CN113980234A - Polyurethane acrylate with good pigment wetting performance and preparation method thereof - Google Patents
Polyurethane acrylate with good pigment wetting performance and preparation method thereof Download PDFInfo
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- CN113980234A CN113980234A CN202111444373.4A CN202111444373A CN113980234A CN 113980234 A CN113980234 A CN 113980234A CN 202111444373 A CN202111444373 A CN 202111444373A CN 113980234 A CN113980234 A CN 113980234A
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- caprolactone
- pigment
- diisocyanate
- wetted
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 21
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- 239000000049 pigment Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000009736 wetting Methods 0.000 title claims abstract description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 4
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 17
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 8
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 8
- -1 caprolactone modified hydroxy acrylate Chemical class 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 22
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000013638 trimer Substances 0.000 claims description 8
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 4
- 235000021342 arachidonic acid Nutrition 0.000 claims description 4
- 229940114079 arachidonic acid Drugs 0.000 claims description 4
- 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 4
- 238000000034 method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical class OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 claims description 3
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims description 3
- 229940090949 docosahexaenoic acid Drugs 0.000 claims description 3
- 235000020673 eicosapentaenoic acid Nutrition 0.000 claims description 3
- 229960005135 eicosapentaenoic acid Drugs 0.000 claims description 3
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 claims description 3
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 3
- YUFFSWGQGVEMMI-JLNKQSITSA-N (7Z,10Z,13Z,16Z,19Z)-docosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCCCC(O)=O YUFFSWGQGVEMMI-JLNKQSITSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 241000526900 Camellia oleifera Species 0.000 claims description 2
- 235000021294 Docosapentaenoic acid Nutrition 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- JTDWCIXOEPQECG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC(C)(C)C Chemical compound N=C=O.N=C=O.CCCCCC(C)(C)C JTDWCIXOEPQECG-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 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
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- 229960002969 oleic acid Drugs 0.000 claims description 2
- 230000036632 reaction speed Effects 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 238000001723 curing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000012360 testing method 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
- C08G18/28—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
- 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
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
-
- 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
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)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses polyurethane acrylate with good pigment wetting performance and a preparation method thereof. According to the invention, through a large number of experimental screens, the unsaturated long-chain structure of unsaturated fatty acid and the saturated long-chain structure of long-chain caprolactone modified hydroxy acrylate are combined, and the advantages of the two aspects are integrated, so that the photosensitive polyurethane acrylate resin with excellent reaction speed and pigment wettability is obtained.
Description
Technical Field
The invention relates to an oligomer for a photocureable coating, in particular to polyurethane acrylate with good pigment wetting property and a preparation method thereof, belonging to the technical field of high polymer materials.
Background
Ultraviolet (UV) curing technology is a new coating technology starting at the end of the last 60 s of the century. The technology is mainly characterized in that oligomers (light-cured resin and light-cured monomer) and a photoinitiator are subjected to light cross-linking reaction under the irradiation of ultraviolet light to be cured into a target product. The UV curing technology is gradually a mainstream curing technology under the development trend of higher and higher environmental protection requirements in recent years due to the outstanding advantages of fast curing, low energy consumption, low pollution, excellent performance and the like. In recent years, the application field of the photo-curing system has been gradually developed to the field of the color ink which is difficult to solve before and the like due to the wider application of the photo-curing system, but the wettability of the pigment is always a problem which is difficult to solve due to the shrinkage problem of the photo-curing system.
Disclosure of Invention
Aiming at the defects of the prior art, the invention innovatively prepares a polyurethane acrylate resin with excellent reaction activity and pigment wettability by combining common unsaturated fatty acid and caprolactone modified hydroxyl acrylate through a large number of experimental screens and introducing the unsaturated fatty acid and the caprolactone modified hydroxyl acrylate into a polyurethane structure by utilizing the characteristics of long chain and light-curable double bond.
Another object of the present invention is to provide a process for preparing the pigment-wetted urethane acrylate resin.
Technical solution to achieve the above object, the present invention adopts the following technical solutions:
a preparation method of a polyurethane acrylate resin with a well-wetted pigment comprises the following steps:
(1) firstly, carrying out ring-opening condensation on a certain mass part of unsaturated fatty acid and a certain mass part of glycidyl methacrylate under certain reaction conditions to obtain an intermediate with hydroxyl;
(2) and (2) uniformly mixing the intermediate obtained in the step (1) with a certain mass part of caprolactone modified hydroxy acrylate, and then reacting with a certain mass part of different polyisocyanates under a certain reaction condition to obtain the photosensitive polyurethane acrylate resin with a good pigment wetting property.
Preferably, the unsaturated fatty acid is one or any combination of camellia oleifera oleic acid, arachidonic acid, alpha-linolenic acid, eicosapentaenoic acid, docosapentaenoic acid and docosahexaenoic acid, preferably arachidonic acid, and the amount is 15-40 parts by mass.
Preferably, the glycidyl methacrylate is used in an amount of 5 to 20 parts by mass.
Preferably, the reaction conditions in the step (1) are 0-1 part by mass of benzyltriethylammonium chloride as a catalyst and 0-1 part by mass of p-hydroxyanisole as a polymerization inhibitor, the reaction temperature is 80-150 ℃, and the reaction time is 1-5 hours.
Preferably, the caprolactone-modified hydroxy acrylate is one or any combination of caprolactone-modified hydroxyethyl acrylate, caprolactone-modified hydroxypropyl acrylate, caprolactone-modified hydroxyethyl methacrylate and caprolactone-modified hydroxypropyl methacrylate, and the amount of the caprolactone-modified hydroxy acrylate is 15 to 45 parts by mass. Caprolactone-modified hydroxypropyl acrylate is preferred.
Preferably, the polyisocyanate is one or any combination of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, trimethylhexane diisocyanate, tetramethylxylylene diisocyanate, polyphenylmethane polyisocyanate, toluene diisocyanate trimer, isophorone diisocyanate trimer, and hexamethylene diisocyanate trimer, and the amount of the polyisocyanate is 10 to 40 parts by mass. Hexamethylene diisocyanate trimer is preferred.
Preferably, the reaction conditions in the step (2) are 0-1 part by mass of dibutyltin dilaurate serving as a catalyst and 0-1 part by mass of p-hydroxyanisole serving as a polymerization inhibitor, the reaction temperature is 40-100 ℃, and the reaction time is 1-5 hours.
Has the advantages that:
according to the invention, through a large number of experimental screens, unsaturated fatty acid and caprolactone modified hydroxy acrylate are combined and then introduced into a polyurethane structure, and a polyurethane acrylate resin with excellent reaction activity and pigment wettability is innovatively prepared by utilizing the characteristics of long chain and light-curable double bond. The polyurethane acrylate resin prepared by the invention has the advantages that a paint film obtained after UV curing has excellent pigment wettability, surface hardness, better flexibility and excellent storage stability.
Detailed Description
Example 1
A preparation method of a polyurethane acrylate resin with a well-wetted pigment comprises the following steps:
(1) firstly, performing ring-opening condensation reaction on 29.1 parts by mass of arachidonic acid and 13.6 parts by mass of glycidyl methacrylate at the reaction temperature of 110 ℃ for 2 hours in the presence of 0.5 part by mass of benzyltriethylammonium chloride serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor to obtain an intermediate with hydroxyl;
(2) and (2) uniformly mixing the intermediate with hydroxyl in the step (1) and 23.7 parts by mass of caprolactone modified hydroxyethyl acrylate, and then reacting with 32 parts by mass of hexamethylene diisocyanate trimer, 0.1 part by mass of dibutyltin dilaurate serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor at the reaction temperature of 85 ℃ for 4 hours to obtain the final photosensitive polyurethane acrylate resin.
Example 2
A preparation method of a polyurethane acrylate resin with a well-wetted pigment comprises the following steps:
(1) firstly, carrying out ring-opening condensation reaction on 32.2 parts by mass of docosahexaenoic acid and 13.9 parts by mass of glycidyl methacrylate at the reaction temperature of 110 ℃ for 2 hours under the conditions of 0.5 part by mass of benzyltriethylammonium chloride serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor to obtain an intermediate with hydroxyl;
(2) and (2) uniformly mixing the intermediate with hydroxyl in the step (1) and 35.3 parts by mass of caprolactone-modified hydroxypropyl methacrylate, and reacting with 17 parts by mass of toluene diisocyanate at the reaction temperature of 70 ℃ for 4 hours in the presence of 0.1 part by mass of dibutyltin dilaurate serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor to obtain the final photosensitive polyurethane acrylate resin.
Example 3
A preparation method of a polyurethane acrylate resin with a well-wetted pigment comprises the following steps:
(1) firstly, performing ring-opening condensation reaction on 29.6 parts by mass of eicosapentaenoic acid and 13.9 parts by mass of glycidyl methacrylate at the reaction temperature of 115 ℃ for 1.5 hours under the conditions of 0.5 part by mass of benzyltriethylammonium chloride serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor to obtain an intermediate with hydroxyl;
(2) and (2) uniformly mixing the intermediate with hydroxyl in the step (1) and 23.1 parts by mass of caprolactone-modified hydroxyethyl acrylate, and then reacting with 25.6 parts by mass of toluene diisocyanate, 0.1 part by mass of dibutyltin dilaurate serving as a catalyst and 0.5 part by mass of p-hydroxyanisole serving as a polymerization inhibitor at the reaction temperature of 90 ℃ for 3 hours to obtain the final photosensitive polyurethane acrylate resin.
Example 4 performance testing:
the resulting urethane acrylate resin prepared in examples 1, 2 and 3 and photoinitiator 1173 were thoroughly mixed in a ratio of 97:3 and mixed well at 80mW/cm2Is cured under the intensity of ultraviolet light (the curing speed is once expressed by 80 mW/cm)2The energy of (3) can be completely cured, and the times are times multiplied by 80mW/cm2The energy data obtained is the energy required for full cure), the results of the performance tests obtained are shown in table 1 below
TABLE 1 Performance test results
Note: the curing speed in the table is 80mW/cm directly on a UV curing machine2The light intensity of (2) was measured.
The hardness testing method adopts a pencil scratching method according to the standard GB/T6739-; the flexibility is measured by a paint film elasticity tester and is GB/T1731-79 according to the standard.
The experimental results show that compared with other examples, the medium polyurethane acrylate resin prepared in the embodiment 1 of the invention has better dryness, and a paint film obtained after UV curing has excellent pigment wettability, surface hardness, flexibility and storage stability, so that a good technical effect is achieved. The different raw material compositions have different reaction conditions, and the properties of the obtained resin have obvious differences.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of polyurethane acrylate resin with good pigment wetting performance is characterized by comprising the following steps:
(1) firstly, carrying out ring-opening condensation on a certain mass part of unsaturated fatty acid and a certain mass part of glycidyl methacrylate under certain reaction conditions to obtain an intermediate with hydroxyl;
(2) and (2) uniformly mixing the intermediate obtained in the step (1) with a certain mass part of caprolactone modified hydroxy acrylate, and then reacting with a certain mass part of different polyisocyanates under a certain reaction condition to obtain the photosensitive polyurethane acrylate resin with a good pigment wetting property.
2. The method for producing a pigment-wetted urethane acrylate according to claim 1, wherein the unsaturated fatty acid is one or any combination of camellia oleifera oil oleic acid, arachidonic acid, α -linolenic acid, eicosapentaenoic acid, docosapentaenoic acid, and docosahexaenoic acid, and is used in an amount of 15 to 40 parts by mass.
3. The method for producing a pigment-wetted urethane acrylate according to claim 1, wherein the glycidyl methacrylate is used in an amount of 5 to 20 parts by mass.
4. The method for preparing a pigment-wetted urethane acrylate according to claim 1, wherein the reaction conditions in the step (1) are as follows: 0-1 part of benzyltriethylammonium chloride serving as a catalyst, 0-1 part of p-hydroxyanisole serving as a polymerization inhibitor, 80-150 ℃ of reaction temperature and 1-5 hours of reaction time.
5. The method for producing a pigment-wetted urethane acrylate according to claim 1, wherein the caprolactone-modified hydroxy acrylate is one or any combination of caprolactone-modified hydroxyethyl acrylate, caprolactone-modified hydroxypropyl acrylate, caprolactone-modified hydroxyethyl methacrylate and caprolactone-modified hydroxypropyl methacrylate, and the amount of the caprolactone-modified hydroxypropyl methacrylate is 15 to 45 parts by mass.
6. The method for producing a pigment-wetted urethane acrylate according to claim 1, wherein the polyisocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, lysine diisocyanate, trimethylhexane diisocyanate, tetramethylxylylene diisocyanate, polyphenylmethane polyisocyanate, toluene diisocyanate trimer, isophorone diisocyanate trimer, hexamethylene diisocyanate trimer, or any combination thereof, and is used in an amount of 10 to 40 parts by mass.
7. The method for preparing a pigment-wetted urethane acrylate according to claim 1, wherein the reaction conditions in the step (2) are as follows: 0-1 part of dibutyltin dilaurate serving as a catalyst and 0-1 part of p-hydroxyanisole serving as a polymerization inhibitor, wherein the reaction temperature is 40-100 ℃, and the reaction time is 1-5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111444373.4A CN113980234A (en) | 2021-11-30 | 2021-11-30 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111444373.4A CN113980234A (en) | 2021-11-30 | 2021-11-30 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113980234A true CN113980234A (en) | 2022-01-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111444373.4A Pending CN113980234A (en) | 2021-11-30 | 2021-11-30 | Polyurethane acrylate with good pigment wetting performance and preparation method thereof |
Country Status (1)
| Country | Link |
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| CN (1) | CN113980234A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0048117A2 (en) * | 1980-09-17 | 1982-03-24 | Ici Americas Inc. | In-mold coating compositions containing a non-isocyanate-reactive unsaturated resin, a non-isocyanate-reactive monomer and a free isocyanate-containing compound |
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