CN106750154B - A kind of mercaptan modified polyurethane photocuring prepolymer and preparation method and photocuring elastic coating prepared therefrom - Google Patents
A kind of mercaptan modified polyurethane photocuring prepolymer and preparation method and photocuring elastic coating prepared therefrom Download PDFInfo
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- CN106750154B CN106750154B CN201611145105.1A CN201611145105A CN106750154B CN 106750154 B CN106750154 B CN 106750154B CN 201611145105 A CN201611145105 A CN 201611145105A CN 106750154 B CN106750154 B CN 106750154B
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- mercaptan
- modified polyurethane
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000004814 polyurethane Substances 0.000 title claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 55
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011248 coating agent Substances 0.000 title claims abstract description 9
- 238000000576 coating method Methods 0.000 title claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 23
- -1 hydroxy acryl Chemical group 0.000 claims abstract description 16
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 229920005862 polyol Polymers 0.000 claims description 30
- 150000003077 polyols Chemical class 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000000498 cooling water Substances 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000012974 tin catalyst Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 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 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-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
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- LTOVZUHVYHATET-UHFFFAOYSA-N 1,2-diisocyanatoethylcyclohexane Chemical compound O=C=NCC(N=C=O)C1CCCCC1 LTOVZUHVYHATET-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- IMQFZQVZKBIPCQ-UHFFFAOYSA-N 2,2-bis(3-sulfanylpropanoyloxymethyl)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(CC)(COC(=O)CCS)COC(=O)CCS IMQFZQVZKBIPCQ-UHFFFAOYSA-N 0.000 claims description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 2
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-M 3-mercaptopropionate Chemical compound [O-]C(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-M 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- LCQXCCZEHCSQSA-UHFFFAOYSA-N SCCC(=O)O.SCCC(=O)O.SCCC(=O)O.C(C)OC(C(CO)(CO)CO)C Chemical compound SCCC(=O)O.SCCC(=O)O.SCCC(=O)O.C(C)OC(C(CO)(CO)CO)C LCQXCCZEHCSQSA-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- RUDUCNPHDIMQCY-UHFFFAOYSA-N [3-(2-sulfanylacetyl)oxy-2,2-bis[(2-sulfanylacetyl)oxymethyl]propyl] 2-sulfanylacetate Chemical compound SCC(=O)OCC(COC(=O)CS)(COC(=O)CS)COC(=O)CS RUDUCNPHDIMQCY-UHFFFAOYSA-N 0.000 claims description 2
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 11
- 150000002148 esters Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 abstract description 3
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical group F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- DBTDEFJAFBUGPP-UHFFFAOYSA-N Methanethial Chemical compound S=C DBTDEFJAFBUGPP-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 6
- 150000003573 thiols Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 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 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- GEXVUFWVPUWPJB-UHFFFAOYSA-N ClC1=CC=2SC3=CC=CC=C3S(C2C=C1)=O Chemical compound ClC1=CC=2SC3=CC=CC=C3S(C2C=C1)=O GEXVUFWVPUWPJB-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000003848 UV Light-Curing Methods 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
- 238000005299 abrasion Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KDONFNVMZBKJTJ-UHFFFAOYSA-N diethoxyphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CCOP(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C KDONFNVMZBKJTJ-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 1
- 238000004383 yellowing Methods 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
- C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
- C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of mercaptan modified polyurethane photocuring prepolymers and preparation method and photocuring elastic coating prepared therefrom, have the following structure formula:Wherein: R1Are as follows: ；R2, R3, R5It is identical or different, it is independent of each other to be expressed as H or CH3；R4Are as follows:n1=1-3；n2, n3=1-4；m=1-6.The present invention is modified urethane acrylate by mercaptan, and obtaining mercaptan modified polyurethane acrylate prepolymer has many advantages, such as that high laser curing velocity, elasticity is good, wear-resisting property is good, good weatherability；Present invention process is first reacted with hydroxy acryl acid ester with the mercaptan of various degrees of functionality, eliminates sulfydryl, then is reacted with isocyanates and then blocked with hydroxy acryl acid ester, simple process, is remained in finished product without sulfydryl, finished product is not easy gel.
Description
Technical Field
The invention belongs to the technical field of photocuring materials, and particularly relates to a mercaptan modified polyurethane photocuring prepolymer, a preparation method thereof and a photocuring elastic coating prepared from the same.
Background
One of the most important components of the UV curing system is a light curing prepolymer, and the existing light curing prepolymer generally comprises polyurethane acrylate, polyester acrylate, epoxy acrylate and the like. Because the polyurethane acrylate prepolymer has large adjustable range of composition, structure and performance, and the cured product has excellent performance, and is a main class of photocuring prepolymers, but the faster the curing speed, the harder the curing speed and the crisper the curing speed, the application of the polyurethane acrylate prepolymer in elastic hand-feeling paint can be realized by adding a plurality of elastic powder and other fillers, and the prepolymer is softer. The addition of excessive elastic powder and other fillers can result in slower curing speed, lower crosslinking density, poorer surface dryness and poorer scratch resistance, and the coating is easy to be back-adhered with the increase of time and the surface becomes sticky and can not be used.
The mercaptan is directly added into the light-cured coating formula to improve the curing speed, the elasticity, the crosslinking density and the like. However, the exposed thiol group in thiol is very easy to generate Michael addition reaction with double bond, which causes the viscosity of the finished product to be increased, gel, scrap and the like in the process of maintaining the finished product. Particularly, in the transportation process, the temperature of the container compartment can reach 80 ℃ in summer, and the UV finished product containing mercaptan is easy to gel.
Disclosure of Invention
In order to solve the defects of the prior art, the invention mainly aims to provide the thiol-modified polyurethane photocuring prepolymer with high photocuring speed, elasticity, wear resistance and good weather resistance.
The invention also aims to provide a preparation method of the mercaptan modified polyurethane photocuring prepolymer, which has the advantages of simple process and no residual mercapto.
The invention is realized by the following technical scheme:
a thiol-modified polyurethane photocuring prepolymer has the following structural formula:
wherein: r1Comprises the following steps:
；
R2，R3 ，R5identical or different, independently of one another, are represented by H or CH3；
R4Comprises the following steps:
；
n1=1-3；
n2，n3=1-4；
m=1-6。
the preparation method of the thiol-modified polyurethane photocuring prepolymer can adopt any one of the following two methods:
the method comprises the following steps: the method comprises the following steps:
(1) preparation of thiol-modified polyol: adding 16-35 parts by weight of mercaptan, 0.1-0.5 part by weight of polymerization inhibitor and 0.1-0.5 part by weight of catalyst 1 into a reaction container, heating to 30-120 ℃, dropwise adding 15-30 parts by weight of hydroxyl-containing acrylate, introducing cooling water, controlling the reaction temperature at 30-120 ℃, keeping the temperature at 30-120 ℃ for 1 hour after dropwise adding is finished, keeping the whole reaction time for 3-8 hours, and discharging to obtain mercaptan modified polyol; the reaction formula is as follows:
wherein,represents a thiol; r2 ，R3Is H or CH3(ii) a m is 1 to 6; n is1Is 1 to 3; n is2From 1 to 4.
(2) Preparing mercaptan modified polyurethane acrylate: adding 25-45 parts by weight of isocyanate, 0.1-0.5 part by weight of catalyst 2 and 0.1-0.5 part by weight of polymerization inhibitor into a reaction container, heating to 30-100 ℃, dropwise adding 10-30 parts by weight of hydroxyl-containing acrylate, introducing cooling water, controlling the reaction temperature to 30-100 ℃, keeping the temperature of 30-100 ℃ for 1 hour after dropwise adding, adding 25-60 parts by weight of mercaptan modified polyol prepared in the step (1) in batches, controlling the temperature to 50-100 ℃, reacting for 3-8 hours, detecting the% NCO to be less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate. The reaction formula is as follows:
wherein R is4Comprises the following steps:
；
R5is H orCH3；n3=1-4。
The second method comprises the following steps: the method comprises the following steps:
(1) preparation of thiol-modified polyol: according to the weight portion, 15 to 30 portions of hydroxyl-containing acrylate and 0.1 to 0.5 portion
Adding a polymerization inhibitor and 0.1-0.5 part of catalyst 1 into a reaction container, heating to 30-120 ℃, dropwise adding 16-35 parts of mercaptan, introducing cooling water, controlling the reaction temperature to 30-120 ℃, keeping the temperature of 30-120 ℃ for 1 hour after dropwise adding is finished, keeping the whole reaction time for 3-8 hours, and discharging to obtain mercaptan modified polyol; the reaction formula is as follows:
wherein,represents a thiol; r2 ，R3Is H or CH3(ii) a m is 1 to 6; n is1Is 1 to 3; n is2From 1 to 4.
(2) Preparing mercaptan modified polyurethane acrylate: adding 25-45 parts by weight of isocyanate, 0.1-0.5 part by weight of catalyst 2 and 0.1-0.5 part by weight of polymerization inhibitor into a reaction container, heating to 30-100 ℃, dropwise adding 25-60 parts by weight of mercaptan modified polyol prepared in the step (1), introducing cooling water, controlling the reaction temperature to be 30-100 ℃, keeping the temperature of 30-100 ℃ for 1 hour after dropwise adding, adding 10-30 parts by weight of hydroxyl-containing acrylate in batches, controlling the temperature to be 50-100 ℃, controlling the reaction time to be 3-8 hours, detecting that the% NCO is less than 0.1%, and discharging to obtain mercaptan modified polyurethane acrylate, wherein the reaction formula is as follows:
R4comprises the following steps:
；
R5is H or CH3；n3=1-4。
The mercaptan is pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), ethoxytrimethylolpropane tris (3-mercaptopropionate), 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, tris (3-mercaptoacetate) ethyl isocyanurate, dipentaerythritol (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptobutyrate) or a combination of several thereof.
The hydroxyl-containing acrylate is one or a combination of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate.
The isocyanate is one or a mixture of more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or cyclohexyl dimethylene diisocyanate.
The catalyst 1 is one or a combination of more of triethylamine, triethanolamine, N-dipropyl-1-propylamine or N, N-dimethylaniline; the catalyst 2 is one or a combination of several of organic tin catalysts or organic bismuth catalysts.
The polymerization inhibitor is one or a combination of more of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
The reaction principle of the invention is as follows: the mercaptan with various degrees of functionality reacts with the acrylate containing hydroxyl to eliminate the mercapto group, then reacts with the isocyanate, and is terminated by the acrylate containing hydroxyl, so that the mercaptan modified polyurethane acrylate prepolymer has the advantages of high photocuring speed, good elasticity, good wear resistance, good weather resistance and the like, no mercapto group residue exists in a finished product, and the finished product is not easy to gel. Taking pentaerythritol tetrakis (3-mercaptopropionate) as an example, the synthesis reaction formula is as follows:
the invention also provides a photocuring elastic coating which is prepared by taking the mercaptan modified polyurethane photocuring prepolymer as a main body and adding a photoinitiator, an active diluent, a conventional auxiliary agent and the like through a common production method known in the field.
The photoinitiator may be one or more of 1-hydroxycyclohexyl phenyl ketone 184, 2-hydroxy-2-methyl-1-phenyl-1-propanone 1173, α dimethoxy- α -phenyl acetophenone, α -diethoxy acetophenone, isopropylphenyl-2-hydroxy-2-methyl acetone, 2-methyl-1- (4-methylmercapto phenyl) -2-morpholine-1-propanone, 2-phenyl-2, 2-dimethylamino-1- (4-morpholine phenyl) -1-butanone, diethyl 2,4, 6-trimethylbenzoylphosphonate, 2,4, 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) - (4 ', 4 ' -dimethyloctyl-2) phosphine oxide, benzophenone, tetramethylmichler's ketone, 2-chlorothianthrone, isopropylthioxanthone and 2, 4-diethylthioxanthone.
The reactive diluent can be one or a mixture of isobornyl acrylate, morpholine acrylate, hydroxybutyl acrylate or hydroxypropyl methacrylate.
The conventional auxiliary agents can be antioxidants 1010, 168, 1076 and 1035; defoaming agents, silicone oils, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention modifies urethane acrylate by mercaptan to obtain the prepolymer of mercaptan modified urethane acrylate
The product has the advantages of high photocuring speed, good elasticity, good wear resistance, good weather resistance and the like;
(2) the process of the present invention is to react thiol with hydroxyl-containing acrylate to eliminate mercapto group and then react thiol with isocyano
The acid ester reaction is terminated by acrylate containing hydroxyl, the process is simple, no sulfhydryl residue is left in the finished product, and the finished product is not easy to gel.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the embodiments of the present invention, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions and alterations are intended to be included in the scope of the present invention.
Example 1: synthesis of tetra (3-mercaptopropionic acid) pentaerythritol ester modified polyurethane acrylate
(1) Preparation of thiol-modified polyol: adding 30 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), 0.3 part by weight of p-hydroxyanisole and 0.3 part by weight of triethylamine into a reaction container, heating to 80 ℃, dropwise adding 28.5 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 80 ℃, keeping the temperature at 80 ℃ for 1 hour after dropwise adding, and discharging to obtain thiol modified polyol A, wherein the whole reaction time is 5 hours; the yield is 98.5%;1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）;4.22 CH2（CH2-OCO）;2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 3.94 CH2{C-(CH2)4}。
the reaction formula is as follows:
(2) preparing mercaptan modified polyurethane acrylate: adding 30 parts by weight of isophorone diisocyanate (IPDI), 0.3 part by weight of organic tin catalyst and 0.3 part by weight of p-hydroxyanisole into a reaction vessel, heating to 80 ℃, dropwise adding 15.7 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 80 ℃, keeping the temperature at 80 ℃ for 1 hour after dropwise adding, adding 39 parts by weight of mercaptan modified polyol A prepared in the step (1) in batches, controlling the temperature at 60 ℃, controlling the reaction time at 5 hours, detecting that the% NCO is less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate with the yield of 99.6%.1HNMR(CDCl3,PPM)：δ4.31 CH2（CH2-OCO）;2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 3.94 CH2{C-(CH2)4}; 7.67 NH; 3.54H (N-CH), 1.08, 1.33, 1.42, 1.67 CH2 (on the alicyclic ring); 0.87, 0.93 CH3(on the fat ring); 2.69, 2.94 CH2（N- CH2）;6.76 NH; 4.31 CH2（CH2-OCO）;5.85、6.12、6.41 H(CH=CH2);4.38CH2（CH2-OCO- CH=CH2）。
The reaction formula is as follows:
。
example 2: synthesis of trimethylolpropane tri (3-mercaptopropionic acid) ester modified polyurethane acrylate
(1) Preparation of thiol-modified polyol: 25 parts by weight of trimethylolpropane tris (A), (B) and (C)3-mercaptopropionic acid) ester, 0.2 part of p-hydroxyanisole and 0.2 part of triethylamine are added into a reaction vessel, the reaction vessel is heated to 70 ℃, 24.5 parts of hydroxyethyl methacrylate is added dropwise, cooling water is introduced, the reaction temperature is controlled to 70 ℃, the dropwise addition is finished, the temperature of 70 ℃ is kept for 1 hour, the whole reaction time is 6 hours, and mercaptan modified polyol B is obtained after discharging, wherein the yield is 98.8%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）; 4.36 CH2（CH2-OCO）;2.70 CH（CHCO）; 2.65、2.90 CH2（CH2S）; 1.17 CH3（CH3-CH）;2.83 CH2（CH2S）; 2.58 CH2（CH2-CO）； 3.94 CH2（C-CH2-OCO）;1.69 CH2（C-CH2）;0.83CH3（CH3-CH2-C）；
The reaction formula is as follows:
(2) preparing mercaptan modified polyurethane acrylate: adding 25 parts by weight of isophorone diisocyanate (IPDI), 0.3 part by weight of organic tin catalyst and 0.3 part by weight of p-hydroxyanisole into a reaction container, heating to 30-100 ℃, dropwise adding 13 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 70 ℃, keeping the temperature at 70 ℃ for 1 hour after the dropwise adding is finished, adding 29.6 parts by weight of mercaptan modified polyol B prepared in the step (1) in batches, controlling the temperature at 50 ℃, controlling the reaction time at 8 hours, detecting the% NCO to be less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate. The yield thereof was found to be 99.2%.1HNMR(CDCl3,PPM)：δ4.36 CH2（CH2-OCO）;2.70 CH（CHCO）; 2.65、2.90 CH2（CH2S）; 1.17 CH3（CH3-CH）;2.83 CH2（CH2S）; 2.58 CH2（CH2-CO）； 3.94 CH2（C-CH2-OCO）;1.69 CH2（C-CH2）;0.83 CH3（CH3-CH2-C）; 7.67 NH；3.54 H (N-CH);1.08、1.33、1.42、1、67 CH2(on the fat ring); 0.87, 0.94CH3(on the fat ring); 2.69, 2.94 CH2（N- CH2）; 6.76 NH; 4.31 CH2（CH2-OCO）; 5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）。
The reaction formula is as follows:
example 3: synthesis of bis (3-mercaptopropionic acid) ethylene glycol ester modified polyurethane acrylate
(1) Preparation of thiol-modified polyol: according to the weight portion, 20 portions of ethylene glycol bis (3-mercaptopropionate), 0.2 portion of p-hydroxyanisole and 0.2 portion of triethylamine are added into a reaction container, the mixture is heated to 70 ℃, 19.5 portions of hydroxyethyl acrylate are added dropwise, cooling water is introduced, the reaction temperature is controlled at 70 ℃, the dropwise addition is finished, the temperature is kept at 70 ℃ for 1 hour, the whole reaction time is 6 hours, and mercaptan modified polyol C is obtained after discharging, and the yield is 99.3%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）;4.22 CH2（CH2-OCO）;2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 4.31 CH2（CH2-OCO）；
The reaction formula is as follows:
(2) preparing mercaptan modified polyurethane acrylate: based on the weight portion, the weight portion of the material,adding 25 parts of isophorone diisocyanate (IPDI), 0.3 part of organic tin catalyst and 0.3 part of p-hydroxyanisole into a reaction container, heating to 30-100 ℃, dropwise adding 13 parts of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 70 ℃, keeping the temperature at 70 ℃ for 1 hour after dropwise adding, adding 26.5 parts of the mercaptan modified polyol C prepared in the step (1) in batches, controlling the temperature at 50 ℃, controlling the reaction time at 8 hours, detecting the% NCO to be less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate. The yield thereof was found to be 99.1%.1HNMR(CDCl3,PPM)：δ 5.85、6.12、6.41 H(CH=CH2); 4.38 CH2（CH2-OCO- CH=CH2）; 4.31 CH2（CH2-OCO）;6.76 NH; 2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3(on the fat ring) 1.08, 1.33, 1.42, 1, 67CH2(on the fat ring); 3.54H (N-CH), 7.67 NH, 4.31 CH2（CH2-OCO）；2.83 CH2（CH2S）;2.58 CH2（CH2CO）。
The reaction formula is as follows:
example 4: synthesis of ethoxy trimethylolpropane tri (3-mercaptopropionic acid) ester modified polyurethane acrylate
(1) Preparation of thiol-modified polyol: according to parts by weight, 25 parts of ethoxy trimethylolpropane tris (3-mercaptopropionic acid) ester, 0.2 part of p-hydroxyanisole and 0.2 part of triethylamine are added into a reaction vessel, the reaction vessel is heated to 70 ℃, 16.4 parts of hydroxyethyl acrylate is added dropwise, cooling water is introduced, the reaction temperature is controlled at 70 ℃, the dropwise addition is finished, the temperature is kept at 70 ℃ for 1 hour, the whole reaction time is 6 hours, and mercaptan modified polyol D is obtained after discharging, wherein the yield is 99.2%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54CH2（CH2-OH）; 4.22 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 4.2 CH2（CH2-OCO）; 3.63 CH2（CH2-O）; 3.79 CH2（C-CH2）; 1.69 CH2（C-CH2）; 0.83 CH3（CH3-CH2-C）。
The reaction formula is as follows:
(2) preparing mercaptan modified polyurethane acrylate: adding 25 parts by weight of isophorone diisocyanate (IPDI), 0.3 part by weight of organic tin catalyst and 0.3 part by weight of p-hydroxyanisole into a reaction vessel, heating to 70 ℃, dropwise adding 13 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 70 ℃, finishing dropwise adding, keeping the temperature at 70 ℃ for 1 hour, adding 33 parts by weight of the mercaptan modified polyol D prepared in the step (1) in batches, controlling the temperature at 50 ℃, controlling the reaction time at 8 hours, detecting the% NCO to be less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate. The yield thereof was found to be 99%.1HNMR(CDCl3,PPM)：δ5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）；4.31 CH2（CH2-OCO）; 6.76 NH;2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3(on the fat ring) 1.08, 1.33, 1.42, 1, 67CH2(on the fat ring); 3.54H (N-CH), 7.67 NH; 4.31 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）;4.2 CH2（CH2-OCO）; 3.63 CH2（CH2-O）; 3.79 CH2（C-CH2）; 1.69 CH2（C-CH2）; 0.83 CH3（CH3-CH2-C）。
The reaction formula is as follows:
example 5: synthesis of tri (3-mercaptoacetic acid) ethyl isocyanurate modified polyurethane acrylate
(1) Preparation of thiol-modified polyol: adding 25 parts by weight of tris (3-mercaptoacetic acid) ethyl isocyanurate, 0.2 part by weight of p-hydroxyanisole and 0.2 part by weight of triethylamine into a reaction vessel, heating to 70 ℃, dropwise adding 16.6 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 70 ℃, keeping the temperature at 70 ℃ for 1 hour after dropwise adding, discharging to obtain mercaptan modified polyol E, wherein the yield is 98.9%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）; 4.22 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 4.51CH2（CH2-OCO）; 3.46CH2（CH2-N）。
The reaction formula is as follows:
(2) preparing mercaptan modified polyurethane acrylate: adding 25 parts by weight of isophorone diisocyanate (IPDI), 0.3 part by weight of organic tin catalyst and 0.3 part by weight of p-hydroxyanisole into a reaction vessel, heating to 70 ℃, dropwise adding 13 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 70 ℃, finishing dropwise adding, keeping the temperature at 70 ℃ for 1 hour, adding 33 parts by weight of mercaptan modified polyol E prepared in the step (1) in batches, controlling the temperature at 50 ℃, controlling the reaction time at 8 hours, detecting the% NCO to be less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate. The yield thereof was found to be 98.9%.1HNMR(CDCl3,PPM)：δ5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）；4.31 CH2（CH2-OCO）; 6.76 NH;2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3(on the fat ring) 1.08, 1.33, 1.42, 1, 67CH2(on the fat ring); 3.54H (N-CH), 7.67 NH; 4.31 CH2（CH2-OCO）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）;4.51CH2（CH2-OCO）; 3.46 CH2（CH2-N）。
The reaction formula is as follows:
example 6: synthesis of dipentaerythritol (3-mercaptopropionic acid) ester modified polyurethane acrylate
(1) Preparation of thiol-modified polyol: adding 25 parts by weight of dipentaerythritol (3-mercaptopropionic acid) ester, 0.2 part by weight of p-hydroxyanisole and 0.2 part by weight of triethylamine into a reaction vessel, heating to 70 ℃, dropwise adding 22.3 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 70 ℃, finishing dropwise adding, keeping the temperature at 70 ℃ for 1 hour, keeping the whole reaction time for 6 hours, discharging to obtain mercaptan modified polyol F, wherein the yield is 99.3%.1HNMR(CDCl3,PPM)：δ4.89 OH; 3.54 CH2（CH2-OH）;4.22 CH2（CH2-OC）; 2.58 CH2（CH2CO）; 2.83 CH2（CH2S）; 3.94 CH2（CH2-C）。
The reaction formula is as follows:
(2) preparing mercaptan modified polyurethane acrylate: adding 30 parts by weight of isophorone diisocyanate (IPDI), 0.3 part by weight of organic tin catalyst and 0.3 part by weight of p-hydroxyanisole into a reaction vessel, heating to 80 ℃, dropwise adding 15.7 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 80 ℃, keeping the temperature at 80 ℃ for 1 hour after dropwise adding, adding 33.3 parts by weight of mercaptan modified polyol A prepared in the step (1) in batches, controlling the temperature at 60 ℃, controlling the reaction time at 5 hours, detecting that the% NCO is less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate with the yield of 99%.1HNMR(CDCl3,PPM)：δ 5.85、6.12、6.41 H(CH=CH2);4.38 CH2（CH2-OCO- CH=CH2）；4.31 CH2（CH2-OCO）;6.76 NH; 2.69、2.94 CH2（N- CH2）; 0.87、0.94 CH3(on the fat ring) 1.08, 1.33, 1.42, 1, 67CH2(on the fat ring); 3.54H (N-CH), 7.67 NH; 4.31 CH2（CH2-OCO）; 2.58 CH2（CH2CO）; 2.83CH2（CH2S）; 3.94 CH2（CH2-C）。
The reaction formula is as follows:
comparative example 1: adding 30 parts by weight of isophorone diisocyanate (IPDI), 0.3 part by weight of triethylamine and 0.3 part by weight of p-hydroxyanisole into a reaction vessel, heating to 30 ℃, dropwise adding 16.5 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate), keeping the temperature at 70 ℃ for 1 hour, adding 15.7 parts by weight of hydroxyethyl acrylate, introducing cooling water, controlling the reaction temperature at 100 ℃, controlling the reaction time to be 10 hours, detecting that the% NCO is less than 0.1%, discharging to obtain the pentaerythritol tetrakis (3-mercaptopropionate) modified polyurethane acrylate, wherein the yield is 99.4%.
95 percent of thiol-modified polyurethane photocuring prepolymer prepared in examples 1-6 and comparative example 1 and 5 percent of photoinitiator are uniformly dissolved by heating, and the performance of the thiol-modified polyurethane photocuring prepolymer is tested after curing with 300mj of energy, and the results are shown in Table 1:
table 1: performance test results of thiol-modified polyurethane photocuring prepolymer
Examples 7 to 12
According to the parts by weight, 65 parts of the thiol-modified polyurethane photocuring prepolymer prepared in examples 1-6 and comparative example 1, 5 parts of photoinitiator 1-hydroxycyclohexyl phenyl ketone, and 15 parts of reactive diluents isobornyl acrylate and hydroxypropyl methacrylate are respectively mixed and stirred uniformly to obtain the photocuring elastic coating, and the performance test results are shown in table 2.
Table 2: performance test results of photo-curable elastic coating
As can be seen from the performance test results of the embodiment, the thiol-modified urethane acrylate prepolymer obtained by the invention has the advantages of high photocuring speed, good elasticity, good wear resistance, good weather resistance and the like. As can be seen from the comparison between example 1 and comparative example 1, in comparative example 1, the mercapto group in the mercaptan directly reacts with the isocyanate and then is blocked with the hydroxyl-containing acrylate, the mercapto group reacts with the isocyanate with an amine catalyst, and the mercapto group is easily remained, so that the finished product is easy to gel and has poorer weather resistance than example 1.
Each performance test method or standard:
yellowing resistance: ASTM G-151;
elongation at break: GB 3880-1997;
TAB abrasion resistance: ASTM-D1044.
Curing energy: and (5) putting an energy meter while curing, and measuring the energy when the surface of the material is not sticky.
Claims (9)
1. A thiol-modified polyurethane photocuring prepolymer has the following structural formula:
wherein: r1Comprises the following steps:
；
R2，R3 ，R5identical or different, independently of one another, are represented by H or CH3；
R4Comprises the following steps:
；
n1=1-3；
n2，n3=1-4；
m=1-6。
2. the method for preparing the thiol-modified polyurethane photocurable prepolymer as claimed in claim 1, which comprises
The method comprises the following steps:
(1) preparation of thiol-modified polyol: adding 16-35 parts by weight of mercaptan, 0.1-0.5 part by weight of polymerization inhibitor and 0.1-0.5 part by weight of catalyst 1 into a reaction container, heating to 30-120 ℃, dropwise adding 15-30 parts by weight of hydroxyl-containing acrylate, introducing cooling water, controlling the reaction temperature at 30-120 ℃, keeping the temperature at 30-120 ℃ for 1 hour after dropwise adding is finished, keeping the whole reaction time for 3-8 hours, and discharging to obtain mercaptan modified polyol;
(2) preparing mercaptan modified polyurethane acrylate: adding 25-45 parts by weight of isocyanate, 0.1-0.5 part by weight of catalyst 2 and 0.1-0.5 part by weight of polymerization inhibitor into a reaction container, heating to 30-100 ℃, dropwise adding 10-30 parts by weight of hydroxyl-containing acrylate, introducing cooling water, controlling the reaction temperature to 30-100 ℃, keeping the temperature of 30-100 ℃ for 1 hour after dropwise adding, adding 25-60 parts by weight of mercaptan modified polyol prepared in the step (1) in batches, controlling the temperature to 50-100 ℃, reacting for 3-8 hours, detecting the% NCO to be less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate.
3. The method for preparing the thiol-modified polyurethane photocurable prepolymer as claimed in claim 1, which comprises
The method comprises the following steps:
(1) preparation of thiol-modified polyol: adding 15-30 parts by weight of hydroxyl-containing acrylate, 0.1-0.5 part by weight of polymerization inhibitor and 0.1-0.5 part by weight of catalyst 1 into a reaction container, heating to 30-120 ℃, dropwise adding 16-35 parts by weight of mercaptan, introducing cooling water, controlling the reaction temperature at 30-120 ℃, keeping the temperature at 30-120 ℃ for 1 hour after dropwise adding is finished, keeping the whole reaction time for 3-8 hours, and discharging to obtain mercaptan modified polyol;
(2) preparing mercaptan modified polyurethane acrylate: adding 25-45 parts by weight of isocyanate, 0.1-0.5 part by weight of catalyst 2 and 0.1-0.5 part by weight of polymerization inhibitor into a reaction container, heating to 30-100 ℃, dropwise adding 25-60 parts by weight of mercaptan modified polyol prepared in the step (1), introducing cooling water, controlling the reaction temperature to be 30-100 ℃, keeping the temperature at 30-100 ℃ for 1 hour after dropwise adding, adding 10-30 parts by weight of hydroxyl-containing acrylate in batches, controlling the temperature to be 50-100 ℃, controlling the reaction time to be 3-8 hours, detecting that the% NCO is less than 0.1%, and discharging to obtain the mercaptan modified polyurethane acrylate.
4. The method for preparing the thiol-modified polyurethane photocurable prepolymer according to claim 2 or 3, the method is characterized in that the mercaptan is pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), ethoxytrimethylolpropane tris (3-mercaptopropionate), 2, 3-bis (thio (2-mercaptoethyl)) -1-n-propanethiol, tris (3-mercaptoacetate) ethyl isocyanurate, dipentaerythritol (3-mercaptopropionate) or pentaerythritol tetrakis (3-mercaptobutyrate) or a combination of a plurality of the components.
5. The method for preparing the thiol-modified polyurethane photocuring prepolymer as claimed in claim 2 or 3, wherein the hydroxyl-containing acrylate is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
6. The method for preparing the thiol-modified polyurethane photocuring prepolymer as claimed in claim 2 or 3, wherein the isocyanate is one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and cyclohexyldimethylene diisocyanate.
7. The method for preparing the thiol-modified polyurethane photocuring prepolymer as claimed in claim 2 or 3, wherein the catalyst 1 is one or more of triethylamine, triethanolamine, N-dipropyl-1-propylamine or N, N-dimethylaniline; the catalyst 2 is one or a combination of several of organic tin catalysts or organic bismuth catalysts.
8. The method for preparing the thiol-modified polyurethane photocuring prepolymer as claimed in claim 2 or 3, wherein the polymerization inhibitor is one or a combination of p-hydroxyanisole, hydroquinone, 2-tert-butylhydroquinone or 2, 5-di-tert-butylhydroquinone.
9. A photocurable elastomeric coating comprising the thiol-modified polyurethane photocurable prepolymer of claim 1.
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| CN108329749B (en) * | 2018-03-21 | 2021-03-19 | 湖北中烟工业有限责任公司 | UV offset printing sun-proof ink |
| CN108611042A (en) * | 2018-03-22 | 2018-10-02 | 深圳市姿彩科技有限公司 | LED solidification drop glue |
| CN108503792A (en) * | 2018-03-22 | 2018-09-07 | 深圳市姿彩科技有限公司 | Aqueous polyurethane acrylate resin and preparation method |
| CN108586755A (en) * | 2018-04-12 | 2018-09-28 | 中科广化（重庆）新材料研究院有限公司 | A kind of Photocurable Silicone Material and its preparation method and application |
| CN108503794A (en) * | 2018-04-14 | 2018-09-07 | 上海伟星光学有限公司 | One kind having diffusing reflection high transmittance polyurethane film and preparation method thereof |
| CN108892763B (en) * | 2018-05-28 | 2019-08-30 | 岭南师范学院 | A kind of polyurethane binary mercaptan prepolymer, photosensitive resin composition and its preparation method and application |
| CN109880347A (en) * | 2019-03-07 | 2019-06-14 | 禾聚实业有限公司 | Polyurethane materials |
| CN112142944B (en) * | 2020-10-12 | 2022-01-28 | 河源然生新材料有限公司 | Low-energy UV-curable polyurethane acrylate prepolymer, preparation method thereof and UV-curable coating |
| CN114874694B (en) * | 2022-05-17 | 2023-05-16 | 广东希贵光固化材料有限公司 | Anti-oxidation polymerization-inhibition UVLED paint |
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