CN104558500A - Ultraviolet light cured urethane acrylate elastic resin and preparation method thereof - Google Patents
Ultraviolet light cured urethane acrylate elastic resin and preparation method thereof Download PDFInfo
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- CN104558500A CN104558500A CN201410750590.XA CN201410750590A CN104558500A CN 104558500 A CN104558500 A CN 104558500A CN 201410750590 A CN201410750590 A CN 201410750590A CN 104558500 A CN104558500 A CN 104558500A
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- 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
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- 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
Abstract
The invention relates to urethane acrylate elastic resin. Ultraviolet light cured urethane acrylate elastic resin is composed of the following components in parts by weight: 12-32 parts of diisocyanate, 52-80 parts of poly(epsilon-caprolactone)di-OH, 1-9 parts of dibasic alcohol containing side chain, 1-8 parts of (methyl)acrylic hydroxy ester and 1-18 parts of pentaerythritol triacrylate; the ultraviolet light cured urethane acrylate elastic resin further contains a catalyst and a polymerization inhibitor, and the mass sum of the catalyst and the polymerization inhibitor is 0.03-0.06% of the total mass of the raw materials; the ultraviolet light cured urethane acrylate elastic resin further contains a diluting monomer, and the mass of the diluting monomer is 20-40% of the total mass of the raw materials. The ultraviolet light cured urethane acrylate elastic resin provided by the invention has the following characteristics that: the outline is water white or slight yellow transparent liquid, the solid content is higher than 99%, and the stretch rate is higher than 250% (the specification of a paint film is 10cm*1cm, and the thickness of the paint film is 100 microns).
Description
Technical field
The present invention relates to a kind of urethane acrylate elastic resin, particularly a kind of urethane acrylate elastic resin of ultraviolet light polymerization, also relates to its preparation method.
Background technology
Along with the development of imitation leather industry, the appearance modification of exquisite leatherware more and more comes into one's own.Therefore, the coating for leatherware arises at the historic moment.Because the snappiness of leatherware is better, so higher to the flexibility requirements of coating.
The people such as Guo Qing disclose a kind of synthetic method of water-base polyurethane/acrylate composite elastic resin in Chinese patent CN 1670052A.In patent, description admixtured polyether, tolylene diisocyanate, active emulsifier etc. prepare the elastic resin of excellent performance.
The people such as Bao Baiqing disclose a kind of dual-component aqueous polyurethane elastic resin and coating in Chinese patent CN 103641977A.Resin described in patent has excellent high tenacity by urethane hydroxy component and the composite resin of polyisocyanate curing agent.
The people such as Chen Zhixiang disclose a kind of flexible unsaturated polyester resin in Chinese patent CN 103396540A.Flexible unsaturated polyester resin described in patent adds thinner by diprotic acid or acid anhydrides and dibasic alcohol and dilutes and form after polycondensation.Gained resin has very high elongation at break and impelling strength.
Resin described in above patent of invention all has excellent performance, but its curing mode all belongs to traditional thermofixation, has power consumption high, the defects such as curing speed is slow.
Summary of the invention
For the deficiency such as existing elastic coating length time of drying, solid content low and high energy consumption, contaminate environment, technical problem to be solved by this invention is to provide a kind of UV-cured polyurethane acrylate elastic resin of excellent combination property, additionally provide its preparation method, this resin has the advantages such as solid content is high, rate of drying fast, energy-saving and environmental protection, can meet the demand of leather finishing coating and furniture wood skin finishing coating industry.
Technical problem to be solved by this invention is achieved by the following technical programs:
A kind of UV-cured polyurethane acrylate elastic resin, is made up of the component of following mass fraction:
Five kinds of raw materials below:
Vulcabond 12 ~ 32,
Polycaprolactone diols 52 ~ 80,
Containing side chain dibasic alcohol 1 ~ 9,
(methyl) crylic acid hydroxy ester 1 ~ 8,
Pentaerythritol triacrylate 1 ~ 18;
Also containing catalyzer, stopper, the quality sum of described catalyzer and stopper is 0.03 ~ 0.06% of above-mentioned raw materials total mass;
Also containing diluting monomer, the quality of described diluting monomer is 20 ~ 40% of above-mentioned raw materials total mass.
Further, described vulcabond adopts one or more in following material: tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI).
Further, described polycaprolactone diols adopts one or more in following material: polycaprolactone diols-1000(molecular weight is 1000), polycaprolactone diols-2000(molecular weight is 2000).
Further, described containing side chain dibasic alcohol adopt in following material one or more: 2，2-dimethyl-1，3-propanediol (NPG), 2-butyl-2-ethyl-1,3-PD (BEPD), 2,4-diethyl-1,5-PD (DEPD).
Further, described (methyl) crylic acid hydroxy ester adopts one or more in following material: Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA).
Further, described pentaerythritol triacrylate is not for synthesis level and containing pentaerythritol diacrylate.
Further, described catalyzer adopts one or more in following material: dibutyl tin laurate, K-KAT6212(organic zirconium class catalyzer, U.S. Jin Shi auxiliary agent Products).
Further, described stopper adopts one or more in following material: Tert. Butyl Hydroquinone, MEHQ, 2-methoxyl group Resorcinol.
Further, described diluting monomer is single functionality reactive monomer, adopts one or more in following material: isobornyl acrylate, isobornyl methacrylate, N-acryloyl morpholine.
The present invention also provides a kind of preparation method of UV-cured polyurethane acrylate elastic resin, and this preparation method comprises the following steps:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add vulcabond, then add the polycaprolactone of melting, be warming up to 65 ~ 70 DEG C, add catalyzer, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds the dibasic alcohol containing side chain to performed polymer I and is dissolved with the diluting monomer of stopper, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, (methyl) crylic acid hydroxy ester and pentaerythritol triacrylate is added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5 h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
use activity diluting monomerregulate the viscosity of UV-cured polyurethane acrylate elastic resin, and add light trigger preparation priming paint.By prepared priming paint roller coating on wooden skin, be UV-irradiation 25 ~ 40 s of 80 ~ 100 W/cm by ultraviolet lamp power, wooden skin can reach
bending180 ° are not wrecked.
UV-cured polyurethane acrylate elastic resin of the present invention has following characteristics:
1. UV-cured polyurethane acrylate elastic resin is water-white or micro-yellow transparent liquid.
2. UV-cured polyurethane acrylate elastic resin, solid content more than 99%.
3. UV-cured polyurethane acrylate elastic resin, extensibility is (paint film specification: 10cm × 1cm, film thickness: 100 μm) more than 250%.
Accompanying drawing explanation
Accompanying drawing 1 is the tension tester test pattern of embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, is not limitation of the invention.
Embodiment 1:
UV-cured polyurethane acrylate elastic resin of the present invention, be made up of the raw material of following portions by weight:
Vulcabond 12.2;
Polycaprolactone diols-2,000 73.1;
2-butyl-2-ethyl-1,3-PD 2.9;
Hydroxyethyl acrylate 1;
Pentaerythritol triacrylate 10.8;
Dibutyl tin laurate 0.03;
Tert. Butyl Hydroquinone 0.04;
Isobornyl acrylate 40;
The preparation method of this UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add vulcabond 12.2 parts, add the polycaprolactone-2000 of 73.1 parts of meltings again, be warming up to 65 ~ 70 DEG C, add dibutyl tin laurate 0.03 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 2.9 parts of 2-butyl-2-ethyl-1,3-PDs to performed polymer I and is dissolved with the isobornyl acrylate 40 parts of 0.04 part of Tert. Butyl Hydroquinone, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, 1 part of Hydroxyethyl acrylate and 10.8 parts of pentaerythritol triacrylates are added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 2:
UV-cured polyurethane acrylate elastic resin of the present invention, be made up of the raw material of following mass fraction:
Dicyclohexyl methane diisocyanate 31.3;
Polycaprolactone diols-1,000 59.7;
2，2-dimethyl-1，3-propanediol 5;
Hydroxyethyl methylacrylate 2.7;
Pentaerythritol triacrylate 1.3;
Dibutyl tin laurate 0.06;
MEHQ 0.03;
Isobornyl methacrylate 20;
The preparation method of this UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add dicyclohexyl methane diisocyanate 31.3 parts, add the polycaprolactone-1000 of 59.7 parts of meltings again, be warming up to 65 ~ 70 DEG C, add dibutyl tin laurate 0.06 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 5 parts of 2，2-dimethyl-1，3-propanediol to performed polymer I and is dissolved with the diluting monomer 20 parts of 0.03 part of stopper, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, 2.7 parts of hydroxyethyl methylacrylates and 1.3 parts of pentaerythritol triacrylates are added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 3:
A kind of UV-cured polyurethane acrylate elastic resin, be made up of the raw material of following mass fraction:
Dicyclohexyl methane diisocyanate 27.4;
Polycaprolactone diols-1,000 52.2;
2,4-diethyl-1,5-PD 4;
Propylene glycol monoacrylate 1;
Pentaerythritol triacrylate 15.4;
Dibutyl tin laurate 0.04;
2-methoxyl group Resorcinol 0.06;
N-acryloyl morpholine 20.
The preparation method of the present embodiment UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add dicyclohexyl methane diisocyanate 27.4 parts, add the polycaprolactone-1000 of 52.2 parts of meltings again, be warming up to 65 ~ 70 DEG C, add dibutyl tin laurate 0.06 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I,
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 4 parts of 2,4-diethyl-1,5-PDs to performed polymer I and is dissolved with the N-acryloyl morpholine 20 parts of 0.04 part of 2-methoxyl group Resorcinol, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II,
(3) under agitation, in 75 ~ 80 DEG C, in base polyurethane prepolymer for use as II, 1 part of Propylene glycol monoacrylate and 15.4 parts of pentaerythritol triacrylates are added.Then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 4:
A kind of UV-cured polyurethane acrylate elastic resin, be made up of the raw material of following mass fraction:
Dicyclohexyl methane diisocyanate 18.1;
Polycaprolactone diols-2,000 69.2;
2，2-dimethyl-1，3-propanediol 1.6;
Rocryl 410 1;
Pentaerythritol triacrylate 10.1;
K-KAT6212(organic zirconium) 0.03;
2-methoxyl group Resorcinol 0.06;
Isobornyl acrylate 40;
The preparation method of the present embodiment UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add dicyclohexyl methane diisocyanate 18.1 parts, add the polycaprolactone-2000 of 69.2 parts of meltings again, be warming up to 65 ~ 70 DEG C, add 0.03 part of K-KAT6212(organic zirconium), be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 1.6 parts of 2，2-dimethyl-1，3-propanediol to performed polymer I and is dissolved with the isobornyl acrylate 40 parts of 0.06 part of 2-methoxyl group Resorcinol, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, in base polyurethane prepolymer for use as II, 1 part of Rocryl 410 and 10.1 parts of pentaerythritol triacrylates are added.Then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 5:
A kind of UV-cured polyurethane acrylate elastic resin, be made up of the raw material of following mass fraction:
Hexamethylene diisocyanate 22.6;
Polycaprolactone diols-1,000 64.7;
2-butyl-2-ethyl-1,3-PD 8.3;
Hydroxyethyl acrylate 3;
Pentaerythritol triacrylate 1.4;
K-KAT6212(organic zirconium) 0.04;
MEHQ 0.05;
N-acryloyl morpholine 20.
The preparation method of the present embodiment UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add hexamethylene diisocyanate 22.6 parts, add the polycaprolactone-1000 of 64.7 parts of meltings again, be warming up to 65 ~ 70 DEG C, add K-KAT6212(organic zirconium) 0.04 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 8.3 parts of 2-butyl-2-ethyl-1,3-PDs to performed polymer I and is dissolved with the N-acryloyl morpholine 20 parts of 0.05 part of MEHQ, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, 3 parts of Hydroxyethyl acrylates and 1.4 parts of pentaerythritol triacrylates are added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 6:
A kind of UV-cured polyurethane acrylate elastic resin, be made up of the raw material of following mass fraction:
Tolylene diisocyanate 22.2;
Polycaprolactone diols-1,000 63.8;
2，2-dimethyl-1，3-propanediol 3.3;
Hydroxyethyl acrylate 7.3;
Pentaerythritol triacrylate 3.4;
K-KAT6212(organic zirconium) 0.06;
Tert. Butyl Hydroquinone 0.05;
N-acryloyl morpholine 30.
The preparation method of the present embodiment UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add tolylene diisocyanate 22.2 parts, add the polycaprolactone-1000 of 63.8 parts of meltings again, be warming up to 65 ~ 70 DEG C, add K-KAT6212(organic zirconium) 0.06 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 3.3 parts of 2，2-dimethyl-1，3-propanediol to performed polymer I and is dissolved with the N-acryloyl morpholine 30 parts of 0.05 part of Tert. Butyl Hydroquinone, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, in base polyurethane prepolymer for use as II, 7.3 parts of Hydroxyethyl acrylates and 3.4 parts of pentaerythritol triacrylates are added.Then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 7:
A kind of UV-cured polyurethane acrylate elastic resin, be made up of the raw material of following mass fraction:
Tolylene diisocyanate 20.4;
Polycaprolactone diols-1,000 58.3;
2，2-dimethyl-1，3-propanediol 3;
Hydroxyethyl acrylate 1;
Pentaerythritol triacrylate 17.3;
Dibutyl tin laurate 0.04;
2-methoxyl group Resorcinol 0.05;
Isobornyl methacrylate 30.
The preparation method of the present embodiment UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add tolylene diisocyanate 20.4 parts, add the polycaprolactone-1000 of 58.3 parts of meltings again, be warming up to 65 ~ 70 DEG C, add dibutyl tin laurate 0.04 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 3 parts of 2，2-dimethyl-1，3-propanediol to performed polymer I and is dissolved with the isobornyl methacrylate 30 parts of 0.05 part of 2-methoxyl group Resorcinol, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, 1 part of Hydroxyethyl acrylate and 17.3 parts of pentaerythritol triacrylates are added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Embodiment 8:
A kind of UV-cured polyurethane acrylate elastic resin, be made up of the raw material of following mass fraction:
Tolylene diisocyanate 13.9;
Polycaprolactone diols-2,000 80;
2，2-dimethyl-1，3-propanediol 3.3;
Hydroxyethyl acrylate 1.8;
Pentaerythritol triacrylate 1;
K-KAT6212(organic zirconium) 0.03;
MEHQ 0.06;
N-acryloyl morpholine 40.
The preparation method of the present embodiment UV-cured polyurethane acrylate elastic resin is:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add tolylene diisocyanate 13.9 parts, add the polycaprolactone-2000 of 80 parts of meltings again, be warming up to 65 ~ 70 DEG C, add K-KAT6212(organic zirconium) 0.03 part, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds 3.3 parts of 2，2-dimethyl-1，3-propanediol to performed polymer I and is dissolved with the N-acryloyl morpholine 40 parts of 0.06 part of MEHQ, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, 1 part of Hydroxyethyl acrylate and 1.8 parts of pentaerythritol triacrylates are added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
Below by way of test, the performance of the embodiment of the present invention 1 ~ 8 is verified:
The paint film preparation technology of the UV-cured polyurethane acrylate elastic resin that embodiment 1 ~ 8 obtains and parameter, implement by following proportioning and condition:
UV-cured polyurethane acrylate elastic resin 97 mass parts;
Light trigger 1,173 3 mass parts;
UV lamp predominant wavelength 365 nm;
Photocuring power 100 W/cm;
Light application time 25 s;
Luminous range 10 cm;
Film thickness 100 μm.
Concrete grammar is: the UV-cured polyurethane acrylate elastic resin of each embodiment and light trigger 1173 are mixed by above-mentioned mass fraction, with on the thickness coated glass plate of 100 μm, under above-mentioned ultraviolet light conditions, carries out hardening with radiation.Then, paint film is made following specification: 10cm × 1cm, by the paint film property prepared by tension tester test.
Wherein, the tension tester test pattern of embodiment 1 as shown in Figure 1.
The tensile test data of embodiment 1 ~ 8 are as following table:
Visible, elastic resin of the present invention has excellent tensile property.
Claims (9)
1. a UV-cured polyurethane acrylate elastic resin, is characterized in that, comprises the component of following mass fraction:
Five kinds of raw materials below:
Vulcabond 12 ~ 32,
Polycaprolactone diols 52 ~ 80,
Containing side chain dibasic alcohol 1 ~ 9,
(methyl) crylic acid hydroxy ester 1 ~ 8,
Pentaerythritol triacrylate 1 ~ 18;
Also containing catalyzer, stopper, the quality sum of described catalyzer and stopper is 0.03 ~ 0.06% of above-mentioned raw materials total mass;
Also containing diluting monomer, the quality of described diluting monomer is 20 ~ 40% of above-mentioned raw materials total mass.
2. UV-cured polyurethane acrylate elastic resin according to claim 1, it is characterized in that, described vulcabond adopts one or more in following material: tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexyl methane diisocyanate (HMDI), hexamethylene diisocyanate (HDI).
3. UV-cured polyurethane acrylate elastic resin according to claim 1, is characterized in that, described polycaprolactone diols adopts one or more in following material: polycaprolactone diols-1000, polycaprolactone diols-2000.
4. UV-cured polyurethane acrylate elastic resin according to claim 1, it is characterized in that, described containing side chain dibasic alcohol adopt in following material one or more: 2,2-dimethyl-1, ammediol (NPG), 2-butyl-2-ethyl-1, ammediol (BEPD), 2,4-diethyl-1,5-PD (DEPD).
5. UV-cured polyurethane acrylate elastic resin according to claim 1, it is characterized in that, described (methyl) crylic acid hydroxy ester adopts one or more in following material: Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA).
6. UV-cured polyurethane acrylate elastic resin according to claim 1, is characterized in that, described catalyzer adopts one or more in following material: dibutyl tin laurate, K-KAT6212.
7. UV-cured polyurethane acrylate elastic resin according to claim 1, is characterized in that, described stopper adopts one or more in following material: Tert. Butyl Hydroquinone, MEHQ, 2-methoxyl group Resorcinol.
8. UV-cured polyurethane acrylate elastic resin according to claim 1, it is characterized in that, described diluting monomer is single functionality reactive monomer, adopts one or more in following material: isobornyl acrylate, isobornyl methacrylate, N-acryloyl morpholine.
9. a preparation method for UV-cured polyurethane acrylate elastic resin according to claim 1, is characterized in that comprising the steps:
(1) synthesis of base polyurethane prepolymer for use as I: load onto four-hole boiling flask, mechanical stirrer and reflux condensing tube on heating jacket, first in four-hole boiling flask, add vulcabond, add the polycaprolactone of melting again, be warming up to 65 ~ 70 DEG C and add catalyzer, be slowly warming up to 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as I;
(2) synthesis of base polyurethane prepolymer for use as II: under agitation, adds the dibasic alcohol containing side chain to performed polymer I and is dissolved with the diluting monomer of stopper, and controlling temperature of reaction in 85 ~ 90 DEG C; Then, insulation reaction 1 ~ 1.5 h, measures isocyanate group content, when isocyanate group content reaches theoretical value, obtains base polyurethane prepolymer for use as II;
(3) under agitation, in 75 ~ 80 DEG C, (methyl) crylic acid hydroxy ester and pentaerythritol triacrylate is added in base polyurethane prepolymer for use as II, then, under 85 ~ 90 DEG C of conditions, insulation reaction 2 ~ 2.5h, when system isocyanate base content reduces to zero, obtains UV-cured polyurethane acrylate elastic resin.
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| CN106700024A (en) * | 2015-11-15 | 2017-05-24 | 惠州市长润发涂料有限公司 | Preparation method of UV-curable polyurethane acrylate self-repair resin |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
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| CN106700024A (en) * | 2015-11-15 | 2017-05-24 | 惠州市长润发涂料有限公司 | Preparation method of UV-curable polyurethane acrylate self-repair resin |
| CN110023361A (en) * | 2016-11-23 | 2019-07-16 | 美国斯帕泰克塑料加工有限责任公司 | Carbamate-urea-acrylic acid casting plate material |
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| CN109503808A (en) * | 2018-10-31 | 2019-03-22 | 上纬新材料科技股份有限公司 | Low viscous high-strength polyurethane acrylic resin of one kind and preparation method thereof |
| CN112048051A (en) * | 2019-06-05 | 2020-12-08 | 万华化学（北京）有限公司 | Polyurethane acrylate resin and preparation method thereof |
| CN112807246A (en) * | 2019-11-15 | 2021-05-18 | 万华化学集团股份有限公司 | Ultraviolet-curing optically variable nail polish and preparation method thereof |
| CN112807246B (en) * | 2019-11-15 | 2023-01-13 | 万华化学集团股份有限公司 | Ultraviolet-curing optically variable nail polish and preparation method thereof |
| CN111688311A (en) * | 2020-05-27 | 2020-09-22 | 林金瑛 | Functional card protection structure and processing method thereof |
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| CN113788928A (en) * | 2021-09-07 | 2021-12-14 | 肇庆市宝骏化工有限公司 | High-temperature-resistant and high-elongation polyurethane acrylic resin and application thereof in preparation of ultraviolet-cured peelable glue |
| CN114249872A (en) * | 2021-09-22 | 2022-03-29 | 中昊北方涂料工业研究设计院有限公司 | Fluorine-containing acrylic acid modified polyurethane wear-resistant resin and preparation method thereof |
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