WO2022153095A1 - Photo-curable multifunction acrylated/ methacrylated epoxy resin and one-pot preparation thereof - Google Patents
Photo-curable multifunction acrylated/ methacrylated epoxy resin and one-pot preparation thereof Download PDFInfo
- Publication number
- WO2022153095A1 WO2022153095A1 PCT/IB2021/051937 IB2021051937W WO2022153095A1 WO 2022153095 A1 WO2022153095 A1 WO 2022153095A1 IB 2021051937 W IB2021051937 W IB 2021051937W WO 2022153095 A1 WO2022153095 A1 WO 2022153095A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- tetra
- acrylated
- bisphenol
- methacrylated
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 124
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 124
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 63
- 230000008569 process Effects 0.000 claims abstract description 54
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 29
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000011347 resin Substances 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 60
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 51
- 239000004593 Epoxy Substances 0.000 claims description 48
- 229930185605 Bisphenol Natural products 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 31
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 31
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 28
- 239000011964 heteropoly acid Substances 0.000 claims description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 20
- 125000005641 methacryl group Chemical group 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 7
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 6
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- 229940086542 triethylamine Drugs 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 claims description 2
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical group FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 2
- 229940063557 methacrylate Drugs 0.000 claims 10
- 239000003999 initiator Substances 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 abstract description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- -1 coatings Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 8
- 229940106691 bisphenol a Drugs 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 231100001261 hazardous Toxicity 0.000 description 7
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 6
- 230000002588 toxic effect Effects 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 235000006708 antioxidants Nutrition 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000010533 azeotropic distillation Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002118 epoxides Chemical group 0.000 description 5
- 239000005010 epoxy-amino resin Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 3
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 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 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 101100223811 Caenorhabditis elegans dsc-1 gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
Definitions
- the present disclosure pertains to organic synthesis.
- the present disclosure pertains to organic synthesis of photo-curable acrylate/ methacrylate resins.
- UV-radiation curing is one of the most efficient ways to rapidly convert the liquid photosensitive resin to solid polymer within a fraction of a second.
- Ultraviolet-curable resins are the resins most suitable to the requirements of the times such as low pollution, resource conservation, high performance and functionalization.
- the oligomers and monomers commonly used in UV-curable formulations include acrylated compounds such as epoxy acrylate/ methacrylate (vinyl ester) resins, urethane acrylates, polyester and polyether acrylates and epoxy acrylate nanocomposites.
- Epoxy acrylate/methacrylate resins are (semi-) polymeric substances called oligomers with variable chain lengths that are widely applied as photo-sensitive substrate in various industries and manufacture because of the distinct properties such as great adhesion, corrosion resistance and hardness.
- di-functional acrylates i.e, diacrylated epoxy resins are most commonly synthesized.
- the method of preparation of diacrylated epoxy resins typically involves the reaction of different epoxy resins (different phenols) with acrylic acid.
- diglycidal ethers comprising two epoxide functional groups are reacted with acrylic acid in the presence of quaternary ammonium compounds, alkyl amines, alkyl/aryl phosphines and Lewis acid catalyst, resulting in ring opening of epoxide or end-capping the epoxide groups with acrylate group to obtain diacrylated epoxy resin, as shown in Scheme 1.
- the diacrylated epoxy resin thus obtained has two secondary hydroxyl groups on the backbone of the oligomer chain, which do not further react with acrylic acid to form ester linkage, as their reaction is very sluggish. Additionally, the presence of secondary OH groups hinders the curing speed and also reduces the crosslinking density of the polymer, thus, weakening the physical, mechanical, chemical and thermal properties of the UV-cured
- acryloyl chloride as an active ingredient for end-capping the epoxide and hydroxyl groups with acrylate function groups also has drawbacks.
- Acryloyl chloride is highly toxic, flammable, has a lachrymatory effect and is not very stable as it decomposes on contact with moisture, thus it cannot be stored in open environment. Moreover, toxic fumes of hydrochloric acid are generated throughout the reaction. [0007] In another reported procedure in patent no.
- tetra-methacrylated epoxy resins have been synthesized starting from resorcinol diglycidal ether, which is reacted with methacrylic acid using base as a catalyst to form di -methacrylic Epoxy Resin.
- the dimethacrylated epoxy resin thus obtained, is then reacted with methacryloyl chloride in presence of base catalyst triethylamine (EtsN) to end-cap secondary hydroxyl groups, resulting in tetra-methacrylic epoxy resin.
- EtsN triethylamine
- methacryloyl chloride has limitations similar to the use of acryloyl chloride such as methacryloyl chloride is flammable with low stability, toxic, corrosive, lachrymatory and generates extremely hazardous byproducts (toxic fumes of hydrochloric acid are generated throughout the
- An object of the present disclosure is to provide an improved photo-curable tetra- acrylated/ methacrylated epoxy resin and process for its synthesis, which can overcome deficiencies associated with the known arts.
- Another object of the present disclosure is to provide a photo-curable multifunctional, tetra- acrylated/ methacrylated epoxy resin that demonstrates improved crosslinking and curing speed.
- Yet another object of the present disclosure is to provide a photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin that improves the physical, mechanical, chemical and thermal properties of the cured product.
- Another object of the present disclosure is to provide a photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin that can be synthesized in high purity and without any harmful byproduct formation.
- Still another object of the present disclosure is to provide a one pot synthetic process for the synthesis of multifunctional tetra-acrylated/ methacrylated epoxy resin that does not involve any hazardous starting materials and provides product in high purity.
- the present disclosure relates to one pot synthesis process for the preparation of photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, including forming a di-acryl/ methacryl epoxy resin by reacting diglycidal ether with acrylic acid/ methacrylic acid in the presence of a catalyst; and converting di-acryl/methacryl epoxy resin into tetra-acrylated/ methacrylated epoxy resin by reaction with acrylic acid/ methacrylic acid in the presence of a heteropolyacid catalyst; wherein the di-acryl/ methacryl epoxy resin is not isolated after its formation and is in-situ reacted with acrylic acid/ methacrylic acid in the presence of heteropolyacid catalyst to obtain tetra-acrylated/ methacrylated epoxy resin.
- the single pot process for the synthesis of multifunctional tetra-acrylated/ methacrylated epoxy resin enables the synthesis of tetra- acrylated / methacrylated epoxy resin in high purity and yield, without any harmful byproduct formation and the process does not involve any hazardous starting materials.
- the present disclosure relates to a photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, synthesized by one pot synthesis process, wherein the tetra-acrylated / methacrylated epoxy resin demonstrates improved crosslinking and curing speed that improves the physical, mechanical, chemical and thermal properties of the cured product.
- the numbers expressing quantities of ingredients, properties such as concentration, process conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
- aspects of the present disclosure relate to one pot synthesis process for the preparation of photo-curable multifunctional tetra- acrylated/ methacrylated epoxy resin.
- the single pot process for the synthesis of multifunctional tetra-acrylated/ methacrylated epoxy resin according to the present disclosure enables the synthesis of tetra-acrylated/ methacrylated epoxy resin in high purity and yield, without any harmful byproduct formation and the process does not involve any hazardous starting materials. Further, the process of the present disclosure avoids the isolation of intermediate, thus making the process more efficient and cost-effective.
- Photo-curable resins are cured using radiation source such as UV light, visible light, electron beam and the like. Typically, UV radiation is used for curing epoxy resins since UV radiation is more energetic.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, including forming a di-acryl/ methacryl epoxy resin by reacting diglycidal ether with acrylic acid/ methacrylic acid in the presence of a catalyst; and converting di-acryl/ methacryl epoxy resin into tetra-acrylated/ methacrylated epoxy resin by reaction with acrylic acid/ methacrylic acid in the presence of a heteropolyacid catalyst; wherein the di-acryl/ methacryl epoxy resin is not isolated after its formation and is in-situ reacted with acrylic acid/ methacrylic acid in the presence of heteropolyacid catalyst to obtain tetra-acrylated/ methacrylated epoxy resin.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein the reaction of di-acryl/ methacryl epoxy resin with acrylic acid/ methacrylic acid can occur at a temperature in the range of 40 °C to 100 °C and at pressure in the range of atmospheric pressure to 5 bars. In a preferred embodiment, the reaction can be carried out at 90 °C.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin
- the catalyst for the synthesis of di-acryl/methacryl epoxy resin can be selected from but not limited to quaternary ammonium compounds such as tetra- n-butylammonium bromide (TBAB), cetyl trimethyl ammonium bromide (CTAB), trimethylammonium chloride; alkyl amines such as triethyl amine, dimethylbenzylamine; organophosphorus compound such as triphenylphosphine and lewis acid such as boron trifluoride.
- the reaction for the synthesis of di-acryl/methacryl epoxy resin can also take place in the presence of inhibitor such as hydroquinone (HQ) and anti-oxidant such as butylated hydroxy toluene (BHT).
- HQ hydroquinone
- BHT butylated hydroxy toluene
- the catalyst can be a quaternary ammonium compound tetra-n-butylammonium bromide.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated epoxy resin, wherein the one pot process results in the synthesis of bisphenol based tetra- acrylated epoxy resin, as shown in Scheme 6.
- the one pot process results in the synthesis of bisphenol based tetra- acrylated epoxy resin, as shown in Scheme 6.
- diglycidyl ether of bisphenol reacts with acrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-acrylate of bisphenol, which is further reacted in the same pot with acrylic acid using heteropolyacid catalyst resulting in epoxy tetra- acrylate of bisphenol.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- methacrylated epoxy resin, wherein the one pot process results in the synthesis of bisphenol based tetra-methacrylated epoxy resin, as shown in Scheme 7.
- the one pot process results in the synthesis of bisphenol based tetra-methacrylated epoxy resin, as shown in Scheme 7.
- diglycidyl ether of bisphenol reacts with methacrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-methacrylate of bisphenol, which is further reacted in the same pot with methacrylic acid using heteropolyacid catalyst resulting in epoxy tetra-methacrylate of bisphenol.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional, tetra- acrylated epoxy resin, wherein the one pot process results in the synthesis of aromatic or aliphatic diols based tetra-acrylated epoxy resin, as shown in Scheme 8.
- the one pot process results in the synthesis of aromatic or aliphatic diols based tetra-acrylated epoxy resin, as shown in Scheme 8.
- diglycidyl ether of diol aromatic or aliphatic
- reacts with acrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-acrylate of diol, which is further reacted in the same pot with acrylic acid using heteropolyacid catalyst resulting in epoxy tetra-acrylate of the starting diol.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional, tetra- methacrylated epoxy resin, wherein the one pot process results in the synthesis of aromatic or aliphatic diols based tetra-methacrylated epoxy resin, as shown in Scheme 9.
- diglycidyl ether of diol aromatic or aliphatic
- methacrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-methacrylate of diol, which is further reacted in the same pot with methacrylic acid using heteropolyacid catalyst resulting in epoxy tetra-methacrylate of the starting diol.
- the heteropoly acid is a class of acid made up of a combination of hydrogen and oxygen with particular metals and non-metals.
- a heteropoly acid compound must contain an “addenda atom” (transition metal such as tungsten, molybdenum, vanadium, cobalt, zinc etc.); a “hetero atom” (such as silicon, phosphorus, arsenic etc.); oxygen, linked to the metal atom and acidic hydrogen atoms.
- the metal addenda atoms linked by oxygen atoms form a cluster with the hetero-atom inside bonded via oxygen atoms. Examples with more than one type of metal addenda atom in the cluster are well known.
- the conjugate anion of a heteropoly acid is known as a polyoxometalate.
- Different combinations of addenda atoms and different types of heteroatom can result in several different types of heteropolyacids.
- Two polyacids groups based on Keggin (HXMAU) and Dawson (H r ,X 2 M 18 O 62 ) structures can be represented as shown in the below Table.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein the heteropolyacid catalyst can be an acid catalyst selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and the like.
- the heteropolyacid catalyst can be phosphotungstic acid.
- the heteropolyacid according to the embodiments of the present disclosure can be used in catalytic amount in the range of 0.1 to 5 wt%. , preferably in the range of 0.2 to 2 wt% and most preferably in the range of 0.3 to 1 wt%.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein the byproduct is water, which can be removed by reverse azeotropic distillation using dichloromethane as the solvent.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein the product tetra-acrylated/ methacrylated epoxy resin can be formed in high purity and yield in the range of 95-98%.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein ratio of di-acryl/ methacryl epoxy resin and acrylic acid/ methacrylic acid used can be in the range of 1:2 to 1:2.5 equivalent.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein di-acrylated/ methacrylated epoxy resin can be prepared starting from diglycidyl ether selected from but not limited to resorcinol diglycidyl ether, bisphenol S-diglycidal ether, bisphenol A-diglycidal ether, bisphenol E-diglycidal ether, bisphenol F-diglycidal ether, butanediol diglycidal ether, hexanediol diglycidal ether, propanediol diglycidal ether, pentanediol diglycidal ether and the like.
- diglycidyl ether selected from but not limited to resorcinol diglycidyl ether, bisphenol S-diglycidal ether, bisphenol A-diglycidal ether, bisphenol E-diglycidal ether, bisphenol F-diglycid
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein di-acrylated/ methacrylated epoxy resin can be selected from but not limited to resorcinol based di-acrylated/ methacrylated epoxy resin, bisphenol S- based di-acrylated/ methacrylated epoxy resin, bisphenol A- based di-acrylated/ methacrylated epoxy resin, bisphenol E- based di-acrylated/ methacrylated epoxy resin, bisphenol F-based di-acrylated/ methacrylated epoxy resin, butanediol based di-acrylated/ methacrylated epoxy resin, hexanediol based di-acrylated/ methacrylated epoxy resin, propanediol based di-acrylated/ methacrylated epoxy resin, pentanediol based di-acrylated/ methacrylated epoxy resin and the like.
- di-acrylated/ methacrylated epoxy resin can be selected from
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein the tetra-acrylated/methyacrylated epoxy resin can be selected from but not limited to resorcinol-based epoxy tetra-acrylate/methacrylate, bisphenol S- based epoxy tetra-acrylate/methacrylate, bisphenol A- based epoxy tetra- acrylate/methacrylate, bisphenol E- based epoxy tetra-acrylate/methacrylate, bisphenol F- based epoxy tetra-acrylate/methacrylate, butanediol based epoxy tetra-acrylate/methacrylate, hexanediol based epoxy tetra-acrylate/methacrylate, propanediol based epoxy tetra- acrylate/methacrylate, pentanedio
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylate epoxy resin, wherein the di-acrylated/ methacrylate epoxy resin has free secondary hydroxyl groups.
- the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylate epoxy resin, wherein the tetra-acrylated/ methacrylate epoxy resin does not have any free secondary hydroxyl groups.
- the present disclosure relates to a UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, synthesized by one pot synthesis process, wherein the tetra-acrylated/ methacrylated epoxy resin demonstrates improved crosslinking and curing speed that improves the physical, mechanical, chemical and thermal properties of the cured product.
- the present disclosure relates to UV- curable multifunctional tetra- acrylated/ methacrylated epoxy resin that can be synthesized in high purity and without any harmful byproduct formation.
- the present disclosure relates to UV-curable multifunctional tetra- acrylated / methacrylated epoxy resin, synthesized by the one pot synthesis process, wherein the tetra- acrylated/ methacrylate epoxy resin, thus obtained can be further blended with suitable reactive diluents (viscosity modifiers), additives and photoinitiators according to the end application and irradiated under suitable wavelength of UV radiation, for curing and crosslinking.
- suitable reactive diluents viscosity modifiers
- additives and photoinitiators according to the end application and irradiated under suitable wavelength of UV radiation, for curing and crosslinking.
- the diluents typically used in such reactions include polyester acrylate or urethane acrylate selected from TMPTA (Trimethylol propane triacrylate), HDDA (Hexanediol diacrylate), TPGDA (Tripropylene glycol diacrylate), PEGDA (Polyethylene glycol diacrylate), BDDA (Butanediol diacrylate) and the like.
- Additives that can be blended with tetra- acrylated/ methacrylate epoxy resin prepared according to the process of the present disclosure can include inhibitors, plasticizers, light stabilizers and the like.
- Photoinitiators that can be used can be selected from free radical (type 1 and type 2), cationic and anionic photoinitiators.
- free radical type 1 photoinitiators are used for the curing process, wherein the photoinitiators are selected from but not limited to Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure 819, Ciba), 1 -Hydroxycyclohexyl -phenyl ketone (Irgacure 184, Ciba), Diphenyl (2 4 6- trimethylbenzoyl) phosphine oxide (TPO) and the like.
- the photoinitiators are selected from but not limited to Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure 819, Ciba), 1 -Hydroxycyclohexyl -phenyl ketone (Irgacure 184, Ciba), Diphenyl (2 4 6- trimethylbenzoyl) phosphine oxide (TPO) and the like.
- the process of the present disclosure can be applied to prepare products with functionalities in the range of three to eight or more, depending upon the number of epoxides in the starting material used.
- Example 1 Preparation of resorcinol based epoxy tetraacrylate
- Reaction temperature was raised to 90 °C and maintained for 8 h. At the end, part of the reaction mass was taken out to determine the acid value which is preferred less than 5 mg KOH/g. Further solvent was distilled under partial vacuum to obtain the desired product epoxy di-acrylate of Bisphenol-S.
Abstract
The present disclosure pertains to UV-curable epoxy acrylate/ methacrylate resins and process for their synthesis. Specifically, the present disclosure pertains to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, resulting in tetra-acrylated/ methacrylated epoxy resin with improved crosslinking and curing speed.
Description
PHOTO-CURABLE MULTIFUNCTION ACRYLATED/ METHACRYLATED
EPOXY RESIN AND ONE-POT PREPARATION THEREOF
FIELD OF THE INVENTION
[0001] The present disclosure pertains to organic synthesis. In particular, the present disclosure pertains to organic synthesis of photo-curable acrylate/ methacrylate resins.
BACKGROUND OF THE INVENTION
[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.
[0003] In recent years, photo-induced polymerization has become a well-known technology owing to its large variety of industrial applications such as printing inks, coatings, adhesives, sealants, etc. Among numerous methods, ultraviolet (UV)-radiation curing is one of the most efficient ways to rapidly convert the liquid photosensitive resin to solid polymer within a fraction of a second. Ultraviolet-curable resins are the resins most suitable to the requirements of the times such as low pollution, resource conservation, high performance and functionalization. The oligomers and monomers commonly used in UV-curable formulations include acrylated compounds such as epoxy acrylate/ methacrylate (vinyl ester) resins, urethane acrylates, polyester and polyether acrylates and epoxy acrylate nanocomposites. Epoxy acrylate/methacrylate resins are (semi-) polymeric substances called oligomers with variable chain lengths that are widely applied as photo-sensitive substrate in various industries and manufacture because of the distinct properties such as great adhesion, corrosion resistance and hardness.
[0004] Amongst the epoxy acrylate resins, di-functional acrylates i.e, diacrylated epoxy resins are most commonly synthesized. The method of preparation of diacrylated epoxy resins typically involves the reaction of different epoxy resins (different phenols) with acrylic acid. Generally, diglycidal ethers comprising two epoxide functional groups are reacted with acrylic acid in the presence of quaternary ammonium compounds, alkyl amines, alkyl/aryl phosphines and Lewis acid catalyst, resulting in ring opening of epoxide or end-capping the epoxide groups with acrylate group to obtain diacrylated epoxy resin, as shown in Scheme 1.
Scheme 1: General Scheme for Epoxy Di-Acrylate
[0005] The diacrylated epoxy resin thus obtained has two secondary hydroxyl groups on the backbone of the oligomer chain, which do not further react with acrylic acid to form ester linkage, as their reaction is very sluggish. Additionally, the presence of secondary OH groups hinders the curing speed and also reduces the crosslinking density of the polymer, thus, weakening the physical, mechanical, chemical and thermal properties of the UV-cured
Scheme 2: Formation of Di- and Tetra-Acrylated Bisphenol A based Epoxy Resin
[0006] In attempts to synthesize multifunctional epoxy resins, in recent years, work towards the synthesis of tetra- acrylated epoxy resins is being reported. In one such process reported in US patent 5,650,462, depicted in Scheme 2, Bisphenol A diglycidal ether is reacted with acryloyl chloride in the presence of basic catalyst triethylamine (Et^N), resulting in formation of a mixture of di- and tetra-acrylated epoxy resins. Thus, though this process yields tetra- acrylated epoxy resin, the purity of the product obtained is very less. Furthermore, this reaction yields byproducts that are extremely hazardous; treatment and disposal of the effluents is an issue. The use of acryloyl chloride as an active ingredient for end-capping the epoxide and hydroxyl groups with acrylate function groups also has drawbacks. Acryloyl chloride is highly toxic, flammable, has a lachrymatory effect and is not very stable as it decomposes on contact with moisture, thus it cannot be stored in open environment. Moreover, toxic fumes of hydrochloric acid are generated throughout the reaction.
[0007] In another reported procedure in patent no. US 3,845,009 as shown in Scheme 3, tetra-methacrylated epoxy resins have been synthesized starting from resorcinol diglycidal ether, which is reacted with methacrylic acid using base as a catalyst to form di -methacrylic Epoxy Resin. The dimethacrylated epoxy resin, thus obtained, is then reacted with methacryloyl chloride in presence of base catalyst triethylamine (EtsN) to end-cap secondary hydroxyl groups, resulting in tetra-methacrylic epoxy resin. The use of methacryloyl chloride has limitations similar to the use of acryloyl chloride such as methacryloyl chloride is flammable with low stability, toxic, corrosive, lachrymatory and generates extremely hazardous byproducts (toxic fumes of hydrochloric acid are generated throughout the
Scheme 3: Tetra-Methacrylated epoxy of resorcinol
[0008] Another reported method of synthesizing tetra-acrylated epoxy amino resin has been reported by Mohtadizadeh et al.; Progress in Organic Coatings', 2015, 231-239, wherein tetra-functional epoxy amino resin, namely tetra- amino -glycidyl ether is reacted with acrylic acid in presence of a basic catalyst, resulting in the formation of tetra-acrylated epoxy amino resin, as shown in Scheme 4. However, the secondary hydroxyl groups generated during this reaction do not react further and remain as such in the final compound. The presence of free secondary hydroxyl groups in this tetra-acrylated epoxy amino resin results in reduced crosslinking density and hinders the curing speed. The product thus obtained, weakens the physical, mechanical, chemical and thermal properties of the UV-cured product.
Scheme 4: Synthesis of tetra-functional epoxy amino resin
[0009] Thus there is an urgent need to develop an improved UV-curable tetra- acrylated/ methacrylated epoxy resin and synthetic procedure for its synthesis, which can overcome the deficiencies associated with the known arts. Need is also felt for an improved UV-curable tetra- acrylated/ methacrylated epoxy resin, which has increased functionality, can be synthesized in high purity without any toxic byproduct formation, demonstrates improved crosslinking and curing speed and improves the physical, mechanical, chemical and thermal properties of the cured product.
OBJECTS OF THE INVENTION
[0010] An object of the present disclosure is to provide an improved photo-curable tetra- acrylated/ methacrylated epoxy resin and process for its synthesis, which can overcome deficiencies associated with the known arts.
[0011] Another object of the present disclosure is to provide a photo-curable multifunctional, tetra- acrylated/ methacrylated epoxy resin that demonstrates improved crosslinking and curing speed.
[0012] Yet another object of the present disclosure is to provide a photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin that improves the physical, mechanical, chemical and thermal properties of the cured product.
[0013] Another object of the present disclosure is to provide a photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin that can be synthesized in high purity and without any harmful byproduct formation.
[0014] Still another object of the present disclosure is to provide a one pot synthetic process for the synthesis of multifunctional tetra-acrylated/ methacrylated epoxy resin that does not involve any hazardous starting materials and provides product in high purity.
[0015] The other objects and preferred embodiments and advantages of the present disclosure will become more apparent from the following description of the present disclosure when read in conjunction with the accompanying examples and figures, which are not intended to limit scope of the present disclosure in any manner.
SUMMARY OF THE INVENTION
[0016] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in Detailed Description section. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0017] The foregoing and other objects are attained by the present disclosure, which relates to photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin and one pot synthetic process for its synthesis.
[0018] In the first aspect, the present disclosure relates to one pot synthesis process for the preparation of photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, including forming a di-acryl/ methacryl epoxy resin by reacting diglycidal ether with acrylic acid/ methacrylic acid in the presence of a catalyst; and converting di-acryl/methacryl epoxy resin into tetra-acrylated/ methacrylated epoxy resin by reaction with acrylic acid/ methacrylic acid in the presence of a heteropolyacid catalyst; wherein the di-acryl/ methacryl epoxy resin is not isolated after its formation and is in-situ reacted with acrylic acid/ methacrylic acid in the presence of heteropolyacid catalyst to obtain tetra-acrylated/ methacrylated epoxy resin.
[0019] The single pot process for the synthesis of multifunctional tetra-acrylated/ methacrylated epoxy resin according to the present disclosure enables the synthesis of tetra- acrylated / methacrylated epoxy resin in high purity and yield, without any harmful byproduct formation and the process does not involve any hazardous starting materials.
[0020] In the second aspect, the present disclosure relates to a photo-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, synthesized by one pot synthesis process, wherein the tetra-acrylated / methacrylated epoxy resin demonstrates improved crosslinking and curing speed that improves the physical, mechanical, chemical and thermal properties of the cured product.
[0021] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.
DETAILED DESCRIPTION
[0022] The following is a detailed description of embodiments of the present disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
[0023] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”
[0024] Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
[0025] As used in the description herein and throughout the claims that follow, the meaning of “a,” “an,” and “the” includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise.
[0026] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, process conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
[0027] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.
[0028] All methods described herein can be performed in suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0029] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0030] Various terms are used herein. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
[0031] Aspects of the present disclosure relate to one pot synthesis process for the preparation of photo-curable multifunctional tetra- acrylated/ methacrylated epoxy resin. The single pot process for the synthesis of multifunctional tetra-acrylated/ methacrylated epoxy resin according to the present disclosure enables the synthesis of tetra-acrylated/ methacrylated epoxy resin in high purity and yield, without any harmful byproduct formation and the process does not involve any hazardous starting materials. Further, the process of the present disclosure avoids the isolation of intermediate, thus making the process more efficient and cost-effective. Photo-curable resins are cured using radiation source such as UV light, visible light, electron beam and the like. Typically, UV radiation is used for curing epoxy resins since UV radiation is more energetic.
[0032] In the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, including forming a di-acryl/ methacryl epoxy resin by reacting diglycidal ether with acrylic acid/ methacrylic acid in the presence of a catalyst; and converting di-acryl/ methacryl epoxy resin into tetra-acrylated/ methacrylated epoxy resin by reaction with acrylic acid/ methacrylic acid in the presence of a heteropolyacid catalyst; wherein the di-acryl/ methacryl epoxy resin is not isolated after its formation and is in-situ reacted with acrylic acid/ methacrylic acid in the presence of heteropolyacid catalyst to obtain tetra-acrylated/ methacrylated epoxy resin. A general scheme depicting the one pot process is described in Scheme 5, wherein when R=H, the compound is acrylic acid and when R=CHs, the compound is known as methacrylic acid. Depending upon the acid used, i.e., acrylic acid or methacrylic acid, the corresponding di- or tetra- epoxy resin is obtained. The one pot process is therefore more efficient and cost-effective than the processes of prior art, because it obviates isolation and/or purification of the di-acryl/ methacryl epoxy resin. Further, the process according to the first aspect of the present disclosure provides tetra-acrylated/ methacrylated epoxy resin in high purity and without any harmful byproduct formation. The process of the present disclosure does not involve any hazardous starting materials like acid chlorides that are toxic, hazardous, lachrymatory and unstable.
Scheme 5: General Scheme for the synthesis of tetra -acrylated/ methacrylated epoxy resin
[0033] In another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein the reaction of di-acryl/ methacryl epoxy resin with acrylic acid/ methacrylic acid can occur at a temperature in the range of 40 °C to 100 °C and at pressure in the range of atmospheric pressure to 5 bars. In a preferred embodiment, the reaction can be carried out at 90 °C.
[0034] In another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein the catalyst for the synthesis of di-acryl/methacryl epoxy resin can be selected from but not limited to quaternary ammonium compounds such as tetra- n-butylammonium bromide (TBAB), cetyl trimethyl ammonium bromide (CTAB), trimethylammonium chloride; alkyl amines such as triethyl amine, dimethylbenzylamine; organophosphorus compound such as triphenylphosphine and lewis acid such as boron trifluoride. The reaction for the synthesis of di-acryl/methacryl epoxy resin can also take place in the presence of inhibitor such as hydroquinone (HQ) and anti-oxidant such as butylated hydroxy toluene (BHT).
[0035] In a preferred embodiment, the catalyst can be a quaternary ammonium compound tetra-n-butylammonium bromide.
[0036] In an exemplary embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated epoxy resin, wherein the one pot process results in the synthesis of bisphenol based tetra- acrylated epoxy resin, as shown in Scheme 6. According to Scheme 6, diglycidyl ether of bisphenol reacts with acrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-acrylate of bisphenol, which is further reacted in the same pot with acrylic acid using heteropolyacid catalyst resulting in epoxy tetra- acrylate of bisphenol.
Scheme 6: Synthesis of Bisphenol based tetra-acrylated epoxy resin
[0037] In another exemplary embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- methacrylated epoxy resin, wherein the one pot process results in the synthesis of bisphenol based tetra-methacrylated epoxy resin, as shown in Scheme 7. According to Scheme 7, diglycidyl ether of bisphenol reacts with methacrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-methacrylate of bisphenol, which is further reacted in the same pot with methacrylic acid using heteropolyacid catalyst resulting in epoxy tetra-methacrylate of bisphenol.
Scheme 7: Synthesis of Bisphenol based tetra-methacrylated epoxy resin
[0038] In another exemplary embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional, tetra- acrylated epoxy resin, wherein the one pot process results in the synthesis of aromatic or aliphatic diols based tetra-acrylated epoxy resin, as shown in Scheme 8. According to Scheme 8, diglycidyl ether of diol (aromatic or aliphatic) reacts with acrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-acrylate of diol, which is further reacted in the same pot with acrylic acid using heteropolyacid catalyst resulting in epoxy tetra-acrylate of the starting diol.
Scheme 8: Synthesis of diol based tetra-acrylated epoxy resin
[0039] In another exemplary embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional, tetra- methacrylated epoxy resin, wherein the one pot process results in the synthesis of aromatic or aliphatic diols based tetra-methacrylated epoxy resin, as shown in Scheme 9. According to Scheme 9, diglycidyl ether of diol (aromatic or aliphatic) reacts with methacrylic acid in the presence of quaternary ammonium compound resulting in epoxy di-methacrylate of diol, which is further reacted in the same pot with methacrylic acid using heteropolyacid catalyst resulting in epoxy tetra-methacrylate of the starting diol.
Scheme 9: Synthesis of diol based tetra-acrylated epoxy resin
[0040] According to the embodiments of the present disclosure, the heteropoly acid is a class of acid made up of a combination of hydrogen and oxygen with particular metals and non-metals. A heteropoly acid compound must contain an “addenda atom” (transition metal such as tungsten, molybdenum, vanadium, cobalt, zinc etc.); a “hetero atom” (such as silicon, phosphorus, arsenic etc.); oxygen, linked to the metal atom and acidic hydrogen atoms. The metal addenda atoms linked by oxygen atoms form a cluster with the hetero-atom inside bonded via oxygen atoms. Examples with more than one type of metal addenda atom in the cluster are well known. The conjugate anion of a heteropoly acid is known as a polyoxometalate. Different combinations of addenda atoms and different types of heteroatom can result in several different types of heteropolyacids. Two polyacids groups based on
Keggin (HXMAU) and Dawson (Hr,X2M18O62) structures can be represented as shown in the below Table.
[0041] In one embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein the heteropolyacid catalyst can be an acid catalyst selected from phosphotungstic acid, phosphomolybdic acid, silicotungstic acid and the like. In a preferred embodiment, the heteropolyacid catalyst can be phosphotungstic acid. The heteropolyacid according to the embodiments of the present disclosure can be used in catalytic amount in the range of 0.1 to 5 wt%. , preferably in the range of 0.2 to 2 wt% and most preferably in the range of 0.3 to 1 wt%.
[0042] In yet another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein the byproduct is water, which can be removed by reverse azeotropic distillation using dichloromethane as the solvent.
[0043] In still another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein the product tetra-acrylated/ methacrylated epoxy resin can be formed in high purity and yield in the range of 95-98%.
[0044] In another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein ratio of di-acryl/ methacryl epoxy resin and acrylic acid/ methacrylic acid used can be in the range of 1:2 to 1:2.5 equivalent.
[0045] In another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, wherein di-acrylated/ methacrylated epoxy resin can be prepared starting from diglycidyl ether selected from but not limited to resorcinol diglycidyl ether, bisphenol S-diglycidal ether, bisphenol A-diglycidal ether, bisphenol E-diglycidal ether,
bisphenol F-diglycidal ether, butanediol diglycidal ether, hexanediol diglycidal ether, propanediol diglycidal ether, pentanediol diglycidal ether and the like.
[0046] In another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein di-acrylated/ methacrylated epoxy resin can be selected from but not limited to resorcinol based di-acrylated/ methacrylated epoxy resin, bisphenol S- based di-acrylated/ methacrylated epoxy resin, bisphenol A- based di-acrylated/ methacrylated epoxy resin, bisphenol E- based di-acrylated/ methacrylated epoxy resin, bisphenol F-based di-acrylated/ methacrylated epoxy resin, butanediol based di-acrylated/ methacrylated epoxy resin, hexanediol based di-acrylated/ methacrylated epoxy resin, propanediol based di-acrylated/ methacrylated epoxy resin, pentanediol based di-acrylated/ methacrylated epoxy resin and the like.
[0047] In another embodiment of the first aspect, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra- acrylated/ methacrylated epoxy resin, wherein the tetra-acrylated/methyacrylated epoxy resin can be selected from but not limited to resorcinol-based epoxy tetra-acrylate/methacrylate, bisphenol S- based epoxy tetra-acrylate/methacrylate, bisphenol A- based epoxy tetra- acrylate/methacrylate, bisphenol E- based epoxy tetra-acrylate/methacrylate, bisphenol F- based epoxy tetra-acrylate/methacrylate, butanediol based epoxy tetra-acrylate/methacrylate, hexanediol based epoxy tetra-acrylate/methacrylate, propanediol based epoxy tetra- acrylate/methacrylate, pentanediol based epoxy tetra-acrylate/methacrylate and the like.
[0048] In another embodiment, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylate epoxy resin, wherein the di-acrylated/ methacrylate epoxy resin has free secondary hydroxyl groups. [0049] In another embodiment, the present disclosure relates to one pot synthesis process for the preparation of UV-curable multifunctional tetra-acrylated/ methacrylate epoxy resin, wherein the tetra-acrylated/ methacrylate epoxy resin does not have any free secondary hydroxyl groups.
[0050] In the second aspect, the present disclosure relates to a UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin, synthesized by one pot synthesis process, wherein the tetra-acrylated/ methacrylated epoxy resin demonstrates improved crosslinking and curing speed that improves the physical, mechanical, chemical and thermal properties of the cured product.
[0051] In one embodiment of the second aspect, the present disclosure relates to UV- curable multifunctional tetra- acrylated/ methacrylated epoxy resin that can be synthesized in high purity and without any harmful byproduct formation.
[0052] In another embodiment of the second aspect, the present disclosure relates to UV-curable multifunctional tetra- acrylated / methacrylated epoxy resin, synthesized by the one pot synthesis process, wherein the tetra- acrylated/ methacrylate epoxy resin, thus obtained can be further blended with suitable reactive diluents (viscosity modifiers), additives and photoinitiators according to the end application and irradiated under suitable wavelength of UV radiation, for curing and crosslinking. The diluents typically used in such reactions include polyester acrylate or urethane acrylate selected from TMPTA (Trimethylol propane triacrylate), HDDA (Hexanediol diacrylate), TPGDA (Tripropylene glycol diacrylate), PEGDA (Polyethylene glycol diacrylate), BDDA (Butanediol diacrylate) and the like. Additives that can be blended with tetra- acrylated/ methacrylate epoxy resin prepared according to the process of the present disclosure can include inhibitors, plasticizers, light stabilizers and the like. Photoinitiators that can be used can be selected from free radical (type 1 and type 2), cationic and anionic photoinitiators. In a preferred embodiment free radical type 1 photoinitiators are used for the curing process, wherein the photoinitiators are selected from but not limited to Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (Irgacure 819, Ciba), 1 -Hydroxycyclohexyl -phenyl ketone (Irgacure 184, Ciba), Diphenyl (2 4 6- trimethylbenzoyl) phosphine oxide (TPO) and the like.
[0053] According to the embodiments of the present disclosure, the process of the present disclosure can be applied to prepare products with functionalities in the range of three to eight or more, depending upon the number of epoxides in the starting material used.
[0054] While the foregoing description discloses various embodiments of the disclosure, other and further embodiments of the invention may be devised without departing from the basic scope of the disclosure. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.
[0055] The present disclosure is further explained in the form of following examples. However, it is to be understood that the foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
[0056] All the raw materials used are commercially available and were purchased from local vendors. Diglycidal ether of Bisphenol A, Bisphenol F and Resorcinol were received from Atul Ltd and Bisphenol S was obtained from Hindustan Monomers Pvt. Ltd. Other raw materials were purchased from Merck. FT-IR was determined using Perkin Elmer Spectrum 100 FTIR. Agilent Cary 60 UV-Vis was for determining UV/Visible spectra. Waters 2414 RI detector 515 HPLC Pump was used for GPC. Mettler Toledo DSC 3 with Software version: STARe SW 16.00 was used for Differential Scanning Calorimetry (DSC). Perkin Elmer DMA 8000 with Software version Pyris 13.3.2.0030 was used as Dynamic Mechanical Analyzer (DMA). Mettler Toledo TGA/DSC 1 with Software version STARe SW 16.00, was used for Thermogravimetric Analysis (TGA). Bruker Advance 400Hz was used to record C Nuclear Magnetic Resonance (C NMR).
[0057] Example 1: Preparation of resorcinol based epoxy tetraacrylate
[0058] Under nitrogen atmosphere, diglycidal ether of resorcinol (222.24 g, 1 mole) was reacted with acrylic acid (158.5 g, 2.2 mole) in presence of quaternary ammonium compound tetra-n-butyl ammonium bromide (2.7 g, 0.5 wt%) which is used as phase transfer catalyst, inhibitor hydroquinone (0.27 g, 0.05 wt%) and antioxidant butylated hydroxytoluene (0.27 g, 0.05 wt%). Reaction temperature was raised to 90 °C and maintained for 12 h. At the end, part of the reaction mass was taken out to determine the acid value which is preferred less than 5 mg KOH/g. The product obtained is epoxy diacrylate of resorcinol.
[0059] In same pot having epoxy di-acrylate of Resorcinol, was further added acrylic acid (158.5g, 2.2 mole) in presence of heteropolyacid catalyst phosphotungstic acid (0.27 g, 0.05 wt%), solvent dichloromethane (80 g, 15 wt%) and inhibitor hydroquinone (0.27 g, 0.05 wt%). Reaction temperature was raised to 80 °C and esterification reaction was carried out using reverse azeotropic distillation where water of reaction was removed. At the end of the reaction the catalyst was filtered out, the product was alkali washed and vacuum distilled to remove solvent and water from it to obtain the final product epoxy tetra-acrylate of resorcinol
(455 g, 96 %). 13C-NMR (5, ppm): 159.59, 131.99, 131.42, 128.24, 127.78, 107.23, 101.76, 68.71, 67.92, 60.88. FT-IR (X, cm'1): 1729, 1635, 809.
[0060] Example 2: Preparation of Bisphenol S-based epoxy tetraacrylate
[0061] Under nitrogen atmosphere, diglycidal ether of bisphenol-S (362 g, 1 mole) was reacted with acrylic acid (158.5 g, 2.2 mole) in presence of quaternary ammonium compound tetra-n-butyl ammonium bromide (3.4 g, 0.5 wt%), which is used as phase transfer catalyst, accelerator copper(I) chloride (CuCl, 0.07 g, 0.01 wt%), solvent 1,4 dioxane (136 g, 20 wt%), inhibitor hydroquinone (0.34 g, 0.05 wt%) and antioxidant butylated hydroxytoluene (0.34 g, 0.05 wt%). Reaction temperature was raised to 90 °C and maintained for 8 h. At the end, part of the reaction mass was taken out to determine the acid value which is preferred less than 5 mg KOH/g. Further solvent was distilled under partial vacuum to obtain the desired product epoxy di-acrylate of Bisphenol-S.
[0062] In same pot having epoxy di-acrylate of bisphenol-S was further added acrylic acid (158.5g, 2.2 mole) in the presence of heteropolyacid catalyst phosphotungstic acid (3.4 g, 0.5 wt%), solvent dichloro -methane (102 g, 15 wt%) and inhibitor hydroquinone (0.34 g, 0.05 wt%). Reaction temperature was raised to 80 °C and esterification reaction was carried out using reverse azeotropic distillation where water of reaction was removed. At the end of the reaction the catalyst was filtered out, the product was alkali washed and vacuum distilled to remove solvent and water from it to obtain the final product epoxy tetra-acrylate of Bisphenol-S (601 g, 98 %). 13C-NMR (5, ppm): 170.87, 162.07, 133.68, 132.22, 129.35, 127.81, 115.08, 67.78, 66.71, 60.59. FT-IR (X, cm'1): 1729, 1635, 809.
[0063] Example 3: Preparation of Bisphenol -A based epoxy tetra-acrylate
[0064] Under nitrogen atmosphere, diglycidal ether of bisphenol- A (340.41 g, 1 mole) was reacted with acrylic acid (158.5 g, 2.2 mole) in presence of quaternary ammonium compound tetra-n-butyl ammonium bromide (3.3 g, 0.5 wt%), which is used as phase transfer catalyst, inhibitor hydroquinone (0.33 g, 0.05 wt%) and antioxidant butylated hydroxytoluene (0.33 g, 0.05 wt%). Reaction temperature was raised to 90 °C and maintained for 12 h. At the end, part of the reaction mass was taken out to determine the acid value which is preferred less than 5 mg KOH/g. Further solvent was distilled under partial vacuum to obtain the desired product epoxy di-acrylate of Bisphenol-A.
[0065] In same pot having epoxy di-acrylate of bisphenol-A was further added acrylic acid (158.5g, 2.2 mole) in the presence of heteropolyacid catalyst phosphotungstic acid (3.3 g, 0.5 wt%), solvent dichloro -methane (99 g, 15 w%) and inhibitor hydroquinone (0.33 g, 0.05 wt%). Reaction temperature was raised to 80 °C and esterification reaction was carried out using reverse azeotropic distillation where water of reaction was removed. At the end of the reaction the catalyst was filtered out, the product was alkali washed and vacuum distilled to remove solvent and water from it to obtain the final product epoxy tetra-acrylate of Bisphenol-A (580 g, 98 %). 13C-NMR (5, ppm): 166.43, 143.63, 131.62, 128.33, 128.12, 114.05, 68.72, 66.21, 60.21, 41.69, 31.04. FT-IR (X, cm 1): 1729, 1635, 809.
[0066] Example 4: Preparation of Bisphenol-F based epoxy tetra-acrylate
[0067] Under nitrogen atmosphere, diglycidal ether of bisphenol-A (312.36 g, 1 mole) was reacted with acrylic acid (158.5 g, 2.2 mole) in presence of quaternary ammonium
compound tetra-n-butyl ammonium bromide (3.15 g, 0.5 wt%), which is used as phase transfer catalyst, inhibitor hydroquinone (0.31 g, 0.05 wt%) and antioxidant butylated hydroxytoluene (0.31 g, 0.05 wt%). Reaction temperature was raised to 90 °C and maintained for 12 h. At the end, part of the reaction mass was taken out to determine the acid value which is preferred less than 5 mg KOH/g. Further solvent was distilled under partial vacuum to obtain the desired product epoxy di-acrylate of Bisphenol-F.
[0068] In same pot having epoxy di-acrylate of bisphenol-F was further added acrylic acid (158.5g, 2.2 mole) in the presence of heteropolyacid catalyst phosphotungstic acid (3.15 g, 0.5 wt%), solvent dichloro-methane (94g, 15 wt%) and inhibitor hydroquinone (0.31 g, 0.05 wt%). Reaction temperature was raised to 80 °C and esterification reaction was carried out using reverse azeotropic distillation where water of reaction was removed. At the end of the reaction the catalyst was filtered out, the product was alkali washed and vacuum distilled to remove solvent and water from it to obtain the final product epoxy tetra-acrylate of Bisphenol-F (547 g, 97 %). 13C-NMR (5, ppm): 166.37, 166.12, 131.68, 131.39, 128.26, 114.61, 68.81, 66.13, 59.92, 40.11. FT-IR (X, cm 1): 1729, 1635, 809.
[0069] Using the procedures described in Examples 1, 2, 3 and 4, and by replacing acrylic acid with methacrylic acid, diglycidal ether of resorcinol was converted to resorcinol based epoxy tetra-methacrylate, bisphenol-S diglycidal ether was converted to epoxy tetramethacrylate of bisphenol-S, bisphenol-A diglycidal ether was converted to epoxy tetramethacrylate of bisphenol-A and bisphenol-F diglycidal ether was converted to epoxy tetramethacrylate of bisphenol-F.
[0070] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
Claims
1. A one pot synthetic process for the preparation of UV-curable multifunctional tetra- acrylated/metharcylated epoxy resin, comprising: forming a di-acryl/ methacryl epoxy resin by reacting a diglycidal ether with acrylic acid/ methacrylic acid in the presence of a catalyst; and reacting the di-acryl/ methacryl epoxy resin with acrylic acid/ methacrylic acid in the presence of a heteropolyacid catalyst to yield the UV-curable multifunctional tetra- acrylated epoxy resin; wherein the di-acryl/ methacryl epoxy resin is not isolated after its formation.
2. The process as claimed in claim 1, wherein the reaction of di-acryl/ methacryl epoxy resin with acrylic acid/ methacrylic acid occurs at a temperature in the range of 40 °C to 100 °C, preferably at 90 °C and at pressure in the range of atmospheric pressure to 5 bars.
3. The process as claimed in claim 1, wherein the catalyst for the synthesis of di- acryl/methacryl epoxy resin is selected from quaternary ammonium compounds such as tetra-n-butylammonium bromide, cetyl trimethyl ammonium bromide, trimethylammonium chloride; alkyl amines such as triethyl amine, dimethylbenzylamine; organophosphorus compound such as triphenylphosphine and lewis acid such as boron trifluoride.
4. The process as claimed in claim 3, wherein the catalyst is tetra-n-butyl ammonium bromide.
5. The process as claimed in claim 1, wherein the heteropolyacid catalyst is an acid catalyst selected from phosphotungstic acid, phosphomolybdic acid or silicotungstic acid; and is used in the range of 0.1 to 5 wt%, preferably in the range of 0.2 to 2 wt% and most preferably in the range of 0.3 to 1 wt%.
6. The process as claimed in claim 5, wherein the heteropolyacid catalyst is phosphotungstic acid.
7. The process as claimed in claim 1, wherein ratio of di-acryl/ methacryl epoxy resin and acrylic acid/ methacrylic acid used is in the range of 1:2 to 1:2.5 equivalent.
8. The process as claimed in claim 1, wherein diglycidyl ether is selected from resorcinol diglycidyl ether, bisphenol S-diglycidal ether, bisphenol A-diglycidal ether, bisphenol E-diglycidal ether, bisphenol F-diglycidal ether, butanediol diglycidal ether, hexanediol diglycidal ether, propanediol diglycidal ether and pentanediol diglycidal ether.
9. The process as claimed in claim 1, wherein di-acryl/ methacryl epoxy resin is selected from resorcinol based di-acrylated/ methacrylated epoxy resin, bisphenol S- based di- acrylated/ methacrylated epoxy resin, bisphenol A- based di-acrylated/ methacrylated epoxy resin, bisphenol E- based di-acrylated/ methacrylated epoxy resin, bisphenol F- based di-acrylated/ methacrylated epoxy resin, butanediol based di-acrylated/ methacrylated epoxy resin, hexanediol based di-acrylated/ methacrylated epoxy resin, propanediol based di-acrylated/ methacrylated epoxy resin and pentanediol based di- acrylated/ methacrylated epoxy resin.
10. The process as claimed in claim 1, wherein tetra-acryl/ methacryl epoxy resin is selected from resorcinol-based epoxy tetra-acrylate/methacrylate, bisphenol S- based epoxy tetra-acrylate/methacrylate, bisphenol A- based epoxy tetra- acrylate/methacrylate, bisphenol E- based epoxy tetra-acrylate/methacrylate, bisphenol F- based epoxy tetra-acrylate/methacrylate, butanediol based epoxy tetra- acrylate/methacrylate, hexanediol based epoxy tetra-acrylate/methacrylate, propanediol based epoxy tetra-acrylate/methacrylate and pentanediol based epoxy tetra- acrylate/meth acrylate .
11. The process as claimed in claim 1, wherein the tetra- acrylated/methacrylated epoxy resin does not have any free secondary hydroxyl groups.
12. The process as claimed in claim 1, wherein the product tetra-acrylated/ methacrylated epoxy resin is formed in high purity and yield in the range of 95-98%.
13. A UV-curable multifunctional tetra-acrylated/ methacrylated epoxy resin prepared by the process as claimed in claims 1-12.
14. The tetra-acrylated epoxy resin as claimed in claim 13, wherein the resin has improved crosslinking and curing speed.
15. The tetra-acrylated epoxy resin as claimed in claim 13, wherein the resin improves the physical, mechanical, chemical and thermal properties of the cured product.
The tetra- acrylated epoxy resin as claimed in claim 13, wherein the tetra- acrylated/ methacrylate epoxy resin, is further blended with reactive diluents (viscosity modifiers), additives and photo -initiators and irradiated under UV radiation, for curing and crosslinking.
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| US5650462A (en) * | 1995-09-20 | 1997-07-22 | Societe Nationale Industrielle Et Aerospatiale | Composite material having a fibrous reinforcement and matrix obtained by the polymerization of acrylic monomers and its production |
| WO2009088087A1 (en) * | 2008-01-10 | 2009-07-16 | Nipponkayaku Kabushikikaisha | Epoxidation catalyst, process for production of epoxidation catalyst, process for production of epoxy compounds, curable resin compositions, and products of curing of the compositions |
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2021
- 2021-03-09 WO PCT/IB2021/051937 patent/WO2022153095A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650462A (en) * | 1995-09-20 | 1997-07-22 | Societe Nationale Industrielle Et Aerospatiale | Composite material having a fibrous reinforcement and matrix obtained by the polymerization of acrylic monomers and its production |
| WO2009088087A1 (en) * | 2008-01-10 | 2009-07-16 | Nipponkayaku Kabushikikaisha | Epoxidation catalyst, process for production of epoxidation catalyst, process for production of epoxy compounds, curable resin compositions, and products of curing of the compositions |
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| MOHTADIZADEH, F. ET AL.: "Tetra-functional epoxy-acrylate as crosslinker for UV curable resins: Synthesis, spectral, and thermo-mechanical studies", PROGRESS IN ORGANIC COATINGS, vol. 89, 30 October 2015 (2015-10-30), pages 231 - 239, XP029307503, DOI: 10.1016/j.porgcoat.2015.09.002 * |
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