CN112225868A - Two-three functionality mixed polyurethane acrylate resin and preparation method thereof - Google Patents
Two-three functionality mixed polyurethane acrylate resin and preparation method thereof Download PDFInfo
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- CN112225868A CN112225868A CN202011069183.4A CN202011069183A CN112225868A CN 112225868 A CN112225868 A CN 112225868A CN 202011069183 A CN202011069183 A CN 202011069183A CN 112225868 A CN112225868 A CN 112225868A
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
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- 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
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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
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- 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 belongs to the technical field of polyurethane acrylate, and discloses a two-three functionality degree mixed polyurethane acrylate resin and a preparation method thereof. The method comprises the following steps: adding diisocyanate into a reaction container filled with a dihydroxy monomer, a trihydroxy monomer and a catalyst at 50-70 ℃, and reacting for 2-4 h; and then adding a mixture of hydroxyl acrylate and a polymerization inhibitor at the temperature of 60-80 ℃, and continuously reacting for 2-4 hours to obtain the mixed polyurethane acrylate resin. The method is simple, and the perfect mixing of the two types of functionality polyurethane acrylate is realized by one pot, so that the synergistic effect of the two types of functionality polyurethane acrylate is exerted. The prepared mixed polyurethane acrylate resin has low viscosity, excellent adhesive force and storage stability, and has excellent flexibility, luster, pencil hardness, wear resistance, water resistance, acid resistance, alkali resistance and other properties after being cured.
Description
Technical Field
The invention belongs to the technical field of polyurethane acrylate, relates to a mixed polyurethane acrylate resin, and particularly relates to a two/three-functionality mixed polyurethane acrylate resin and a preparation method thereof.
Background
In recent years, the application of conventional solvent-based coatings has been increasingly limited because they do not meet environmental requirements. The research and development and production of environment-friendly and green water-based paint and ultraviolet curing paint (UVCC) are rapidly developed. However, the water-based products have slow curing of the coating film due to the presence of water, and the product performance is difficult to compare favorably with solvent-based coatings. UVCC is fast in curing speed, 100% in curing, environment-friendly, energy-saving and excellent in coating performance, can be used for thermosensitive substrates such as plastics, paper, wood and the like, and gradually becomes a chasing coating variety for people.
The polyurethane acrylate has strong adhesive force, good wear resistance, good flexibility, good chemical corrosion resistance and high coating glossiness, and is an important class in UVCC resin. The products in the current market are mainly bifunctional products, and the trifunctional polyurethane acrylate resin is less.
Polyurethane acrylate resin produced by the prior art, a difunctional product and a trifunctional product are prepared separately, and the difunctional product and the trifunctional product are respectively weighed and mixed according to the proportion when the performance is required to be adjusted, so that the time and the energy are consumed; and because viscosity is great and need mix both after heating, the mixed degree is not high, and is difficult even, hardly exerts the effective synergy of both performance, also can cause the waste of material because viscosity is big, and resin viscosity is too high, still needs to add a large amount of reactive diluent and adjusts the viscosity. The active diluents have a special pungent odor and high toxicity, so that the active diluents pollute the local environment and are harmful to operators, and the active diluents are expensive, so that the product cost is increased.
In summary, the existing methods for producing urethane acrylate resins have the disadvantages of performance matching, which results in the product performance not being effectively cooperated, the storage of the mixed products is unstable, the viscosity is too high, more active monomers need to be added, and the method is time-consuming, energy-consuming, labor-consuming and cost-increasing. Therefore, the preparation method of the invention can fully improve the comprehensive performance of the resin while saving cost, time and energy consumption, and has positive significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a two/three functionality degree mixed polyurethane acrylate resin capable of being cured by ultraviolet light and a preparation method thereof. The resin prepared by the method has short reaction time, low viscosity, excellent adhesive force and storage stability, and excellent flexibility, luster, pencil hardness, water resistance, acid resistance, alkali resistance and the like after curing.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a two/three functionality mixed polyurethane acrylate resin comprises the following steps:
adding diisocyanate into a reaction container filled with a dihydroxy monomer, a trihydroxy monomer and a catalyst at 50-70 ℃, and reacting for 2-4 h; and then adding a mixture of hydroxyl acrylate and a polymerization inhibitor at the temperature of 60-80 ℃, and continuously reacting for 2-4 hours to obtain the mixed polyurethane acrylate resin.
The amount of the dihydroxy monomer is N, the amount of the trihydroxy monomer is M, and the ratio of N to M is (1-2): (1-6), preferably 2: 1.
The amount of material of the diisocyanate is 2N + 3M.
The molar ratio of diisocyanate to hydroxy acrylate is 1: 1.
the catalyst is dibutyl tin dilaurate; the dosage of the catalyst is 0.05-0.1% of the total mass of reactants, and the reactants are dihydroxy monomer, trihydroxy monomer, acrylic acid hydroxy ester and diisocyanate.
The polymerization inhibitor is hydroquinone and/or p-hydroxyanisole, the dosage of the polymerization inhibitor is 0.06-0.1% of the mass of reactants, and the reactants are dihydroxy monomers, trihydroxy monomers, acrylic acid hydroxy ester and diisocyanate.
The dihydroxy monomer is one or more of polyether diol 1000 (molar mass 1000, number average molecular weight), polyether diol 2000 (molar mass 1000, number average molecular weight), polyester diol 1000 (molar mass 1000, number average molecular weight) and polyester diol 2000 (molar mass 1000, number average molecular weight).
The polyether glycol 1000 is HK-210 and PPG1000 of Shandong Jining; the polyether glycol 2000 is HK-220 and PPG2000 of Shandong Jining; the polyester diol 1000 is PCL210N and HKP-4112 of Shandong Jining, and the polyester diol 2000 is PCL220N and HKP-456.
The trihydroxy monomer is one or more of trimethylolpropane, polyether trihydric alcohol and polyester trihydric alcohol.
The polyether triol is HK-310 and HK-305 of Shandong Jining; the polyester triol is HKP-24112 and HKP-2475 from Shandong Jining.
The hydroxyl acrylate is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
The diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
The diisocyanate is added dropwise in 1-1.5 h.
A mixed polyurethane acrylate resin with two/three functionality is prepared by the method.
The resin is suitable for the field of ultraviolet curing coatings of woodware, metal materials and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention adopts a one-pot method, namely, the resin with two functionalities is synthesized in a reaction kettle simultaneously. The method is designed from a source, two reactions are carried out simultaneously according to the proportion, the full mixing and winding of two resins can be realized on the molecular level, the performance synergy of the two resins is exerted to the maximum extent, compared with a method of mixing during respective preparation and performance adjustment, the method is more full in mixing, and an active diluent is not required to be added for viscosity adjustment during adjustment, so that the labor, time and energy are greatly saved, the preparation process is simplified, the preparation time is shortened, the cost is greatly reduced, and the method is more environment-friendly and more friendly to human bodies; meanwhile, the stability of the product is greatly improved.
Detailed Description
The present invention will be described in further detail with reference to examples for better understanding, but the scope of the present invention is not limited thereto.
Example 1
Adding 100g of polyether glycol 1000(PPG1000, molecular weight is 1000), 13.4g of trimethylolpropane and 0.18g of dibutyltin dilaurate into a reaction vessel, heating to 50 ℃ under stirring, adding 111.15g of isophorone diisocyanate, controlling the addition within 1.5 hours, carrying out heat preservation reaction for 3.5 hours, heating to 70 ℃, adding a mixture of 58g of hydroxyethyl acrylate and 0.19g of p-hydroxyanisole, and carrying out reaction for 3 hours to obtain the di/tri-functionality mixed polyurethane acrylate resin A.
Example 2
100g of polyether glycol 2000(PPG2000, molecular weight of 2000), 13.4g of trimethylolpropane and 0.15g of dibutyltin dilaurate are added into a reaction vessel, the temperature is raised to 60 ℃ under stirring, 100.1g of diphenylmethane diisocyanate is added, the addition is controlled within 1.5 hours, the reaction is kept for 3 hours, the temperature is raised to 75 ℃, a mixture of 46.4g of hydroxyethyl acrylate and 0.18g of hydroquinone is added, and the reaction is carried out for 3.5 hours, so that the di/tri-functionality mixed polyurethane acrylate resin B is prepared.
Example 3
100g of polyester diol 1000(PCL210N, molecular weight of 1000), 6.7g of trimethylolpropane and 0.16g of dibutyltin dilaurate are added into a reaction vessel, the temperature is raised to 70 ℃ under stirring, 60.95g of toluene diisocyanate is added, the addition is controlled within 1.2 hours, the heat preservation reaction is carried out for 2.5 hours, the temperature is raised to 70 ℃, a mixture of 45.5g of hydroxypropyl acrylate and 0.18g of p-hydroxyanisole is added, and the reaction is carried out for 4 hours, so that the di/tri-functionality mixed polyurethane acrylate resin C is prepared.
Example 4
100g of polyester diol 2000(PCL220N, molecular weight of 2000), 6.7g of trimethylolpropane and 0.18g of dibutyltin dilaurate are added into a reaction vessel, the temperature is raised to 65 ℃ under stirring, 42.05g of hexamethylene diisocyanate is added, the addition is controlled within 1.3 hours, the heat preservation reaction is carried out for 4 hours, the temperature is raised to 80 ℃, a mixture of 32.5g of hydroxyethyl methacrylate and 0.15g of hydroquinone is added, and the reaction is carried out for 3.5 hours, so that the di/tri-functionality mixed polyurethane acrylate resin D is prepared.
Example 5
100g of polyether diol 1000(HK-210, molecular weight is 1000), 50g of polyether triol 1000(HK-310, molecular weight is 1000) and 0.21g of dibutyltin dilaurate are added into a reaction vessel, the temperature is raised to 65 ℃ under stirring, 77.81g of isophorone diisocyanate is added, the addition is controlled to be completed within 1.5 hours, the temperature is kept for reaction for 3.5 hours, the temperature is raised to 70 ℃, a mixture of 45.5g of hydroxypropyl acrylate and 0.18g of p-hydroxyanisole is added, and the reaction is carried out for 3.5 hours, so that the di/tri-functionality mixed polyurethane acrylate resin E is prepared.
Example 6
100g of polyester diol 1000(HKP-4112 with a molecular weight of 1000), 50g of polyester triol 1000(HKP-24112 with a molecular weight of 1000) and 0.2g of dibutyltin dilaurate are added into a reaction vessel, the temperature is raised to 65 ℃ under stirring, 60.95g of toluene diisocyanate is added, the addition is controlled to be completed within 1.5 hours, the temperature is kept for reaction for 4 hours, the temperature is raised to 80 ℃, a mixture of 50.4g of hydroxypropyl methacrylate and 0.16g of hydroquinone is added, and the reaction is carried out for 4 hours, so that the di/tri-functionality mixed polyurethane acrylate resin F is prepared.
Comparative example 1 simple difunctional urethane acrylate
Adding 150G of polyether glycol PPG1000, 100G of polyester glycol HKP-4112 and 0.25G of dibutyltin dilaurate into a reaction vessel, heating to 50 ℃ under stirring, adding 111.15G of isophorone diisocyanate, controlling the addition within 1.5 hours, carrying out heat preservation reaction for 3.5 hours, heating to 70 ℃, adding a mixture of 58G of hydroxyethyl acrylate and 0.26G of p-hydroxyanisole, and reacting for 3 hours to obtain the difunctional polyurethane acrylate resin G.
Comparative example 2 purely trifunctional urethane acrylate
30g of polyether triol HK305, 60g of polyester triol HKP-24112, 9.40g of trimethylolpropane and 0.16g of dibutyltin dilaurate are added into a reaction vessel, the temperature is raised to 50 ℃ under stirring, 111.15g of isophorone diisocyanate is added, the addition is controlled to be completed within 1.5 hours, the temperature is kept for reaction for 3.5 hours, the temperature is raised to 70 ℃, a mixture of 58g of hydroxyethyl acrylate and 0.17g of p-hydroxyanisole is added, and the reaction is carried out for 3 hours, so that the trifunctional polyurethane acrylate resin H is prepared.
The data of the performance test of the urethane acrylates prepared in examples 1 to 6 and comparative examples 1 to 2 are shown in Table 1.
TABLE 1 data of Performance test of urethane acrylates prepared in examples 1 to 6 and comparative examples 1 to 2
As can be seen from the table above, the prepared di/tri-functionality mixed polyurethane acrylate resin has better tensile strength and hardness than the di-functionality polyurethane acrylate resin after coating, and simultaneously has better elongation at break, adhesive force and viscosity than the tri-functionality polyurethane acrylate resin, and can be used as the optimal selection of the finish paint of protective coatings of wood metal and the like.
Claims (9)
1. A preparation method of a two/three functionality mixed polyurethane acrylate resin is characterized by comprising the following steps: the method comprises the following steps:
adding diisocyanate into a reaction container filled with a dihydroxy monomer, a trihydroxy monomer and a catalyst at 50-70 ℃, and reacting for 2-4 h; then adding a mixture of hydroxyl acrylate and a polymerization inhibitor at the temperature of 60-80 ℃, and continuously reacting for 2-4 hours to obtain mixed polyurethane acrylate resin;
the amount of the dihydroxy monomer is N, the amount of the trihydroxy monomer is M, and the ratio of N to M is (1-2): (1-6).
2. The method for preparing a di/tri-functional hybrid urethane acrylate resin according to claim 1, wherein: the molar ratio of the dihydroxy monomer to the trihydroxy monomer is 2: 1.
3. The method for preparing a di/tri-functional hybrid urethane acrylate resin according to claim 1, wherein: the dihydroxy monomer is one or more of polyether diol 1000, polyether diol 2000, polyester diol 1000 and polyester diol 2000, and the molecular weight is represented by 1000 and 2000;
the trihydroxy monomer is one or more of trimethylolpropane, polyether trihydric alcohol and polyester trihydric alcohol.
4. The method for preparing a di/tri-functional hybrid urethane acrylate resin according to claim 1, wherein: the hydroxyl acrylate is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
5. The method for preparing a di/tri-functional hybrid urethane acrylate resin according to claim 1, wherein: the amount of the diisocyanate is 2N +3M, the amount of the dihydroxy monomer is N, and the amount of the trihydroxy monomer is M;
the molar ratio of diisocyanate to hydroxy acrylate is 1: 1.
6. the method for preparing a di/tri-functional hybrid urethane acrylate resin according to claim 1, wherein:
the catalyst is dibutyl tin dilaurate;
the polymerization inhibitor is hydroquinone and/or p-hydroxyanisole.
7. The method for preparing a di/tri-functional hybrid urethane acrylate resin according to claim 1, wherein: the dosage of the catalyst is 0.05-0.1% of the total mass of reactants, and the reactants are dihydroxy monomer, trihydroxy monomer, acrylic acid hydroxy ester and diisocyanate. The amount of the polymerization inhibitor is 0.06-0.1% of the mass of the reactants, and the reactants are dihydroxy monomer, trihydroxy monomer, acrylic acid hydroxy ester and diisocyanate.
8. A di/tri-functional hybrid urethane acrylate resin obtained by the preparation method according to any one of claims 1 to 7.
9. Use of a di/tri-functional hybrid urethane acrylate resin according to claim 1 wherein: the two/three functionality mixed polyurethane acrylate resin is used for preparing ultraviolet curing coatings of woodware and metal materials.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114921218A (en) * | 2022-06-27 | 2022-08-19 | 山东一诺威聚氨酯股份有限公司 | UV (ultraviolet)/moisture dual-curing adhesive and preparation method thereof |
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