CN110272537A - A kind of synthetic method solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED - Google Patents
A kind of synthetic method solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED Download PDFInfo
- Publication number
- CN110272537A CN110272537A CN201910555359.8A CN201910555359A CN110272537A CN 110272537 A CN110272537 A CN 110272537A CN 201910555359 A CN201910555359 A CN 201910555359A CN 110272537 A CN110272537 A CN 110272537A
- Authority
- CN
- China
- Prior art keywords
- vinyl
- polyester
- aldehyde
- resin
- aldehyde resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 100
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 65
- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 230000006837 decompression Effects 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000010792 warming Methods 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 7
- 239000008158 vegetable oil Substances 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 23
- -1 aldehyde ketone Chemical class 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000004359 castor oil Substances 0.000 claims description 10
- 235000019438 castor oil Nutrition 0.000 claims description 10
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 239000010773 plant oil Substances 0.000 claims description 5
- 239000002383 tung oil Substances 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- ZJTLZYDQJHKRMQ-UHFFFAOYSA-N menadiol Chemical compound C1=CC=CC2=C(O)C(C)=CC(O)=C21 ZJTLZYDQJHKRMQ-UHFFFAOYSA-N 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 241000196324 Embryophyta Species 0.000 claims 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims 1
- 230000000640 hydroxylating effect Effects 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 235000019198 oils Nutrition 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000008159 sesame oil Substances 0.000 claims 1
- 235000011803 sesame oil Nutrition 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 20
- 238000007711 solidification Methods 0.000 abstract description 12
- 230000008023 solidification Effects 0.000 abstract description 12
- 238000004945 emulsification Methods 0.000 abstract description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003063 flame retardant Substances 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract 2
- 229920005862 polyol Polymers 0.000 abstract 1
- 150000003077 polyols Chemical class 0.000 abstract 1
- 239000004645 polyester resin Substances 0.000 description 10
- 229920001225 polyester resin Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000012423 maintenance Methods 0.000 description 7
- 150000003022 phthalic acids Chemical class 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000006210 lotion Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical class OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PYGXUPRQBBNETH-UHFFFAOYSA-N acetic acid;2-hydroxypropyl prop-2-enoate Chemical compound CC(O)=O.CC(O)COC(=O)C=C PYGXUPRQBBNETH-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- SYJCUYXTMQSJLM-UHFFFAOYSA-N phenylphosphanyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)PC1=CC=CC=C1 SYJCUYXTMQSJLM-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009711 regulatory function Effects 0.000 description 1
- 229920006009 resin backbone Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000002023 wood 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/918—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
- C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses the synthetic methods that a kind of UV-LED solidifies the modified end-vinyl waterborne polyester of aldehyde resin.Its synthetic method are as follows: polyacid, polyalcohol, functional flame retardant type polyol and functional more double bond hydroxylated vegetable oils are added in reaction kettle, and organic solvent is added as water entrainer, under nitrogen protection, is warming up to 180 ~ 210oC, back flow reaction to acid value are lower than 10 mgKOH/g, decompression extraction organic solvent;It is cooled to 120 ~ 150oMaleic anhydride is added in C, reacts 3 ~ 5 h;Vinyl function monomer and polymerization inhibitor containing hydroxyl structure are added, 3 ~ 5 h is reacted, obtains the addition product containing hydrophilic radical and vinyl group;Cool down 40 ~ 60 againoC is added neutralizer and neutralizes, obtains the carboxylic acid type polyester containing vinyl group;Deionized water emulsification is added, 15 ~ 30 min of high speed dispersion obtains UV-LED solidification end-vinyl waterborne polyester.Gained vinyl waterborne polyester of the invention has excellent resistance to medium, hardness of film and flexibility, is highly suitable for UV-LED solidified aqueous coating.
Description
Technical field
The present invention relates to UV-LED solidified aqueous coating fields, and in particular to one kind changes for UV-LED solidification aldehyde resin
The preparation method of property end-vinyl waterborne polyester.
Background technique
Polyester resin system is because it is with excellent glossiness, richness, impact resistance, flexibility, weatherability and attachment
Power etc., and it is widely used in paint field.However, polyester is still based on solvent type at present.With mentioning for people's environmental consciousness
Height, environmental regulation are more and more tighter to the limitation of organic volatile in coating (VOC) content, low the VOC even coating products of Diamond Search
It is increasingly subject to market favor.On the other hand, polyester resin belongs to polyester key copolymer, and finished product film easily hydrolyzes, causes
The corrosion and destruction for protecting substrate, with the promotion of people's quality of the life, the polyester resin with excellent film performance seems outstanding
It is urgent.Therefore, the polyester coating for developing Water-borne modification seems especially urgent.
The Water-borne modification of polyester resin has by introducing in resin structure containing carboxyl or sulfonic hydrophilic radical, addition
Machine amine or inorganic base etc. are neutralized into salt, achieve the purpose that Water-borne modification.Chinese patent CN104193973 A discloses a kind of terminal hydroxy group
Aqueous polyester resin and preparation method thereof.By the introducing of terminal hydroxy group, so that aqueous polyester resin molecular chain structure is tended towards stability, mention
The bond energy of each group chemical key in high strand.But the introducing of hydroxyl, unavoidably causes intermolecular hydrogen bonding to act on, and causes
Resin system viscosity is excessive, is not suitable for industrialized production.Chinese patent CN10726668 A discloses a kind of hydrolytic resistance polyester
And preparation method thereof.Traditional trimellitic anhydride hydrophilic unit is replaced by dihydroxy methylpropane acid, obtains aqueous polyester resin.
Although improving anti-hydrolytic performance of the trimellitic anhydride as hydrophilic unit to a certain extent, do not solve inherently
The defect of the hydrolytic resistance of polyester key and carboxylic resin difference.Chinese patent CN106700050 A discloses one kind and is used to prepare
The composition of hydrophilic polyester, hydrophilic polyester and preparation method thereof.By the polynary carboxylic for introducing sulfonic acid in the molecular structure
Acid prepares highly-hydrophilic even water-soluble polyester resin.Although solving the Water-borne modification of polyester resin, however, due to sulfonic acid
The introducing of salt causes its stability to be remarkably decreased.It the characteristics of introducing of hydrophilic radical simultaneously and this body structure of polyester, necessarily leads
The medium-resistance for causing finished product film poor.Therefore, it is necessary to develop the waterborne polyester coating of excellent combination property to meet environmental protection rule
The fixed and market demand.105062341 B of Chinese patent CN discloses a kind of with the poly- ammonia of polyacetals modified water-soluble for helping film forming function
Ester and the preparation method and application thereof.By aldehyde resin modified aqueous polyurethane dispersoid, the medium-resistance of its film is improved.
South China Science & Engineering University Duan Xiaojun etc. has excellent by aldehyde resin modified water-soluble hydroxypropyl lotion, the two-component coating of preparation
Hardness of film, glossiness and medium-resistance.
UV-LED is coating material solidified to have that energy-saving and environmental protection, curing rate is fast, film performance is excellent, is suitable for extensive construction
Etc. advantages, the growing interest by people.Currently, common UV-LED solidified aqueous coating mainly has watersoluble polyurethane acrylic acid
Ester resin, waterborne epoxy acrylate resin, water polyacrylic acid resin etc..Wherein, aqueous urethane acrylate
Resin price is expensive;The viscosity of the coating of waterborne epoxy acrylate resin preparation is big, flexibility is poor.
Summary of the invention
The present invention is directed to the defect of existing aqueous polyester resin hydrolytic resistance, film performance and poor flame retardant properties, provides one
Kind introduces aldehyde resin and vinyl structure in waterborne polyester structure, and is applied to UV-LED solidified aqueous coating neck
Domain improves the resistance to medium of film and the UV-LED solidification aldehyde resin modified water-soluble end-vinyl waterborne polyester of film performance
Preparation method.
The object of the invention is achieved through the following technical solutions:
Solidify end-vinyl waterborne polyester and its synthetic method for UV-LED, comprising the following steps:
1) synthesis of aldehyde resin modified poly ester: in terms of mass fraction, take 20~40 parts of polyalcohols, 35~55 parts it is polynary
Acid, 5~10 parts of aldehyde resin and the more double bond hydroxylated vegetable oils of 5~10 parts of functionality and 10~30 parts of water entrainers, are added to band
Have in the reaction kettle of reflux unit, under nitrogen protection, is to slowly warm up to 110~140 DEG C, is completely dissolved to raw material, is warming up to
180~210 DEG C, back flow reaction to acid value is lower than 10mgKOH/g, is then cooled to 120~150 DEG C, and decompression extraction water entrainer closes
At more plant oil modified polyester of double bond hydroxyl out;
2) synthesis of the modified end-vinyl polyester of aldehyde resin: in terms of mass fraction, taking for preparing in step 1) is how double
2~6 parts of maleic anhydrides are added in the plant oil modified polyester of key hydroxyl, are added in reaction kettle, react 3~5h, are then added 2
The vinyl function monomer and 0.1~0.4 part of polymerization inhibitor of~6 parts of hydroxyl structures, heat preservation the reaction was continued 3~5h, obtain polyacetals
Resin modified vinyl polyester;
3) synthesis of aldehyde resin modified water-soluble end-vinyl polyester: in terms of mass fraction, in the polyacetals of step 2) preparation
0.5~3 part of neutralizer is added in resin modified vinyl polyester to neutralize, stirs 15~30min, product is transferred to dispersion bucket
It is interior, it is gradually added into 100~200 parts of deionized water, 15~30min of high speed dispersion obtains aldehyde resin modified water-soluble end ethylene
Base polyester.
To further realize the object of the invention, it is preferable that the polyacid is adipic acid, terephthalic acid (TPA), isophthalic two
One of formic acid, phthalic acid, tetrahydrophthalic acid are a variety of.
Preferably, the polyalcohol is propylene glycol, butanediol, neopentyl glycol, hexylene glycol, trimethylolpropane and season penta
One of tetrol is a variety of.
Preferably, aldehyde resin is urea formaldehyde A81, aldehyde ketone resin KR-80F, aldehyde ketone resin KR-120, aldehyde ketone resin
KR120B, aldehyde ketone resin KR-120W, aldehyde ketone resin UK-100, aldehyde ketone resin UK-300, aldehyde ketone resin UK-500, aldehyde ketone resin
One of YHKR-1210, aldehyde ketone resin YHKR-1218 or a variety of.
Preferably, the more double bond hydroxylated vegetable oils of functionality are more double bond hydroxyl tung oil, more double bond hydroxyl flax
It is oily, castor oil one or more.
Preferably, the vinyl function monomer of the hydroxyl structure is hydroxy-ethyl acrylate (HEA), acrylic acid hydroxypropyl
Ester (HPA), hydroxyethyl methacrylate (HEMA), hydroxy propyl methacrylate (HPMA) it is one or more.
Preferably, the water entrainer is the one or more of toluene and dimethylbenzene.
Preferably, the polymerization inhibitor be p methoxy phenol, 2- tert-butyl hydroquinone and methylnaphthohydroquinone one kind or
It is a variety of.
Preferably, the neutralizer be ammonium hydroxide, triethylamine, N, N- dimethylethanolamine it is one or more.
Preferably, vacuum distillation temperature described in step (1) is 120~150 DEG C and vacuum degree is 0.04~0.1MPa
Under conditions of carry out.
Preferably, the additional amount of the neutralizer is the 80~120% of maleic anhydride mole.
One kind for UV-LED solidify end-vinyl waterborne polyester, be made by above-mentioned synthetic method, solid content be 35~
55%, viscosity is 400~5000cP, and emulsion particle diameter is 60~200nm.
It is of the present invention for UV-LED solidify aldehyde resin modification end-vinyl waterborne polyester paint field application,
In terms of mass fraction, 1~5% photoinitiator is added in polyester system, through UV-LED film-forming.The photoinitiator
For 4- methyl benzophenone, 2-hydroxyl-2-methyl-1-phenylacetone, thioxanthone, 2,4,6- trimethylbenzoyl phenyl phosphine
Acetoacetic ester it is one or more.
It is of the present invention to be modified end-vinyl waterborne polyester for UV-LED solidification aldehyde resin, solidify through UV-LED and prepares
Paint film have excellent medium-resistance, flexibility good and the advantages such as hardness of film height, can be applied to water-borne wood coating,
The numerous areas such as aqueous binder and water-based ink.
Of the invention is modified end-vinyl waterborne polyester compared with prior art for UV-LED solidification aldehyde resin, has
As follows a little and the utility model has the advantages that
1) using the natural materials modified water-soluble polyester such as functional more double bond hydroxylated vegetable oils, simple process, safety collar
It protects, is low in cost;The introducing of chain alkyl chain can effectively weaken the interstructural hydrogen bond action of waterborne polyester, reduce resin system
Viscosity.
2) present invention by the double-strand in resin backbone structure, reacted using Diels-Alder, be grafted end-vinyl and
Hydrophilic radical, grafting rate is high, and is not necessarily to heavy metal catalyst.
3) aldehyde resin end-vinyl waterborne polyester of the invention, the property of comprehensive aldehyde resin and polyhydroxylated vegetable oil
Can, so that film is had both excellent medium-resistance and hardness.
4) the modified end-vinyl waterborne polyester of aldehyde resin of the invention improves film by UV-LED film-forming
Medium-resistance, flexibility and hardness of film;Energy conservation simultaneously is suitable for extensive construction.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment, the invention will be further described, but the present invention claims guarantors
The range of shield is not limited to the scope of the embodiments.
Embodiment 1:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 1 (dimethylbenzene is as water entrainer):
Table 1:
Preparation process: in terms of mass fraction, by 50.9 parts of phthalic acids, 35 parts of trimethylolpropanes, 5 parts of castor oil and
5 parts of KR-80F are added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C, reflux is anti-
10mgKOH/g, decompression extraction dimethylbenzene should be lower than to acid value;130 DEG C are cooled to, is added 2 parts of maleic anhydrides, reaction 3~
5h;Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol are added, and reacts 3~5h, is contained
The addition product of hydrophilic radical and vinyl group;40~60 DEG C of cooling is added 0.8 part of triethylamine and neutralizes, obtains containing vinyl group
Carboxylic acid type polyester;150 parts of deionized water emulsifications are added, 15~30min of high speed dispersion obtains UV-LED solidification end-vinyl
Waterborne polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%;Viscosity, 1500cP;Lotion
Partial size, 135nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 2:
Table 2:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 3:
Table 3:
As shown in Table 3, the UV-LED solidification aldehyde resin that is used for of the invention is modified end-vinyl waterborne polyester, has film
The performances such as hardness is high, flexibility is good, glossiness is high, adhesive force is excellent and water resistance is superior.The modified end of aldehyde resin of the invention
Vinyl waterborne polyester is reacted with castor oil, trimethylolpropane, aldehyde resin, phthalate first, by carbon carbon
Double bond and aldehyde resin are introduced into resin body structure, are prepared functional more plant oil modified polyester of double bond, are passed through adjusting
Castor oil and aldehyde resin dosage, can regulate and control resin viscosity, reaction site and film performance;Then Diels-Alder is utilized
Reaction introduces maleic anhydride, regulates and controls its dosage, prepare polyester of the backbone structure containing anhydride group, nothing in reaction process
Extra catalyst is needed to be catalyzed;Finally by regulatory function hydroxy acrylate dosage, the modified end ethylene of aldehyde resin is prepared
The polyester of base and carboxyl structural element;Finally neutralizing emulsification can be obtained for the modified end of UV-LED solidification high-performance aldehyde resin
Vinyl waterborne polyester.The present invention has many advantages, such as energy-saving and environmental protection, low in cost.
Embodiment 2:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 4 (dimethylbenzene is as water entrainer):
Table 4:
Preparation process: in terms of mass fraction, by 50.9 parts of phthalic acids, 5 parts of KR-80F, 35 parts of trimethylolpropanes and
Double bond hydroxylated tung oil is added in reaction kettle more than 5 parts, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190
DEG C, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, 2 parts of maleic acids are added
Acid anhydride reacts 3~5h;Maintenance system is temperature-resistant, is added 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol, and reaction 3~
5h obtains the addition product containing hydrophilic radical and vinyl group;40~60 DEG C of cooling is added 0.8 part of triethylamine and neutralizes, contained
There is the carboxylic acid type polyester of vinyl group;150 parts of deionized water emulsifications are added, it is solid to obtain UV-LED by 15~30min of high speed dispersion
Change end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 40%;Viscosity, 1750cP;Lotion
Partial size, 150nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 5:
Table 5:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 6:
Table 6:
Embodiment 3:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 7 (dimethylbenzene is as water entrainer):
Table 7:
Preparation process: in terms of mass fraction, by 51.8 parts of phthalic acids, 6 parts of UK-100,30 parts of pentaerythrites and 6 parts
Castor oil is added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C, back flow reaction is extremely
Acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, 3 parts of maleic anhydrides are added, reacts 3~5h;Dimension
It is constant to hold system temperature, 3 parts of hydroxypropyl acrylates and 0.2 part of p methoxy phenol are added, reacts 3~5h, obtains containing hydrophilic
The addition product of group and vinyl group;40~60 DEG C of cooling is added 1.1 parts of triethylamines and neutralizes, obtains the carboxylic containing vinyl group
Hydrochlorate type polyester;100 parts of deionized water emulsifications are added, it is modified to obtain UV-LED solidification aldehyde resin by 15~30min of high speed dispersion
End-vinyl waterborne polyester.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 50%;Viscosity,
4500cP;Emulsion particle diameter, 190nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 8:
Table 8:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 9:
Table 9:
Embodiment 4:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 10 (toluene is as water entrainer):
Table 10:
Preparation process: in terms of mass fraction, by 41.6 parts of M-phthalic acids, 10 parts of UK-200,30 parts of neopentyl glycols and 10
The more double bond hydroxylated tung oils of part are added in reaction kettle, and toluene is added as water entrainer, under nitrogen protection, is warming up to 190 DEG C,
Back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, 4 parts of maleic anhydrides are added, instead
Answer 3~5h;Maintenance system is temperature-resistant, is added 4 parts of hydroxyethyl methacrylates and 0.4 part of p methoxy phenol, and reaction 3~
5h obtains the addition product containing hydrophilic radical and vinyl group;40~60 DEG C of cooling is added 2 parts of triethylamines and neutralizes, contained
The carboxylic acid type flame retardant polyester of vinyl group;120 parts of deionized water emulsifications are added, 15~30min of high speed dispersion obtains UV-LED
Solidify end-vinyl waterborne flame retardant polyester.
Solidify the performance of end-vinyl waterborne flame retardant polyester: solid content for UV-LED, 45%;Viscosity, 3200cP;Lotion
Partial size, 175nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 11:
Table 11:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 12:
Table 12:
Embodiment 5:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 13 (toluene is as water entrainer):
Table 13:
Preparation process: in terms of mass fraction, by 50.9 parts of phthalic acids, 5 parts of YHKR-1210,25 parts of trihydroxy methyls third
Alkane, 10 parts of propylene glycol and 5 parts of castor oil are added in reaction kettle, and toluene is added as water entrainer, under nitrogen protection, is warming up to
190 DEG C, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, 2 parts of maleics two are added
Acid anhydrides reacts 3~5h;Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol, reaction 3 is added
~5h obtains the addition product containing hydrophilic radical and vinyl group;40~60 DEG C of cooling is added 0.8 part of triethylamine and neutralizes, obtains
Carboxylic acid type polyester containing vinyl group;150 parts of deionized water emulsifications are added, 15~30min of high speed dispersion obtains UV-LED
Solidify the modified end-vinyl waterborne polyester of aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 40%;Viscosity,
2600cP;Emulsion particle diameter, 155nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 14:
Table 14:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 15:
Table 15:
Embodiment 6:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 4 (dimethylbenzene is as water entrainer):
Table 16:
Preparation process: in terms of mass fraction, by 47.9 parts of phthalic acids, 35 parts of trimethylolpropanes, 2 parts of castor oil, 3
The more double bond hydroxylated tung oils of part and 8 parts of YHKR-1218 are added in reaction kettle, and dimethylbenzene is added as water entrainer, protects in nitrogen
Under shield, 190 DEG C are warming up to, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, is added 2
Part maleic anhydride, reacts 3~5h;Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part is added to methoxyl group
Phenol reacts 3~5h, obtains the addition product containing hydrophilic radical and vinyl group;0.8 part of three second is added in 40~60 DEG C of cooling
Amine neutralizes, and obtains the carboxylic acid type polyester containing vinyl group;150 parts of deionized waters are added to emulsify, high speed dispersion 15~
30min obtains the modified end-vinyl waterborne polyester of UV-LED solidification aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 40%;Viscosity,
27000cP;Emulsion particle diameter, 175nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 17:
Table 17:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 18:
Table 18:
Embodiment 7:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 19 (dimethylbenzene is as water entrainer):
Table 19:
Preparation process: in terms of mass fraction, by 25.9 parts of phthalic acids, 20 parts of terephthalic acid (TPA)s, 35 parts of trihydroxy methyls
Propane, 10 parts of KR-120W and 5 part of castor oil are added in reaction kettle, and addition dimethylbenzene is as water entrainer, under nitrogen protection,
190 DEG C are warming up to, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, 2 parts of addition is suitable
Anhydride maleique reacts 3~5h;Maintenance system is temperature-resistant, and 2 parts of hydroxy-ethyl acrylates and 0.1 part of p methoxy phenol are added,
3~5h is reacted, the addition product containing hydrophilic radical and vinyl group is obtained;40~60 DEG C of cooling, is added in 0.8 part of triethylamine
With obtain the carboxylic acid type polyester containing vinyl group;150 parts of deionized water emulsifications are added, 15~30min of high speed dispersion is obtained
To the modified end-vinyl waterborne polyester of UV-LED solidification aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 40%;Viscosity,
3250cP;Emulsion particle diameter, 185nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 20:
Table 20:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 21:
Table 21:
Embodiment 8:
A kind of synthesis solidifying the modified end-vinyl waterborne polyester of aldehyde resin for UV-LED, the type of feed of each component
And dosage such as table 4 (dimethylbenzene is as water entrainer):
Table 22:
Preparation process: in terms of mass fraction, by 47.9 parts of phthalic acids, 35 parts of trimethylolpropanes, 5 parts of castor oil, 4
UK-200 and 4 part of YHKR-1218 of part is added in reaction kettle, and dimethylbenzene is added as water entrainer, under nitrogen protection, is warming up to
190 DEG C, back flow reaction to acid value is lower than 10mgKOH/g, decompression extraction dimethylbenzene;130 DEG C are cooled to, 2 parts of maleics two are added
Acid anhydrides reacts 3~5h;Maintenance system is temperature-resistant, and 1 part of hydroxy-ethyl acrylate, 1 part of hydroxyethyl methacrylate and 0.1 is added
Part p methoxy phenol, reacts 3~5h, obtains the addition product containing hydrophilic radical and vinyl group;40~60 DEG C of cooling is added
0.8 part of triethylamine neutralizes, and obtains the carboxylic acid type polyester containing vinyl group;150 parts of deionized water emulsifications, high speed dispersion is added
15~30min obtains the modified end-vinyl waterborne polyester of UV-LED solidification aldehyde resin.
Solidify the performance of the modified end-vinyl waterborne polyester of aldehyde resin: solid content for UV-LED, 50%;Viscosity,
4200cP;Emulsion particle diameter, 195nm.
In terms of mass fraction, solidify the preparation composition of the modified end-vinyl waterborne polyester coating of aldehyde resin for UV-LED
Situation such as table 23:
Table 23:
Preparation process: in terms of mass fraction, mixing according to above-mentioned formula, and high speed dispersion is uniform, under being irradiated through UV-LED, Gu
It is melted into film.
Film performance is measured, such as table 24:
Table 24:
Embodiment of the present invention are not limited by the above embodiments, other it is any away from Spirit Essence of the invention with
Modification made by principle changes, substitution, combines and simplify, and should be equivalent substitute mode, should all be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. the synthetic method that a kind of UV-LED solidifies the modified end-vinyl waterborne polyester of aldehyde resin, which is characterized in that including such as
Lower step:
1) polyalcohol, polyacid, aldehyde resin and functional more double bond hydroxylating plants the synthesis of aldehyde resin modified poly ester: are taken
Oil and water entrainer, are added in the reaction kettle with reflux unit, under nitrogen protection, are to slowly warm up to 110 ~ 140oC, to
Raw material is completely dissolved, and is warming up to 180 ~ 210oC, back flow reaction to acid value are lower than 10 mgKOH/g, are then cooled to 120 ~ 150oC, under the conditions of vacuum degree is 0.04 ~ 0.1 Mpa, decompression extraction water entrainer synthesizes more plant oil modified polyester of double bond hydroxyl;
2) synthesis of the modified end-vinyl polyester of aldehyde resin: the more plant oil modified polyester of double bond hydroxyl prepared in step 1)
Maleic anhydride is added, reacts 3 ~ 5 h, then the vinyl function monomer and polymerization inhibitor of addition hydroxyl structure, 120 ~ 150oUnder C, the reaction was continued 3 ~ 5 h obtain aldehyde resin modified vinyl polyester;
3) synthesis of aldehyde resin modified water-soluble end-vinyl polyester: in the aldehyde resin modified vinyl polyester of step 2 preparation
Middle addition neutralizer neutralizes, and stirs 15 ~ 30 min, product is transferred in dispersion bucket, after deionized water is added, 600 ~ 1500
Under r/min revolving speed, 15 ~ 30 min obtain aldehyde resin modified water-soluble end-vinyl polyester.
2. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, according to the mass fraction, the mass fraction of the raw material is polyalcohol 20-40 parts, 35-55 parts of polyacid, polyacetals tree
5-10 parts of rouge, 10-30 parts of water entrainer, 2-6 parts of maleic anhydride, contains hydroxyl at functional more 5-10 parts of double bond hydroxylated vegetable oils
100-200 parts of 0.5 ~ 3 part of 0.1 ~ 0.4 part of 2-6 parts of vinyl function monomer, polymerization inhibitor, the neutralizer of based structures, deionized water.
3. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, polyacid as described in step (1) is adipic acid, terephthalic acid (TPA), M-phthalic acid, phthalic acid or tetrahydro
One of phthalic acid is a variety of.
4. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
Be characterized in that, polyalcohol as described in step (1) be propylene glycol, butanediol, neopentyl glycol, hexylene glycol, trimethylolpropane or
One of pentaerythrite is a variety of.
5. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, aldehyde resin as described in step (1) is urea formaldehyde A81, aldehyde ketone resin KR-80F, aldehyde ketone resin KR-120, aldehyde
Ketone resin KR120B, aldehyde ketone resin KR-120W, aldehyde ketone resin UK-100, aldehyde ketone resin UK-300, aldehyde ketone resin UK-500, aldehyde
One of ketone resin YHKR-1210, aldehyde ketone resin YHKR-1218 or a variety of.
6. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, the more double bond hydroxylated vegetable oils of functionality as described in step (1) are more double bond hydroxyl tung oil, more double bond hydroxyls Asia
One of sesame oil, castor oil are a variety of.
7. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, water entrainer as described in step (1) is toluene and/or dimethylbenzene.
8. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, the vinyl function monomer of hydroxyl structure described in step (2) is hydroxy-ethyl acrylate, acrylic acid hydroxypropyl
One of ester, hydroxyethyl methacrylate or hydroxy propyl methacrylate are a variety of.
9. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, polymerization inhibitor described in step (2) is p methoxy phenol, 2- tert-butyl hydroquinone, one in methylnaphthohydroquinone
Kind is a variety of.
10. UV-LED according to claim 1 solidifies the synthetic method of the modified end-vinyl waterborne polyester of aldehyde resin,
It is characterized in that, neutralizer described in step (3) is ammonium hydroxide, triethylamine, N, one of N- dimethylethanolamine or a variety of.
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