CN116463049A - Photo-curing dual-curing coating - Google Patents
Photo-curing dual-curing coating Download PDFInfo
- Publication number
- CN116463049A CN116463049A CN202310319303.9A CN202310319303A CN116463049A CN 116463049 A CN116463049 A CN 116463049A CN 202310319303 A CN202310319303 A CN 202310319303A CN 116463049 A CN116463049 A CN 116463049A
- Authority
- CN
- China
- Prior art keywords
- caprolactone
- stirred
- hydroxyethyl acrylate
- curing
- heated
- 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
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 30
- 238000001723 curing Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 53
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000003999 initiator Substances 0.000 claims abstract description 29
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 57
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 33
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 32
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 26
- 229920005862 polyol Polymers 0.000 claims description 26
- 150000003077 polyols Chemical class 0.000 claims description 26
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 26
- 229920001610 polycaprolactone Polymers 0.000 claims description 24
- 239000004632 polycaprolactone Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 15
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 15
- -1 caprolactone modified hydroxyethyl acrylate Chemical class 0.000 claims description 15
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical group CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 13
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 13
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 13
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 8
- 238000012360 testing method Methods 0.000 description 48
- 239000000203 mixture Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 238000003848 UV Light-Curing Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- BLAKAEFIFWAFGH-UHFFFAOYSA-N acetyl acetate;pyridine Chemical compound C1=CC=NC=C1.CC(=O)OC(C)=O BLAKAEFIFWAFGH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a photo-curing dual-curing coating which comprises 12.84-27.08 parts by weight of 1, 6-hexanediol diacrylate, 14.8-28.2 parts by weight of caprolactone-modified hydroxyethyl acrylate monomer, 12-24 parts by weight of caprolactone-modified acrylic acid, 8.5-17 parts by weight of photo-curing resin, 1.8-3.6 parts by weight of initiator and 0.06-0.12 part by weight of catalyst I. The invention has the characteristics of high hardness and good low-temperature impact resistance.
Description
Technical Field
The invention belongs to the field of coatings, and particularly relates to a photo-curing dual-curing coating.
Background
The main components of the UV light-cured coating are UV resin (oligomer), active monomer, initiator, auxiliary agent, filler and solvent. The UV light curing coating has the advantages of high curing speed, high production efficiency, saving of semi-finished product stacking space and capability of preventing devices from being deformed due to heating. The UV light curing coating also has the advantages of little pollution and low cost. The UV coating has the characteristics of small molecular weight and high reaction speed, so that the structure of the UV coating determines that the UV coating has higher crosslinking density under higher hardness, and the formed paint film is brittle under the low-temperature condition. The coating with high crosslinking density, good flexibility, high low-temperature impact strength and high hardness in the UV industry cannot be achieved.
Disclosure of Invention
The invention aims to provide a photo-curing dual-curing coating.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a photo-curing dual-curing coating comprises 12.84-27.08 parts by weight of 1, 6-hexanediol diacrylate, 14.8-28.2 parts by weight of caprolactone-modified hydroxyethyl acrylate monomer, 12-24 parts by weight of caprolactone-modified acrylic acid, 8.5-17 parts by weight of photo-curing resin, 1.8-3.6 parts by weight of initiator and 0.06-0.12 part by weight of catalyst I.
Further improved, the initiator is Darocure1173.
Further improved, the catalyst I is tetrabutyl titanate.
Further improved, the photo-curing resin is 6-functionality resin synthesized by polycaprolactone polyol, and the chemical formula of the 6-functionality resin is as follows:
wherein n+m is more than or equal to 7 and less than or equal to 8.
Further improvement, the preparation method comprises the following steps:
s1, dehydrating polycaprolactone polyol, adding polyisocyanate, and heating to 60 ℃ for reacting for 4 hours to obtain a prepolymer with isocyanate at the tail end; the mass ratio of polycaprolactone polyol to polyisocyanate is 300-500:133.5-222.5;
s2: adding pentaerythritol triacrylate and a catalyst II into the prepolymer, heating to 88 ℃ for reaction for 8-8.5h, cooling and discharging to obtain 6-functionality resin synthesized by polycaprolactone polyol with NCO content less than 0.1%; wherein the mass ratio of polycaprolactone polyol to pentaerythritol triacrylate to catalyst II is 300-500:94-157:0.05-0.09; in the above raw materials, since only hydroxyl groups react with isocyanate groups, and the reactivity of two isocyanate groups of IPDI is greatly different, when one isocyanate group reacts, the activity of the other is very low, and the molar amount of IPDI is 2 times that of hydroxyl groups, so that the isocyanate groups with low reactivity are left, only a single hydroxyl group in S2 is blocked by isocyanate with low reactivity, and thus the formed structure is a single, i.e. 6-functional resin chemical structure.
Further, the polycaprolactone polyol is prepared by taking neopentyl glycol as an initiator, and the hydroxyl value of the polycaprolactone polyol is 112mgKOH/g.
Further improvements are made in that the polyisocyanate is isophorone diisocyanate.
Further improved, the catalyst II is tin tetrachloride.
Further improved, the structural formula of the caprolactone-modified hydroxyethyl acrylate monomer is as follows:
a＝2；
the caprolactone-modified hydroxyethyl acrylate monomer is prepared by the following steps:
a1: hydroxyethyl acrylate, caprolactone, hydroxyanisole and stannous octoate are mixed according to the mass ratio of 92.8-116:182.4-228:0.14-0.17:0.13-0.17 is stirred uniformly in a reaction bottle, and a pre-product is obtained after dehydration until the water content is below 200 ppm;
a2: heating the pre-product to 115-160 ℃ and reacting for 13-18 h, then vacuum devolatilizing at 100-115 ℃ for 2.5-3h, cooling and discharging to obtain caprolactone modified hydroxyethyl acrylate monomer, wherein in the reaction, caprolactone can undergo ring opening reaction with hydroxyl, the residual of caprolactone is little through gas phase detection, the residual of hydroxyethyl acrylate is obviously reduced, double bond performance is obviously reflected in the next step, and only the reaction of hydroxyl and caprolactone is possible, wherein a=2 is the average repeating unit number.
Further improved, the structural formula of the caprolactone-modified hydroxyethyl acrylate monomer is as follows:
b＝2；
b1: acrylic acid, caprolactone, tetramethyl piperidine nitroxide free radical phosphite triester, hydroquinone, stannic chloride and tetrapropyl titanate are mixed according to the mass ratio of 64.8-108:205.2-342:0.29-0.48:0.26-0.43:0.13-0.23:0.011-0.075, stirring in a reaction bottle, and dehydrating in vacuum until the water content reaches below 300ppm to obtain a pre-product;
b2: after the pre-product is stirred and heated to 160 ℃ for reaction for 17-18h, then the temperature is reduced to 100 ℃, vacuum devolatilization is carried out for 3h, caprolactone modified acrylic monomer is obtained after cooling and discharging, caprolactone can undergo ring opening reaction with carboxyl, after gas phase detection, caprolactone residue is little, acrylic acid residue is obviously reduced, double bond performance is obviously reflected in the next step, and only the reaction of carboxyl and caprolactone is possible, wherein b=2 is the average repeating unit number.
The beneficial effects of the invention are as follows:
1. the photo-curing resin provided by the invention has high crosslinking, and the prepared coating has good wear resistance, adhesive force and weather resistance, and the characteristics of low viscosity and good toughness are reflected due to the use of polycaprolactone polyol.
2. The two caprolactone-modified acrylic monomers provided by the invention have the characteristics of low viscosity, good compatibility and capability of performing secondary curing, and the two monomers can be matched for use to realize secondary curing which does not reach the performance after photocuring, so that the prepared coating is safe, environment-friendly and excellent in performance.
3. The photo-curing dual-curing coating provided by the invention has the characteristics of high hardness and good low-temperature impact resistance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments.
The testing method comprises the following steps:
the number average molecular weight Mn of the caprolactone-modified acrylic monomer and the caprolactone-modified hydroxyethyl acrylate monomer is determined by GPC, tetrahydrofuran is used as a mobile phase, and polystyrene is used as a standard reference.
The hydroxyl number was determined by the acetic anhydride-pyridine method using industry standard HG 2709-1995-T.
The UV resin viscosity was measured by a bohler cone plate rotor viscometer.
The viscosity of the coating was determined using GB/T1723-93.
The resin nco content was determined by toluene-di-n-butylamine titration using HGT 2409-1992.
Acid number was determined using HG/T2708-2012.
Example 1
500g of polycaprolactone polyol (hydroxyl value 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, added with 222.5g of isophorone diisocyanate, stirred and heated to 60 ℃ for reaction for 4h, added with 157g of pentaerythritol triacrylate and 0.09g of stannic chloride, stirred and heated to 88 ℃, reacted for 8h, cooled to 60 ℃ and discharged. The test viscosity was 28000mpa.s (25 ℃ C.) and NCO content was 0.08%, giving a 6-functionality UV-curable resin P1
116g of hydroxyethyl acrylate, 228g of caprolactone, 0.17g of hydroxyanisole and 0.17g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated in vacuum for 2 hours, stirred and heated to 115 ℃ for reaction for 12 hours after the water content reaches 200ppm, devolatilized in vacuum for 2.5 hours, cooled to 60 ℃ and discharged. The test viscosity is 90mpa.s (25 ℃), the hydroxyl value is 159.54mgKOH/g, and the caprolactone-modified hydroxyethyl acrylate monomer M1 is obtained
72g of acrylic acid, 228g of caprolactone, 0.3g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.3g of Hydroquinone (HQ), 0.15g of stannic chloride and 0.075g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 18 hours after the water content reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 145mpa.s (25 ℃ C.), and the acid value was 186.5mgKOH/g, giving caprolactone-modified acrylic monomer H1
In a dispersing kettle, 27.08g of 1, 6-hexanediol diacrylate, 28.2g of caprolactone-modified hydroxyethyl acrylate monomer (M1) and 24g (H1) of caprolactone-modified acrylic acid are uniformly stirred, 17g of photo-curing resin (P1) is added and uniformly stirred, 3.6g of initiator (Darocure 1173) and 0.12g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1H for filtering, and the mixture is coated with 3 cups of UV photo-curing paint F1 at a test viscosity (25 ℃) for 16 s.
Example 2
450g of polycaprolactone polyol (hydroxyl value 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, 200g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for 4h, 141g of pentaerythritol triacrylate and 0.08g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 8.5h, cooled to 60 ℃ and discharged. The test viscosity was 28200mpa.s (25 ℃ C.) and NCO content was 0.06% to give a 6-functionality UV light-curable resin P2
116g of hydroxyethyl acrylate, 228g of caprolactone, 0.17g of hydroxyanisole and 0.17g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated in vacuum for 2 hours, stirred and heated to 115 ℃ for 13 hours after the water content reaches 200ppm, devolatilized in vacuum for 2.5 hours, cooled to 60 ℃ and discharged. The test viscosity is 91mpa.s (25 ℃), the hydroxyl value is 159.22mgKOH/g, and the caprolactone-modified hydroxyethyl acrylate monomer M2 is obtained
108g of acrylic acid, 342g of caprolactone, 0.48g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.43g of Hydroquinone (HQ), 0.23g of stannic chloride and 0.011g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17 hours after the water content reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 142mpa.s (25 ℃ C.) and the acid value was 187.2mgKOH/g to give caprolactone-modified acrylic monomer H2
In a dispersing kettle, 12.84g of 1, 6-hexanediol diacrylate, 14.8g of caprolactone-modified hydroxyethyl acrylate monomer (M2), 12g of caprolactone-modified acrylic acid (H2) are uniformly stirred, 8.5g of photo-curing resin (P2) is added and uniformly stirred, 1.8g of initiator (Darocure 1173) and 0.06g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1H for filtering, and the mixture is coated with 3 cups of UV photo-curing paint F2 at a test viscosity (25 ℃) for 17 s.
Example 3
300g of polycaprolactone polyol (hydroxyl value 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, added with 133.5g of isophorone diisocyanate, stirred and heated to 60 ℃ for reaction for 4h, added with 94g of pentaerythritol triacrylate and 0.05g of stannic chloride, stirred and heated to 88 ℃, reacted for 8.5h, cooled to 60 ℃ for discharging. The test viscosity was 28400mpa.s (25 ℃ C.) and NCO content was 0.06% to give a 6-functionality UV light-curable resin P3
Adding 92.8g of hydroxyethyl acrylate, 182.4g of caprolactone, 0.14g of hydroxyanisole and 0.13g of stannous octoate into a reaction kettle, stirring and heating to 45 ℃, vacuum dehydrating for 2 hours, stirring and heating to 115 ℃ after the water content reaches 200ppm for reacting for 13 hours, vacuum devolatilizing for 2.5 hours, and cooling to 60 ℃ for discharging. The test viscosity is 91mpa.s (25 ℃), the hydroxyl value is 159.73mgKOH/g, and the caprolactone-modified hydroxyethyl acrylate monomer M3 is obtained
Adding 64.8g of acrylic acid, 205.2g of caprolactone, 0.29g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.26g of Hydroquinone (HQ), 0.13g of stannic chloride and 0.067g of tetrapropyl titanate into a reaction kettle, stirring and heating to 40 ℃, carrying out vacuum dehydration for 2 hours, after the water content reaches below 300ppm, stirring and heating to 160 ℃ for reacting for 17.5 hours, cooling to 100 ℃, carrying out vacuum devolatilization for 3 hours, and cooling to 60 ℃ for discharging. The test viscosity was 148mpa.s (25 ℃ C.) and the acid value was 187.1mgKOH/g to give caprolactone-modified acrylic monomer H3
23.2g of 1, 6-hexanediol diacrylate, 26.55g of caprolactone-modified hydroxyethyl acrylate monomer (M3), 21.6g of caprolactone-modified acrylic acid (H3) are uniformly stirred in a dispersing kettle, 15.3g of photo-curing resin (P3) is added and uniformly stirred, 3.24g of initiator (Darocure 1173) and 0.11g of tetrabutyl titanate are added and uniformly stirred, the mixture is kept stand for 1H for filtering, and 3 cups of UV photo-curing paint F3 is coated for 15s at a test viscosity (25 ℃).
Comparative example 1
500g of adipic acid type polyester polyol (hydroxyl value 112 mgKOH/g) is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2 hours, cooled to 50 ℃, 222.1g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for reaction for 4 hours, 157.1g of pentaerythritol triacrylate and 0.09g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 7 hours, cooled to 60 ℃ for discharging. The test viscosity was 38100mpa.s (25 ℃ C.) and NCO content was 0.07% to give a 6-functionality UV-curable resin K1
116g of hydroxyethyl acrylate, 228g of caprolactone, 0.17g of hydroxyanisole and 0.17g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated in vacuum for 2 hours, stirred and heated to 115 ℃ for 13 hours after the water content reaches 200ppm, devolatilized in vacuum for 2.5 hours, cooled to 60 ℃ and discharged. The test viscosity was 92mpa.s (25 ℃ C.) and the hydroxyl value was 159.43mgKOH/g to obtain caprolactone-modified hydroxyethyl acrylate monomer L1
72g of acrylic acid, 228g of caprolactone, 0.32g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.29g of Hydroquinone (HQ), 0.15g of stannic chloride and 0.075g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 18 hours after the water content reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 141mpa.s (25 ℃ C.) and the acid value was 187.4mgKOH/g to give caprolactone-modified acrylic monomer T1
In a dispersing kettle, 27.08g of 1, 6-hexanediol diacrylate, 28.2g of caprolactone-modified hydroxyethyl acrylate monomer (L1), 24g of caprolactone-modified acrylic acid (T1) are uniformly stirred, 17g of photo-curing resin (K1) is added and uniformly stirred, 3.6g of initiator (Darocure 1173) and 0.12g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1h for filtering, and the mixture is coated with 3 cups of UV photo-curing paint F4 at a test viscosity (25 ℃) for 21 s.
Comparative example 2
Polycaprolactone polyol (hydroxyl value 112 mgKOH/g) with 1.4 butanediol as an initiator is added into a reaction kettle
400g, stirring and heating to 120 ℃, vacuum dehydrating for 2h, cooling to 50 ℃, adding 177.8g of isophorone diisocyanate, stirring and heating to 60 ℃ for reacting for 4h, adding 125.2g of pentaerythritol triacrylate and 0.07g of stannic chloride, stirring and heating to 88 ℃, reacting for 7h, cooling to 60 ℃ and discharging. The test viscosity was 28150mpa.s (25 ℃ C.) and NCO content was 0.04% to give a 6-functionality UV light-curable resin K2.
116g of hydroxyethyl acrylate, 228g of caprolactone, 0.17g of hydroxyanisole and 0.17g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated in vacuum for 2 hours, stirred and heated to 115 ℃ for 16 hours after the water content reaches 200ppm, devolatilized in vacuum for 2.5 hours, cooled to 60 ℃ and discharged. The test viscosity was 95mpa.s (25 ℃ C.) and the hydroxyl value was 159.31mgKOH/g to give caprolactone-modified hydroxyethyl acrylate monomer L2
72g of acrylic acid, 228g of caprolactone, 0.32g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.29g of Hydroquinone (HQ), 0.15g of stannic chloride and 0.075g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for 17.5 hours after the moisture reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 146mpa.s (25 ℃ C.) and the acid value was 187.8mgKOH/g to give caprolactone-modified acrylic monomer T2
26.99g of 1, 6-hexanediol diacrylate, 28.29g of caprolactone-modified hydroxyethyl acrylate monomer (L2) and 24g (T2) of caprolactone-modified acrylic acid are uniformly stirred in a dispersing kettle, 17g of photo-curing resin (K2) is added and uniformly stirred, 3.6g of initiator (Darocure 1173) and 0.12g of tetrabutyl titanate are added and uniformly stirred, the mixture is kept stand for 1h for filtering, and the mixture is coated for 3 cups of 17s at a test viscosity (25 ℃) to obtain the UV photo-curing coating F5.
Comparative example 3
450g of polycaprolactone polyol (hydroxyl value 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, 200g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for 4h, 140.8g of pentaerythritol triacrylate and 0.08g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 7h, cooled to 60 ℃ and discharged. The test viscosity was 28300mpa.s (25 ℃ C.) and the NCO content was 0.07% to give a 6-functionality UV-curable resin K3
Adding 100g of hydroxyethyl acrylate, 196.5g of caprolactone, 0.15g of hydroxyanisole and 0.15g of stannous octoate into a reaction kettle, stirring and heating to 45 ℃, vacuum dehydrating for 2 hours, stirring and heating to 115 ℃ for reacting for 15 hours after the water content reaches 200ppm, vacuum devolatilizing for 2.5 hours, and cooling to 60 ℃ for discharging. The test viscosity is 91mpa.s (25 ℃), the hydroxyl value is 159.69mgKOH/g, and the caprolactone-modified hydroxyethyl acrylate monomer L3 is obtained
61.2g of acrylic acid, 193.8g of caprolactone, 0.27g of tetramethyl piperidine nitroxide phosphate triester (705), 0.25g of Hydroquinone (HQ), 0.13g of stannic chloride and 0.064g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17.5 hours after the moisture reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 141mpa.s (25 ℃ C.) and the acid value was 187.2mgKOH/g to give caprolactone-modified acrylic monomer T3
24.68g of 1, 6-hexanediol diacrylate, 25.06g of caprolactone-modified hydroxyethyl acrylate monomer (L3) and 21.6g (T3) of caprolactone-modified acrylic acid are uniformly stirred in a dispersing kettle, 15.3g of light-cured resin (K3) is added and uniformly stirred, 3.24g of initiator (Darocure 1173) and 0.11g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1h for filtering, and then 3 cups of UV light-cured coating F6 are coated for 18s at a test viscosity (25 ℃).
Comparative example 4
480g of polycaprolactone polyol (hydroxyl value of 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, 213.5g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for 4h, 150.4g of pentaerythritol triacrylate and 0.08g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 7h, cooled to 60 ℃ and discharged. The test viscosity was 28100mpa.s (25 ℃ C.) and NCO content was 0.07% to give a 6-functionality UV-curable resin K4
81.2g of hydroxyethyl acrylate, 159.6g of caprolactone, 0.12g of hydroxyanisole and 0.12g of stannous octoate are added into a reaction kettle, the mixture is stirred and heated to 45 ℃, the mixture is dehydrated for 2 hours under vacuum, after the water content reaches 200ppm, the mixture is stirred and heated to 115 ℃ for 15 hours, the mixture is subjected to vacuum devolatilization for 2.5 hours, and the mixture is cooled to 60 ℃ for discharging. The test viscosity was 94mpa.s (25 ℃ C.) and the hydroxyl value was 159.61mgKOH/g to give caprolactone-modified hydroxyethyl acrylate monomer L4
50.4g of acrylic acid, 159.6g of caprolactone, 0.224g of tetramethyl piperidine nitroxide phosphate triester (705), 0.2g of Hydroquinone (HQ), 0.1g of stannic chloride and 0.05g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17.5 hours after the moisture reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 146mpa.s (25 ℃ C.) and the acid value was 187.5mgKOH/g to give caprolactone-modified acrylic monomer T4
In a dispersing kettle, 25.4g of 1, 6-hexanediol diacrylate, 29.88g of caprolactone-modified hydroxyethyl acrylate monomer (L4), 24g of caprolactone-modified acrylic acid (T4) are uniformly stirred, 17g of photo-curing resin (K4) is added and uniformly stirred, 3.6g of initiator (Darocure 1173) and 0.12g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1h for filtering, and the mixture is coated with 3 cups of UV photo-curing paint F7 at a test viscosity (25 ℃) for 17 s.
Comparative example 5
500g of polycaprolactone polyol (hydroxyl value 102 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, 201.8g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for 4h, 142.4g of pentaerythritol triacrylate and 0.08g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 7h, cooled to 60 ℃ and discharged. The test viscosity was 27800mpa.s (25 ℃ C.) and NCO content was 0.03% to give a 6-functionality UV-curable resin K5
121.8g of hydroxyethyl acrylate, 239.4g of caprolactone, 0.18g of hydroxyanisole and 0.18g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 115 ℃ for 15 hours after the water content reaches 200ppm, devolatilized for 2.5 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 92mpa.s (25 ℃ C.) and the hydroxyl value was 159.3mgKOH/g to obtain caprolactone-modified hydroxyethyl acrylate monomer L5
75.6g of acrylic acid, 239.4g of caprolactone, 0.336g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.3g of Hydroquinone (HQ), 0.15g of stannic chloride and 0.07g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17.5 hours after the moisture reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 143mpa.s (25 ℃ C.) and the acid value was 187.2mgKOH/g to give caprolactone-modified acrylic monomer T5
23.08g of 1, 6-hexanediol diacrylate, 23.97g of caprolactone-modified hydroxyethyl acrylate monomer (L5), 20.4g (T5) of caprolactone-modified acrylic acid are uniformly stirred in a dispersing kettle, 14.55g of light-cured resin (K5) is added and uniformly stirred, 3.06g of initiator (Darocure 1173) and 0.1g of tetrabutyl titanate are added and uniformly stirred, the mixture is kept stand for 1h for filtering, and 3 cups of UV light-cured coating F8 are coated for 17s at the test viscosity (25 ℃).
Comparative example 6
500g of polycaprolactone polyol (hydroxyl value of 125 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, added with 247.5g of isophorone diisocyanate, stirred and heated to 60 ℃ for 4h, added with 174.5g of pentaerythritol triacrylate and 0.10g of stannic chloride, stirred and heated to 88 ℃, reacted for 7h, cooled to 60 ℃ and discharged. The test viscosity was 27800mpa.s (25 ℃ C.) and NCO content was 0.03% to give a 6-functional UV light-curable resin K6
121.8g of hydroxyethyl acrylate, 239.4g of caprolactone, 0.18g of hydroxyanisole and 0.18g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 115 ℃ for 15 hours after the water content reaches 200ppm, devolatilized for 2.5 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 92mpa.s (25 ℃ C.) and the hydroxyl value was 159.3mgKOH/g to obtain caprolactone-modified hydroxyethyl acrylate monomer L6
75.6g of acrylic acid, 239.4g of caprolactone, 0.336g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.3g of Hydroquinone (HQ), 0.15g of stannic chloride and 0.07g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17.5 hours after the moisture reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 143mpa.s (25 ℃ C.) and the acid value was 187.2mgKOH/g to give caprolactone-modified acrylic monomer T6
29.08g of 1, 6-hexanediol diacrylate, 27.54g of caprolactone-modified hydroxyethyl acrylate monomer (L6), 23.4g of caprolactone-modified acrylic acid (T6) are uniformly stirred in a dispersing kettle, 16.55g of light-cured resin (K6) is added and uniformly stirred, 3.06g of initiator (Darocure 1173) and 0.1g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1h for filtering, and then 3 cups of UV light-cured coating F9 are coated for 17s at a test viscosity (25 ℃).
Comparative example 7
600g of polycaprolactone polyol (hydroxyl value 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, 266.6g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for 4h, 187.5g of pentaerythritol triacrylate and 0.11g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 8.5h, cooled to 60 ℃ and discharged. The test viscosity was 28500mpa.s (25 ℃ C.) and NCO content was 0.05% to give a 6-functionality UV-curable resin K7
116g of hydroxyethyl acrylate, 228g of caprolactone, 0.17g of hydroxyanisole and 0.17g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated in vacuum for 2 hours, stirred and heated to 115 ℃ for 13 hours after the water content reaches 200ppm, devolatilized in vacuum for 2.5 hours, cooled to 60 ℃ and discharged. The test viscosity is 91mpa.s (25 ℃), the hydroxyl value is 159.22mgKOH/g, and the caprolactone-modified hydroxyethyl acrylate monomer L7 is obtained
72g of acrylic acid, 342g of caprolactone, 0.41g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.41g of Hydroquinone (HQ), 0.2g of stannic chloride and 0.03g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17 hours after the water content reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 143mpa.s (25 ℃ C.) and the acid value was 135.5mgKOH/g, giving caprolactone-modified acrylic monomer T7
In a dispersing kettle, 27.08g of 1, 6-hexanediol diacrylate, 28.2g of caprolactone-modified hydroxyethyl acrylate monomer (L7), 24g of caprolactone-modified acrylic acid (T7) are uniformly stirred, 17g of photo-curing resin (K7) is added and uniformly stirred, 3.6g of initiator (Darocure 1173) and 0.12g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1h for filtering, and the mixture is coated with 3 cups of UV photo-curing paint F10 at a test viscosity (25 ℃) for 15 s.
Comparative example 8
600g of polycaprolactone polyol (hydroxyl value 112 mgKOH/g) taking neopentyl glycol as an initiator is added into a reaction kettle, stirred and heated to 120 ℃, dehydrated in vacuum for 2h, cooled to 50 ℃, 266.6g of isophorone diisocyanate is added, stirred and heated to 60 ℃ for 4h, 187.5g of pentaerythritol triacrylate and 0.11g of stannic chloride are added, stirred and heated to 88 ℃, reacted for 8.5h, cooled to 60 ℃ and discharged. The test viscosity was 28500mpa.s (25 ℃ C.) and NCO content was 0.05% to give a 6-functionality UV-curable resin K8
116g of hydroxyethyl acrylate, 342g of caprolactone, 0.23g of hydroxyanisole and 0.23g of stannous octoate are added into a reaction kettle, stirred and heated to 45 ℃, dehydrated in vacuum for 2 hours, stirred and heated to 115 ℃ for 13 hours after the water content reaches 200ppm, devolatilized in vacuum for 2.5 hours, cooled to 60 ℃ and discharged. The test viscosity was 130mpa.s (25 ℃ C.) and the hydroxyl value was 118.6mgKOH/g to give caprolactone-modified hydroxyethyl acrylate monomer L8
72g of acrylic acid, 228g of caprolactone, 0.41g of tetramethyl piperidine nitroxide free radical phosphite triester (705), 0.41g of Hydroquinone (HQ), 0.2g of stannic chloride and 0.03g of tetrapropyl titanate are added into a reaction kettle, stirred and heated to 40 ℃, dehydrated for 2 hours under vacuum, stirred and heated to 160 ℃ for reaction for 17 hours after the water content reaches below 300ppm, cooled to 100 ℃, devolatilized for 3 hours under vacuum, cooled to 60 ℃ and discharged. The test viscosity was 143mpa.s (25 ℃ C.) and the acid value was 186.5mgKOH/g, giving caprolactone-modified acrylic monomer T8
In a dispersing kettle, 27.08g of 1, 6-hexanediol diacrylate, 37.74g of caprolactone-modified hydroxyethyl acrylate monomer (L8) and 24g (T8) of caprolactone-modified acrylic acid are uniformly stirred, 17g of photo-curing resin (K8) is added and uniformly stirred, 3.8g of initiator (Darocure 1173) and 0.14g of tetrabutyl titanate are added and uniformly stirred, and the mixture is kept stand for 1h for filtering, and the mixture is coated with 3 cups of UV photo-curing paint F11 at a test viscosity (25 ℃) for 15 s.
The dual-curing UV coatings F1-11 prepared in examples 1-3 and comparative examples 1-8 were tested separately, and the substrates and methods were tested as follows, with the test results shown in Table 1 below.
The paint testing method comprises the following steps: the coating F1-11 was sprayed on the surface of the substrate by means of a spray gun (type W-71 in the field) and leveled for 10 seconds, and then was put into a UV light curing machine (energy of mercury lamp: 300J, speed: 5 m/min, time: 20 seconds), cooled for 5 minutes after UV curing, put into an oven, and cured for 3 hours at 140 ℃.
The test substrates were: tin plate; specification of: 70mm wide, 130mm long and 0.3mm thick
Paint film thickness: 35-40 micrometers
Adhesion force: cross-hatch method GB/T1720
Impact-resistant: GB/T1732-2020
Table 1 properties of the two-component UV-curable coating prepared in examples and comparative examples
As can be seen from the above table, examples 1 to 4 were not affected in adhesion and impact resistance at normal temperature and low temperature, whereas comparative examples 1 to 7 were not greatly changed in adhesion at normal temperature, but were poor in impact resistance at low temperature.
The polyols used in comparative examples 1-2, although identical to those used in examples 1-3 in the production process and coating formulation, were not based on the use of a polycaprolactone-type polyol initiated with neopentyl glycol, and the resulting coating products were poor in low temperature impact resistance, and the raw materials and processes provided in comparative examples 3-4 were identical to those used in examples 1-4, but the two monomers were used in different proportions, exceeding the range of carboxyl: hydroxyl=1:1 to 1.05, and the resulting coating products were extremely poor in low temperature impact resistance. The polycaprolactone polyols provided in comparative examples 5-6 have different hydroxyl numbers and different proportions of the coating formulation, and the resulting coating products have very poor low temperature impact resistance. The two caprolactone-modified monomers provided in comparative examples 7-8 were identical in raw materials, but different in synthesized hydroxyl value, and different in coating formulation ratio, and the resulting coating product was extremely poor in low-temperature impact resistance. The invention can be used as automobile baking paint coating and the like.
Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. A photo-curing dual-curing coating is characterized in that: comprises 12.84 to 27.08 weight parts of 1, 6-hexanediol diacrylate, 14.8 to 28.2 weight parts of caprolactone-modified hydroxyethyl acrylate monomer, 12 to 24 weight parts of caprolactone-modified acrylic acid, 8.5 to 17 weight parts of photo-curing resin, 1.8 to 3.6 weight parts of initiator and 0.06 to 0.12 weight part of catalyst I.
2. The photo-curable dual cure coating of claim 1 wherein the initiator is Darocure1173.
3. The light-curable dual-cure coating of claim 1, wherein the catalyst one is tetrabutyl titanate.
4. The photocurable dual cure coating of claim 1 wherein the photocurable resin is a 6-functional resin synthesized from polycaprolactone polyol, the 6-functional resin having the formula:
wherein n+m is more than or equal to 7 and less than or equal to 8.
5. The photocurable dual cure coating of claim 4 wherein said 6-functional resin is prepared by a process comprising the steps of:
s1, dehydrating polycaprolactone polyol, adding polyisocyanate, and heating to 60 ℃ for reacting for 4 hours to obtain a prepolymer with isocyanate at the tail end; the mass ratio of polycaprolactone polyol to polyisocyanate is 300-500:133.5-222.5;
s2: adding pentaerythritol triacrylate and a catalyst II into the prepolymer, heating to 88 ℃ for reaction for 8-8.5 hours, and cooling and discharging to obtain 6-functionality UV light-cured resin with NCO content less than 0.1%; wherein the mass ratio of polycaprolactone polyol to pentaerythritol triacrylate to catalyst II is 300-500:94-157:0.05-0.09.
6. The photocurable dual cure coating of claim 5, wherein said polycaprolactone polyol is prepared from neopentyl glycol as an initiator and has a hydroxyl value of 112mg koh/g.
7. The photocurable dual cure coating of claim 5 wherein said polyisocyanate is isophorone diisocyanate.
8. The photocurable dual cure coating of claim 5 wherein said catalyst two is tin tetrachloride.
9. The photocurable dual cure coating of claim 1 wherein said caprolactone-modified hydroxyethyl acrylate monomer has the structural formula:
a＝2；
the caprolactone-modified hydroxyethyl acrylate monomer is prepared by the following steps:
a1: hydroxyethyl acrylate, caprolactone, hydroxyanisole and stannous octoate are mixed according to the mass ratio of 92.8-116:
182.4-228:0.14-0.17:0.13-0.17 is stirred uniformly in a reaction bottle, and a pre-product is obtained after dehydration until the water content is below 200 ppm;
a2: heating the pre-product to 115-160 ℃ and reacting for 13-18 h, then vacuum devolatilizing at 100-115 ℃ for 2.5-3h, cooling and discharging to obtain caprolactone modified hydroxyethyl acrylate monomer.
10. The photocurable dual cure coating of claim 1 wherein said caprolactone-modified hydroxyethyl acrylate monomer has the structural formula:
b＝2；
b1: acrylic acid, caprolactone, tetramethyl piperidine nitroxide free radical phosphite triester, hydroquinone, stannic chloride and tetrapropyl titanate are mixed according to the mass ratio of 64.8-108:205.2-342:0.29-0.48:0.26-0.43:0.13-0.23:0.011-0.075, stirring in a reaction bottle, and dehydrating in vacuum until the water content reaches below 300ppm to obtain a pre-product;
b2: and (3) after the pre-product is stirred and heated to 160 ℃ for reaction for 17-18h, then the temperature is reduced to 100 ℃, vacuum devolatilization is carried out for 3h, and caprolactone modified acrylic monomer is obtained after cooling and discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310319303.9A CN116463049B (en) | 2023-03-29 | 2023-03-29 | Photo-curing dual-curing coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310319303.9A CN116463049B (en) | 2023-03-29 | 2023-03-29 | Photo-curing dual-curing coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116463049A true CN116463049A (en) | 2023-07-21 |
| CN116463049B CN116463049B (en) | 2023-10-17 |
Family
ID=87179841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310319303.9A Active CN116463049B (en) | 2023-03-29 | 2023-03-29 | Photo-curing dual-curing coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116463049B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4916254A (en) * | 1981-05-11 | 1990-04-10 | Daicel Chemical Industries, Inc. | Process for producing epsilon-caprolactone-modified hydroxyalkyl acrylate or methacrylate and coating copolymer from the same |
| CN101668786A (en) * | 2007-04-24 | 2010-03-10 | 日立化成工业株式会社 | Curable resin composition, led package, and method for production of the led package, and optical semiconductor |
| CN103360569A (en) * | 2012-03-29 | 2013-10-23 | 展辰涂料集团股份有限公司 | Multiple curing resin and preparation method thereof |
| CN105199076A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of water-based ultraviolet light-cured biology-base polyurethane acrylate resin |
| CN105801795A (en) * | 2016-04-15 | 2016-07-27 | 江苏利田科技股份有限公司 | 6-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof |
| KR20160136503A (en) * | 2015-05-19 | 2016-11-30 | 주식회사 범진인더스트리 | Method for manufacturing uv curable oligomer having self-healing property, and uv curable coating composition |
| CN112625290A (en) * | 2020-12-18 | 2021-04-09 | 深圳市华科创智技术有限公司 | Flexible display substrate |
| WO2022133668A1 (en) * | 2020-12-21 | 2022-06-30 | 张佩嫦 | Uv curable matt resin and preparation method therefor |
-
2023
- 2023-03-29 CN CN202310319303.9A patent/CN116463049B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4916254A (en) * | 1981-05-11 | 1990-04-10 | Daicel Chemical Industries, Inc. | Process for producing epsilon-caprolactone-modified hydroxyalkyl acrylate or methacrylate and coating copolymer from the same |
| CN101668786A (en) * | 2007-04-24 | 2010-03-10 | 日立化成工业株式会社 | Curable resin composition, led package, and method for production of the led package, and optical semiconductor |
| CN103360569A (en) * | 2012-03-29 | 2013-10-23 | 展辰涂料集团股份有限公司 | Multiple curing resin and preparation method thereof |
| KR20160136503A (en) * | 2015-05-19 | 2016-11-30 | 주식회사 범진인더스트리 | Method for manufacturing uv curable oligomer having self-healing property, and uv curable coating composition |
| CN105199076A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of water-based ultraviolet light-cured biology-base polyurethane acrylate resin |
| CN105801795A (en) * | 2016-04-15 | 2016-07-27 | 江苏利田科技股份有限公司 | 6-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof |
| CN112625290A (en) * | 2020-12-18 | 2021-04-09 | 深圳市华科创智技术有限公司 | Flexible display substrate |
| WO2022133668A1 (en) * | 2020-12-21 | 2022-06-30 | 张佩嫦 | Uv curable matt resin and preparation method therefor |
Non-Patent Citations (2)
| Title |
|---|
| 于浩;刘朋飞;刘仁;张丽萍;: "ε-己内酯改性聚氨酯丙烯酸酯的制备及电子束固化涂料性能研究", 影像科学与光化学, no. 01 * |
| 赵海鹏;张烨;: "聚酯多元醇的分类及研究进展", 上海塑料, no. 04 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116463049B (en) | 2023-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0712872B1 (en) | Hydroxy-functional acrylate resins, method for the preparation of such resins and reaction products of such resins | |
| US4137389A (en) | Low-molecular weight acrylate resins and a process for their production | |
| EP0676431B1 (en) | Coating compositions comprising 1,4-cyclohexane dimethanol | |
| NO311300B1 (en) | Hyperbranched polyesters, process for the preparation of such curable polymers comprising such, and use thereof | |
| CN110951041B (en) | Waterborne polyurethane-acrylate hybrid copolymer and preparation method thereof | |
| AU669297B2 (en) | Process for the preparation of copolymers containing OH-groups, and their use in high-solids coating compositions | |
| US20040122172A1 (en) | Polymer-modified resins | |
| CN111777742A (en) | Vegetable oleic acid modified epoxy acrylate photocureable resin and preparation method thereof | |
| CN109135551A (en) | A kind of high-flexibility waterborne UV coating | |
| CN109517183B (en) | Heterozygotic epoxy acrylate side chain modified polyacrylic resin and synthetic method thereof | |
| Mohanty et al. | Synthesis and evaluation of novel acrylic and ester-based polyols for transparent polyurethane coating applications | |
| CN104039861A (en) | Active energy beam-curable water-based resin composition, active energy beam-curable water-based coating and article coated with coating | |
| CN101668823B (en) | Adhesive composition comprising terminal-reactive acrylic polymer, and use thereof | |
| CN116463049B (en) | Photo-curing dual-curing coating | |
| EP2647678B1 (en) | Clear coating composition and method for forming multilayer coating film that uses same | |
| CN103608370B (en) | The method preparing radiation-hardenable composition | |
| CN109476775B (en) | Active energy ray-curable resin composition and primer for metal thin film | |
| WO2021094242A1 (en) | A low voc resin composition, its obtained resin and a coating composition comprising the same | |
| JP2000239334A (en) | Production of branched polymer | |
| Zhang et al. | Synthesis and Characterization of a Novel Low‐Viscosity Unsaturated Hyperbranched Polyester Resin | |
| US20070142591A1 (en) | High temperature polymerization process for making caprolactone-modified branched acrylic polymers | |
| US6787581B2 (en) | Radio hardenable powder paints | |
| CN112625228A (en) | Multifunctional polyester type ultraviolet curing resin, composition and preparation thereof | |
| US6849693B2 (en) | Hydroxyl group-containing polymers, their preparation and use | |
| Otsu et al. | Monomer‐isomerization radical polymerization of di‐tert‐butyl maleate and preparation of poly (fumaric acid) via pyrolysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 424000 Hunan Juren Chemical New Material Technology Co., Ltd., Green Chemical Industry Park, Yunxi District, Yueyang City, Hunan Province Patentee after: Hunan Juren New Materials Co. Country or region after: China Address before: 424000 Hunan Juren Chemical New Material Technology Co., Ltd., Green Chemical Industry Park, Yunxi District, Yueyang City, Hunan Province Patentee before: HUNAN JUREN CHEMICAL NEW MATERIAL TECHNOLOGY CO.,LTD. Country or region before: China |
|
| CP03 | Change of name, title or address |