ═ CH-, R' is- (CH)2)3-、-CH2CH2OCH2CH2-andx is calculated according to the mole fraction of the added phosphaphenanthrene maleic anhydride derivative in the four monomers of the phosphaphenanthrene maleic anhydride derivative, maleic anhydride, fumaric acid and boric acid, y is calculated according to the mole fraction of the added maleic anhydride and fumaric acid in the four monomers, z is calculated according to the mole fraction of the added boric acid in the four monomers, x is 0.12, y is 0.65, and z is 0.23.
Example 7
Adding 0.65mol of diethylene glycol, 0.6mol of 1, 4-butanediol, 0.75mol of maleic anhydride, 0.1mol of addition product of maleic anhydride and DOPO and 0.15mol of boric acid into a 500ml three-neck flask provided with a thermometer, a stirrer and a distillation branch pipe, heating to 150-160 ℃, keeping the temperature for about 2 hours, heating to 180-205 ℃ for reaction, controlling the temperature of a distillation outlet to be lower than 100 ℃, measuring the acid value once every 1 hour, stopping heating when the acid value is lower than 40mg KOH/g, and cooling to 110 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer; adding neopentyl glycol diacrylate and pentaerythritol triacrylate, cooling to room temperature, adding 2, 5-di-tert-butylhydroquinone and 2-phenyl-2-N-dimethylamino-1- (-4-morpholinylphenyl) -butanone (Irgacure369), and stirring at room temperature for 50 minutes to obtain ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester; the mass dosage is 56.6 parts of phosphorus boron flame-retardant unsaturated polyester prepolymer, 20 parts of neopentyl glycol diacrylate, 20 parts of pentaerythritol triacrylate, 0.4 part of 2, 5-di-tert-butyl hydroquinone and 3 parts of 2-phenyl-2-N-dimethylamino-1- (-4-morpholinyl-phenyl) -butanone (Irgacure 369). The structural general formula of the obtained phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
wherein R is
R 'is-CH ═ CH-, R' is- (CH)2)4-and-CH2CH2OCH2CH2X is calculated according to the mole fraction of the added phosphaphenanthrene maleic anhydride derivative in the three monomers of phosphaphenanthrene maleic anhydride derivative, maleic anhydride and boric acid, y is calculated according to the mole fraction of the added maleic anhydride in the three monomers, z is calculated according to the mole fraction of the added boric acid in the three monomers, x is 0.1, y is 0.75 and z is 0.15.
Reference ratio 1
Reacting maleic anhydride, 1, 3-propylene glycol and ethylene glycol at a molar ratio of 3.7: 2.4: 1.4 at 180-210 ℃ until the acid value is below 40mg KOH/g, stopping heating, and cooling to 110 ℃ to obtain an unsaturated polyester prepolymer; adding styrene, cooling to room temperature, and adding a hydroquinone polymerization inhibitor and a dicumyl peroxide initiator; the mass amounts of each substance were 58.5 parts of unsaturated polyester prepolymer, 40 parts of styrene, 0.5 part of hydroquinone and 1 part of dicumyl peroxide.
Reference ratio 2
The flame-retardant unsaturated polyester is prepared according to the method of example 2 in the Chinese patent 'a reaction type transparent halogen-free flame-retardant unsaturated polyester and a preparation method thereof, patent application No. 200810218735.6':
40g (0.13mol) of phenyl phosphonic acid bis (resorcinol) ester, 20.7g (0.14mol) of isophthalic anhydride, 12g (0.10mol) of maleic acid, 18.6g (0.237mol) of 1, 3-propanediol and 8.7g (0.14mol) of ethylene glycol were placed in a 250ml four-necked flask2Stirring under gas protection, heating with an electric heating jacket, slowly heating to 150 deg.C, holding at constant temperature for 1 hr, slowly heating at 10 deg.C/min, and controlling the distillation outlet temperature to be lower than 100 deg.C. Reacting until the acid value of the unsaturated polyester is below 40mg KOH/g, stopping heating, cooling to 110 ℃ after the reaction is finished, and adding phenylethylene according to the mass ratio of the unsaturated polyester prepolymer to the styrene of 6: 4Alkene, cooling to room temperature, and adding 1% and 0.01% of hydroquinone and dicumyl peroxide by mass of the two.
The infrared spectrum of the addition product of itaconic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the above example was 1709cm-1Absorption peaks of stretching vibration at which C ═ O bond is present, 1477 and 1431cm-1Has a P-C bond stretching vibration absorption peak at 1247cm-1Has P ═ O bond stretching vibration absorption peak and 918cm-1Has a P-O bond stretching vibration absorption peak, which1The H-NMR spectrum and the corresponding hydrogen attribution are shown in the attached figure 1; according to the infrared spectrum,1The chemical displacement and peak area of each peak on the H-NMR spectrum show that the structural formula of the product is as follows:
1732 and 1709cm in the IR spectrum of the addition product of maleic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-1Absorption peaks of stretching vibration at which C ═ O bond is present, 1477 and 1431cm-1Has a P-C bond stretching vibration absorption peak at 1244cm-1Has a P ═ O bond stretching vibration absorption peak and 935cm-1Has a P-O bond stretching vibration absorption peak, which1The H-NMR spectrum and the corresponding hydrogen attribution are shown in the attached figure 2; according to the infrared spectrum,1The chemical displacement and peak area of each peak on the H-NMR spectrum show that the structural formula of the product is as follows:
in the examples, the method for measuring the acid value in the reaction process of the phosphorus-boron flame-retardant unsaturated polyester prepolymer is carried out according to GB/T2895-1982. Respectively pouring the non-flame-retardant unsaturated polyester prepared in the embodiments 1-7 and the reference 1 and the flame-retardant unsaturated resin prepared in the reference 2 into a standard-size sample mold, and placing the mold in a state that the light intensity is 103mW/cm2The reaction type resistors synthesized in all examples were irradiated under a high-pressure mercury lamp having a main peak wavelength of 365nm for 2 minutes at an irradiation distance of 10cm and then cured at 120 ℃ for 2 hoursThe product of the flame-retardant unsaturated polyester was transparent in appearance, and was almost indistinguishable in appearance from the unsaturated polyester synthesized in reference example 1. Demoulding to obtain a test standard sample strip of each cured product, and testing the limit oxygen index according to the GB/T2406-93 standard; the flame retardant rating was tested according to the UL94 standard. Taking the cured sample to perform thermogravimetric analysis in the air atmosphere, wherein the temperature rise speed is 10 ℃/min, and the thermal decomposition temperature (T) is 5 percent5％) Indicating thermal oxygen stability. The results of the analyses of the tests are shown in Table 1.
Appearance and flame-retardant test results of products of Table 1, examples and reference examples
As can be seen from Table 1, the limit oxygen index of the flame-retardant unsaturated polyester of the invention exceeds 27% of the prior art, namely reference ratio 2, and the flame-retardant unsaturated polyester can pass through UL94 vertical combustion V-0 grade (3.2mm), which shows that the unsaturated polyester further introduced with boron element has better flame retardant property. T of unsaturated polyester not flame retarded in thermo-oxidative stability5％T of unsaturated polyester flame-retarded with bis (resorcinol) phenylphosphonate addition (i.e. reference example 2) at 275 deg.C5％For 249 ℃, the unsaturated polyester of the present invention, T, is reduced in thermal stability5％Above 275 ℃ higher than that of the unsaturated polyester without flame retardance, and has good thermal-oxidative stability. The volatilization loss rate of the unsaturated polyester in the curing process is below 1 percent and is far lower than the volatilization loss rate of about 15 percent of the unsaturated polyester in the thermal curing process. The unsaturated polyester has the volatilization loss rate of less than 1 percent in the curing process, has transparent appearance before and after curing, vertically burns through UL94V-0 level, and simultaneously has the advantages of low volatilization loss, halogen-free flame retardance, transparency and the like.
Claims (7)
1. An ultraviolet light cured transparent halogen-free flame-retardant unsaturated polyester is characterized in that: the raw material formula comprises the following components in percentage by mass: 49.5 to 65 percent of phosphorus-boron flame-retardant unsaturated polyester prepolymer, 50 to 30 percent of reactive diluent, 0.4 to 4.5 percent of photoinitiator and 0.1 to 0.5 percent of polymerization inhibitor;
the structural general formula of the phosphorus-boron flame-retardant unsaturated polyester prepolymer is as follows:
in the general formula, R is
R' is-CH ═ CH-,
r' is
-CH2CH2OCH2CH2-、-CH2CH2-、
Or
x, y and z are relative fractions of three structural units in sequence, wherein x is 0.55-0.75, y is 0.1-0.2, z is 0.15-0.25, and x + y + z is 1;
the reactive diluent is one or more of a monofunctional reactive diluent, a difunctional reactive diluent and a multifunctional reactive diluent; the monofunctional reactive diluent is hydroxyethyl acrylate, isooctyl acrylate or isobornyl acrylate; the difunctional reactive diluent is triethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol (200) diacrylate, neopentyl glycol diacrylate or propoxylated neopentyl glycol diacrylate; the multifunctional reactive diluent is trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate or pentaerythritol triacrylate.
2. The UV-curable transparent halogen-free flame retardant unsaturated polyester according to claim 1, wherein the photoinitiator is benzoin butyl ether, benzophenone, benzoin dimethyl ether, 4-dimethylaminobenzophenone, 2-isopropyl thioxanthone, chlorothianthrone, 2-hydroxy-methylphenylpropane-1-one, 1-hydroxycyclohexyl benzophenone, 2-phenyl-2-N-dimethylamino-1- (-4-morpholinophenyl) -butanone, iron salt Irgascure 261 or acyl phosphorous oxide BAPO.
3. The UV-curable transparent halogen-free flame-retardant unsaturated polyester according to claim 1, wherein the polymerization inhibitor is hydroquinone, p-tert-butylcatechol, methylhydroquinone, p-benzoquinone, p-hydroxyanisole, 2-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
4. The preparation method of the ultraviolet-curing transparent halogen-free flame-retardant unsaturated polyester as claimed in claim 1, characterized by comprising the following steps:
(1) adding dihydric alcohol and three monomers into a container, heating to 150-160 ℃, keeping the temperature for 1-3 hours, then heating to 180-205 ℃ for reaction, and controlling the temperature of a distillation outlet to be lower than 100 ℃; the three monomers are first unsaturated dicarboxylic anhydride and/or unsaturated dicarboxylic acid; a second class of monomeric phosphaphenanthrene anhydride derivatives; a third type of monomeric boronic acid; the total mole number of the dihydric alcohol is 1-1.5 times of the total mole number of the three types of monomers; the first type monomer, the second type monomer and the third type monomer respectively account for 55-75 percent, 10-20 percent and 15-25 percent of the total mole number of the three types of monomers; the unsaturated dicarboxylic anhydride is maleic anhydride and/or fumaric anhydride, and the unsaturated dicarboxylic acid is maleic acid and/or fumaric acid; the phosphaphenanthrene anhydride derivative is an addition product of maleic anhydride or itaconic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide;
(2) and when the reaction is carried out until the acid value is lower than 40mg KOH/g, reducing the temperature to 100-120 ℃ to obtain a phosphorus-boron flame-retardant unsaturated polyester prepolymer, adding an active diluent, cooling to room temperature, adding a polymerization inhibitor and a photoinitiator, and stirring at room temperature for 30-60 minutes to obtain the ultraviolet-cured transparent halogen-free flame-retardant unsaturated polyester.
5. The method for preparing the ultraviolet-curable transparent halogen-free flame-retardant unsaturated polyester according to claim 4, wherein the dihydric alcohol in the step (1) is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, diethylene glycol and 1, 4-butanediol.
6. The method for preparing the ultraviolet curing transparent halogen-free flame retardant unsaturated polyester as claimed in claim 4, wherein the structural formula of the addition product of maleic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in the specification
7. The method for preparing the ultraviolet-curing transparent halogen-free flame-retardant unsaturated polyester as claimed in claim 4, wherein the structural formula of the addition product of itaconic anhydride and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is shown in the specification
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| CN103275309A (en) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | Phosphorous flame-retardant unsaturated polyester resin and preparation method thereof |
| CN111171704A (en) * | 2020-01-21 | 2020-05-19 | 中电保力（北京）科技有限公司 | Intrinsic flame-retardant cable head flash sealing coating and preparation method thereof |
| CN111378263A (en) * | 2018-12-28 | 2020-07-07 | 浙江荣泰科技企业有限公司 | Single-component halogen-free flame-retardant insulating impregnating resin and preparation method thereof |
| CN112457478A (en) * | 2020-11-25 | 2021-03-09 | 广东晨宝复合材料股份有限公司 | Boric acid modified unsaturated polyester and preparation method thereof |
| CN113667106A (en) * | 2021-08-23 | 2021-11-19 | 肇庆福田化学工业有限公司 | Ultraviolet-cured itaconic acid-based polyester resin and preparation method thereof |
| EP4369098A1 (en) | 2022-11-14 | 2024-05-15 | Cubicure GmbH | Resin composition |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073746A (en) * | 2013-01-10 | 2013-05-01 | 苏州安鸿泰新材料有限公司 | Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof |
| CN103073746B (en) * | 2013-01-10 | 2014-04-23 | 苏州安鸿泰新材料有限公司 | Reactive phosphorus flame retardant containing DOPO and active double bond and preparation method and application thereof |
| CN103275277A (en) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | Unsaturated polyester resin flame-retardant material and preparation method thereof |
| CN103275309A (en) * | 2013-06-26 | 2013-09-04 | 兰州理工大学 | Phosphorous flame-retardant unsaturated polyester resin and preparation method thereof |
| CN111378263A (en) * | 2018-12-28 | 2020-07-07 | 浙江荣泰科技企业有限公司 | Single-component halogen-free flame-retardant insulating impregnating resin and preparation method thereof |
| CN111171704A (en) * | 2020-01-21 | 2020-05-19 | 中电保力（北京）科技有限公司 | Intrinsic flame-retardant cable head flash sealing coating and preparation method thereof |
| CN111171704B (en) * | 2020-01-21 | 2022-01-11 | 中电保力（北京）科技有限公司 | Intrinsic flame-retardant cable head flash sealing coating and preparation method thereof |
| CN112457478A (en) * | 2020-11-25 | 2021-03-09 | 广东晨宝复合材料股份有限公司 | Boric acid modified unsaturated polyester and preparation method thereof |
| CN113667106A (en) * | 2021-08-23 | 2021-11-19 | 肇庆福田化学工业有限公司 | Ultraviolet-cured itaconic acid-based polyester resin and preparation method thereof |
| EP4369098A1 (en) | 2022-11-14 | 2024-05-15 | Cubicure GmbH | Resin composition |
| WO2024105509A1 (en) | 2022-11-14 | 2024-05-23 | Cubicure Gmbh | Resin composition |
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