CN110698642A - Polyurethane modified epoxy acrylate resin and preparation method thereof - Google Patents
Polyurethane modified epoxy acrylate resin and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- 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
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
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- 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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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Abstract
The invention relates to the technical field of resin, in particular to polyurethane modified epoxy acrylate resin and a preparation method thereof, wherein the polyurethane modified epoxy acrylate resin has a structure shown in the following general formula 1, the flexibility of a cured film formed by applying the polyurethane modified epoxy acrylate is far greater than that of the conventional bisphenol A epoxy acrylate, a regular long carbon chain is obtained by applying the ring-opening reaction of-OH and caprolactone, and the viscosity of the resin can be reduced while introducing a flexible chain. The resin can be used for preparing ultraviolet curing coatings and electron beam curing coatings with excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of resin, in particular to polyurethane modified epoxy acrylate resin and a preparation method thereof.
Technical Field
The photocuring curing technology is an environment-Friendly technology, and is applied to various fields such as metal, woodware, paper and the like due to the characteristic of 5E (Efficient efficiency, wide adaptability, Economical economy, Energy Saving by Energy Saving and Environmental Friendly). Bisphenol a epoxy acrylate has become one of the most widely used raw materials in the field of photocuring because of its fast curing rate, high rigidity of cured film, high film transparency, and the like. However, the conventional bisphenol A epoxy acrylate has the defects of large curing shrinkage, high viscosity, brittle cured film and poor yellowing resistance, and the application of the conventional bisphenol A epoxy acrylate is limited. Therefore, more and more researchers begin to develop the application range of the bisphenol a epoxy acrylate through modification, the modification of the epoxy acrylate mainly comprises physical modification and chemical modification, the physical modification mainly achieves the purposes of toughening and reducing the shrinkage rate by adding some pigments and fillers or compounding and curing a plurality of resins into a film, but poor compatibility between the pigments and the main resin and phase separation between different resins often occur in the physical modification process, so that the performance of the final film cannot reach the expectation. For example, CN108341921A discloses a method for preparing a polyurethane modified flexible epoxy acrylate resin, which comprises preparing a semi-adduct of diisocyanate and hydroxy acrylate and a flexible epoxy acrylate, and reacting the diisocyanate with the semi-adduct of hydroxy acrylate and the flexible epoxy acrylate to obtain the polyurethane modified flexible epoxy acrylate resin. However, such chemical modification often increases the molecular weight of the resin and the viscosity, and more reactive diluent is required to be added under the viscosity meeting the construction requirement, which greatly increases the cost, increases the irritation to the human body, and complicates the synthesis process. Therefore, in order to reduce the use of reactive diluents, reduce costs, and simplify synthesis steps, it is necessary to study urethane-modified epoxy acrylate resins and methods for preparing the same.
Disclosure of Invention
In view of the above problems, the present invention provides a polyurethane modified epoxy acrylate resin, wherein the resin has a structure represented by the following general formula 1:
One of them;
R1is represented by
One of them;
R2、R3independently of one another represent
Wherein n + m is 1-6; and x represents a connecting site.
Further, the resin is
And is a connecting site.
The second purpose of the invention is to provide a preparation method of polyurethane modified epoxy acrylate resin, which is characterized by comprising the following specific steps:
step 1, reacting hydroxyl-containing acrylate with caprolactone under the condition of a catalyst to obtain modified acrylate;
and 3, reacting the product modified acrylate in the step 1 with one or more product half-terminated polyurethane prepolymers in the step 2 under the condition of a catalyst to obtain the polyurethane modified epoxy acrylate resin.
Further, when more than one semi-terminated polyurethane prepolymer participating in the reaction in the step 3 is involved, the reaction is performed step by step, firstly, the modified acrylate and one semi-terminated polyurethane prepolymer are reacted under the condition of a catalyst, and then, the other semi-terminated polyurethane prepolymer is added to react under the action of the catalyst, so that the polyurethane modified epoxy acrylate resin is obtained.
Further, the molar ratio of the hydroxyl-containing acrylate to the caprolactone in the step 1 is 1: 0.5-1: 5; the catalyst comprises tin ethyl hexanoate; the temperature of the reaction is 100 ℃ and 120 ℃, and the caprolactone is completely consumed, namely the reaction is finished.
Further, the hydroxyl group-containing acrylate in the step 1 is represented by the following general formula 2
One of them;
R1is represented by
And is a connecting site.
Further, step 2 is to mix diisocyanate and a catalyst, dropwise add acrylate with hydroxyl, monitor the content of NCO groups in the reaction system, and finish the reaction when the NCO value is reduced to 50-60% of the initial value.
Further, the catalyst in the step 2 comprises dibutyltin dilaurate; the temperature is 50-90 ℃.
Further, the diisocyanate in the above-mentioned step 2 and step 3 is represented by the following formula 3
OCN-R5-NCO
Wherein R is5Is composed ofOne kind of the material is selected;
the acrylate having a hydroxyl group in the above-mentioned step 2 and step 3 is represented by the following general formula 4
R6-OH
Further, the catalyst in the step 3 comprises dibutyltin dilaurate, the reaction temperature is 60-90 ℃, and when the NCO content in the reaction system is 0, a certain proportion of another semi-terminated polyurethane prepolymer in the step 2 is added.
Has the advantages that:
according to the polyurethane modified epoxy acrylate provided by the invention, the flexibility of a cured film is far greater than that of the traditional bisphenol A epoxy acrylate, the wear resistance of a coating is enhanced, a regular long carbon chain is obtained by applying a ring-opening reaction of-OH and caprolactone, and the viscosity of resin can be reduced while a flexible chain is introduced. The polyurethane modified epoxy acrylate does not need to add an active diluent in the film forming process, so that the cost is greatly reduced, and the irritation to a human body is avoided.
The preparation method of the polyurethane modified epoxy acrylate provided by the invention is ingenious in arrangement, simple in method, cheap in raw materials, high in product obtaining efficiency, and easy to realize and suitable for large-scale production.
Drawings
FIG. 1 shows the tensile spectra of the cured films of the urethane-modified Epoxy Acrylate (EA) and the commercial Epoxy Acrylate (EA) of example 1
FIG. 2 is a graph comparing the viscosity of a commercial Epoxy Acrylate (EA) and a polyurethane modified Epoxy Acrylate (EA) of example 1
FIG. 3 is an IR spectrum of a urethane-modified epoxy acrylate of example 1
Detailed Description
The embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments described below, and can be carried out with various modifications within the gist thereof.
Example 1
1) To the reactor was added 62 parts of bisphenol a epoxy acrylate (mixture, purchased by the following route: the modified epoxy acrylate is prepared by uniformly stirring 0.2 part of tin ethyl hexanoate and 0.110 part of tin ethyl hexanoate, heating to the temperature of 110-120 ℃ in the system, dropwise adding 37.8 parts of caprolactone (n (hydroxyl-containing bisphenol A epoxy acrylate): n (caprolactone): 1:2) after the temperature is stabilized, and ending the reaction when no caprolactone molecule exists in the system after the dropwise adding is finished within half an hour.
2) Adding 56.5 parts of isophorone diisocyanate and 0.3 part of dibutyltin dilaurate serving as a catalyst into a reaction kettle, introducing nitrogen for about 30min to remove oxygen in a system, heating to 50-60 ℃, dropwise adding 43.2 parts of hydroxyethyl acrylate after the temperature is stable, controlling the temperature of the reaction system to be 50-60 ℃ during dropwise adding, reacting for about 4 hours after dropwise adding is finished, and finishing the reaction to obtain semi-blocked diisocyanate (IPDI-HEA), wherein an infrared spectrum is shown in figure 3.
3) 55.18 parts of the modified epoxy acrylate obtained in the step 1), 44.8 parts of the half-blocked diisocyanate obtained in the step 2) and 0.3 part of dibutyltin dilaurate serving as a catalyst are stirred uniformly, the temperature in a reaction system is raised to 80-90 ℃, and after the reaction is carried out for about 8 hours, the infrared spectrum of the polyurethane modified epoxy acrylate EA is obtained and is shown in figure 3.
The synthetic urethane-modified epoxy acrylate and the commercial epoxy acrylate (the product number RY1102 of Jiangsu Kai-phosphate Ruiyang chemical Co., Ltd.) were subjected to tensile test using a US 5967X tensile tester, and it can be seen from FIG. 1 that the elongation at break of the cured film was increased from the original 2.0% to 3.5% without changing the tensile strength of the cured film. The side chain of the bisphenol A epoxy acrylate is introduced with a caprolactone long chain, and the viscosity of the synthesized resin is low due to the regularity of the long chain. The viscosity test was performed on the synthesized caprolactone-modified epoxy acrylate and the epoxy acrylate not modified with caprolactone at 25 ℃ using a rotational viscometer, and it is seen from FIG. 2 that the viscosity of the synthesized urethane-modified epoxy acrylate is lowered by 20000mPa.s compared with the viscosity not modified with caprolactone.
Note: structures of commercial epoxy acrylates
And (3) detecting the performance of the coating:
formulation design of EA-PUA coating
The coating was made by scratching a standard tinplate with a BYK frame coater to a wet film thickness of about 90 μm. The curing was carried out by 5 exposures using a crawler-type F300 UVA exposure machine from Fusion, with the speed of the conveyor set at 5.4m/min, using UV Power from EITII Total energy measured by ultraviolet radiation meter is 800mJ/cm2。
The photocured coatings were tested, all following national standards, and all test results were averaged 3 times in parallel.
(1) And (3) testing the adhesive force: the adhesion of the cured film is tested according to the national standard GB/T9286-1998.
(2) And (3) testing pencil hardness: and measuring the pencil hardness of the cured film according to the national standard GB 6739-2006.
(3) Testing the hardness of the oscillating bar: the pendulum hardness(s) of the cured film was measured according to ASTM D4366.
(4) And (3) testing impact strength: measured using a CJQ-II paint film impactor according to GB/T6287.4-2000.
(5) And (3) testing the glossiness: the glossiness of the cured film is determined according to the national standard GB/T9754-2007.
Coating basic Performance test
Electron beam cured coating formulation and performance testing
Coating formulation design
The coating was made by scratching a standard tinplate with a BYK frame coater to a wet film thickness of about 90 μm. Radiation curing was performed on a low energy electron accelerator transport beam frame at 200 keV. The irradiation chamber and the front and rear isolation chambers are vacuumized and filled with nitrogen for protection, and the vacuum degree is 1.0 multiplied by 10 < -5 > Pa. The irradiation energy is 100-150 keV, and the beam current range is 50-70 mA.
The coatings were tested, all following national standards, and all test results were averaged 3 times in parallel.
(1) And (3) testing the adhesive force: the adhesion of the cured film is tested according to the national standard GB/T9286-1998.
(2) And (3) testing pencil hardness: and measuring the pencil hardness of the cured film according to the national standard GB 6739-2006.
(3) Testing the hardness of the oscillating bar: the pendulum hardness(s) of the cured film was measured according to ASTM D4366.
(4) And (3) testing impact strength: measured using a CJQ-II paint film impactor according to GB/T6287.4-2000.
(5) And (3) testing the glossiness: the glossiness of the cured film is determined according to the national standard GB/T9754-2007.
Coating basic Performance test
Example 2
1) To the reactor was added 59.2 parts of novolac epoxy acrylate (mixture, purchased by: the preparation method comprises the following steps of (a) uniformly stirring, namely, Jiangsu Guangxi Xin photosensitive new material Co., Ltd.), 0.2 part of tin ethyl hexanoate serving as a catalyst, heating to the temperature of 110-120 ℃ in a system, dropwise adding 40.6 parts of caprolactone (n (phenolic epoxy acrylate containing hydroxyl group): n (caprolactone): 1:3) after the temperature is stable, finishing dropwise adding within half an hour, and finishing the reaction when no caprolactone molecule exists in the system to obtain the modified epoxy acrylate.
2) Adding 57.23 parts of toluene diisocyanate and 0.3 part of catalyst dibutyltin dilaurate into a reaction kettle, introducing nitrogen for about 30min to remove oxygen in a system, heating to 50-60 ℃, dropwise adding 42.47 parts of hydroxypropyl acrylate after the temperature is stabilized, controlling the temperature of the reaction system to be 50-60 ℃ during dropwise adding, reacting for about 5h after dropwise adding is finished, and finishing the reaction to obtain the semi-blocked diisocyanate.
3) 43.2 parts of modified epoxy acrylate obtained in the step 1), 56.5 parts of half-blocked diisocyanate obtained in the step 2) and 0.3 part of dibutyltin dilaurate serving as a catalyst are stirred uniformly, the temperature in a reaction system is increased to 80-90 ℃, and after reaction for about 8 hours, the reaction is finished to obtain polyurethane modified epoxy acrylate EA-2.
The specific reaction equation is as follows:
and (3) detecting the performance of the coating:
formulation design of EA-2-PUA coating
The coating was made by scratching a standard tinplate with a BYK frame coater to a wet film thickness of about 90 μm. The curing was carried out by 5 exposures using a crawler-type F300 UVA exposure machine from Fusion, with the speed of the conveyor set at 5.4m/min, using UV Power from EITII Total energy measured by ultraviolet radiation meter is 800mJ/cm2。
The photocured coatings were tested, all following national standards, and all test results were averaged 3 times in parallel.
(1) And (3) testing the adhesive force: the adhesion of the cured film is tested according to the national standard GB/T9286-1998.
(2) And (3) testing pencil hardness: and measuring the pencil hardness of the cured film according to the national standard GB 6739-2006.
(3) Testing the hardness of the oscillating bar: the pendulum hardness(s) of the cured film was measured according to ASTM D4366.
(4) And (3) testing impact strength: measured using a CJQ-II paint film impactor according to GB/T6287.4-2000.
(5) And (3) testing the glossiness: the glossiness of the cured film is determined according to the national standard GB/T9754-2007.
Coating basic Performance test
Example 3
1) Adding 58.6 parts of bisphenol fluorene epoxy acrylate and 0.2 part of catalyst tin ethyl hexanoate into a reaction kettle, uniformly stirring, heating to the temperature of 110-120 ℃ in the system, dropwise adding 41.2 parts of caprolactone (n (-OH): n (caprolactone): 1) after the temperature is stable, finishing the dropwise adding within half an hour, and finishing the reaction when no caprolactone molecule exists in the system to obtain the modified epoxy acrylate.
2) 56.38 parts of 1, 6-hexanediol diisocyanate and 0.3 part of dibutyltin dilaurate serving as a catalyst are added into a reaction kettle, nitrogen is introduced for about 30min to remove oxygen in the system, the temperature is raised to 50-60 ℃ until the temperature is stabilized, 43.32 parts of hydroxypropyl methacrylate is added dropwise, the temperature of the reaction system is controlled to 50-60 ℃ during dropwise addition, and after dropwise addition is finished, reaction is carried out for about 3h, and the half-blocked diisocyanate is obtained.
3) Stirring uniformly 37.2 parts of the modified epoxy acrylate obtained in the step 1), 62.5 parts of the half-blocked diisocyanate obtained in the step 2) and 0.3 part of dibutyltin dilaurate serving as a catalyst, raising the temperature in a reaction system to 80-90 ℃, and reacting for about 8 hours to finish the reaction of the polyurethane modified epoxy acrylate EA-3.
And (3) detecting the performance of the coating:
formulation design of EA-3-PUA coating
The coating was made by scratching a standard tinplate with a BYK frame coater to a wet film thickness of about 90 μm. The curing was carried out by 5 exposures using a crawler-type F300 UVA exposure machine from Fusion, with the speed of the conveyor set at 5.4m/min, using UV Power from EITII Total energy measured by ultraviolet radiation meter is 800mJ/cm2。
The photocured coatings were tested, all following national standards, and all test results were averaged 3 times in parallel.
(1) And (3) testing the adhesive force: the adhesion of the cured film is tested according to the national standard GB/T9286-1998.
(2) And (3) testing pencil hardness: and measuring the pencil hardness of the cured film according to the national standard GB 6739-2006.
(3) Testing the hardness of the oscillating bar: the pendulum hardness(s) of the cured film was measured according to ASTM D4366.
(4) And (3) testing impact strength: measured using a CJQ-II paint film impactor according to GB/T6287.4-2000.
(5) And (3) testing the glossiness: the glossiness of the cured film is determined according to the national standard GB/T9754-2007.
Coating basic Performance test
Example 4
1) To the kettle was added 39.2 parts of novolac epoxy acrylate (mixture, purchased route: the preparation method comprises the following steps of (a) uniformly stirring, namely Jiangsu Guangxi Xin photosensitive new material Co., Ltd.), 0.2 part of tin ethyl hexanoate serving as a catalyst, heating to the temperature of 110-120 ℃ in a system, dropwise adding 60.6 parts of caprolactone (n (phenolic epoxy acrylate containing hydroxyl group): n (caprolactone): 1) after the temperature is stable, finishing dropwise adding within half an hour, and finishing the reaction when no caprolactone molecule exists in the system to obtain the modified epoxy acrylate.
2) 56.38 parts of 1, 6-hexanediol diisocyanate and 0.3 part of dibutyltin dilaurate serving as a catalyst are added into a reaction kettle, nitrogen is introduced for about 30min to remove oxygen in the system, the temperature is raised to 50-60 ℃ until the temperature is stabilized, 43.32 parts of hydroxypropyl acrylate is added dropwise, the temperature of the reaction system is controlled to 50-60 ℃ during dropwise addition, the reaction lasts for about 3h after the dropwise addition is finished, and the half-blocked diisocyanate is obtained after the reaction is finished.
3) 56.38 parts of 2, 6-toluene diisocyanate and 0.3 part of catalyst dibutyltin dilaurate are added into a reaction kettle, nitrogen is introduced for about 30min to remove oxygen in the system, the temperature is raised to 50-60 ℃, 43.32 parts of hydroxypropyl acrylate is added dropwise after the temperature is stabilized, the temperature of the reaction system is controlled to 50-60 ℃ during dropwise addition, the reaction lasts for about 3h after the dropwise addition is finished, and the semi-blocked diisocyanate is obtained after the reaction is finished.
4) Stirring uniformly 37.2 parts of the modified epoxy acrylate obtained in the step 1), 31.25 parts of the half-blocked diisocyanate obtained in the step 2) and 0.3 part of dibutyltin dilaurate serving as a catalyst, raising the temperature in a reaction system to 80-90 ℃, reacting for about 8 hours, adding 31.25 parts of the half-blocked diisocyanate obtained in the step 3), reacting for 10 hours, and obtaining the modified epoxy acrylate EA-4 after the theoretical NCO value is reached.
Formulation design of EA 4-PUA coating
The coating was made by scratching a standard tinplate with a BYK frame coater to a wet film thickness of about 90 μm. The curing was carried out by 5 exposures using a crawler-type F300 UVA exposure machine from Fusion, with the speed of the conveyor set at 5.4m/min, using UV Power from EITII Total energy measured by ultraviolet radiation meter is 800mJ/cm2。
The photocured coatings were tested, all following national standards, and all test results were averaged 3 times in parallel.
(1) And (3) testing the adhesive force: the adhesion of the cured film is tested according to the national standard GB/T9286-1998.
(2) And (3) testing pencil hardness: and measuring the pencil hardness of the cured film according to the national standard GB 6739-2006.
(3) Testing the hardness of the oscillating bar: the pendulum hardness(s) of the cured film was measured according to ASTM D4366.
(4) And (3) testing impact strength: measured using a CJQ-II paint film impactor according to GB/T6287.4-2000.
(5) And (3) testing the glossiness: the glossiness of the cured film is determined according to the national standard GB/T9754-2007.
Coating basic Performance test
Claims (10)
1. A polyurethane modified epoxy acrylate resin is characterized in that the resin structure is shown as the following general formula 1:
wherein R represents
One of them;
R1is represented by
One of them;
R2、R3independently of one another represent
Wherein n + m is 1-6; and x represents a connecting site.
3. The preparation method of the polyurethane modified epoxy acrylate resin according to claim 1, comprising the following specific steps:
step 1, reacting hydroxyl-containing acrylate with caprolactone under the condition of a catalyst to obtain modified acrylate;
step 2, reacting diisocyanate with acrylate with hydroxyl under the condition of a catalyst to obtain one or more semi-terminated polyurethane prepolymers;
and 3, reacting the product modified acrylate obtained in the step 1 with one or more half-terminated polyurethane prepolymers obtained in the step 2 under the condition of a catalyst to obtain the polyurethane modified epoxy acrylate resin.
4. The method of claim 3, wherein when more than one semi-blocked prepolymer is involved in the reaction in step 3, the reaction is performed in steps, the modified acrylate is reacted with one semi-blocked prepolymer under the condition of a catalyst, and then the other semi-blocked prepolymer is added to react under the action of a catalyst, so as to obtain the polyurethane modified epoxy acrylate resin.
5. The method for preparing the urethane-modified epoxy acrylate resin according to claim 3, wherein the molar ratio of the hydroxyl-containing acrylate to the caprolactone in the step 1 is 1:0.5 to 1: 5; the catalyst comprises tin ethyl hexanoate; the temperature of the reaction is 100 ℃ and 120 ℃, and the caprolactone is completely consumed, namely the reaction is finished.
7. The method for preparing a urethane-modified epoxy acrylate resin according to claim 3, wherein in the step 2, the diisocyanate is mixed with a catalyst, the acrylate having a hydroxyl group is added dropwise, the NCO group content in the reaction system is monitored, and the reaction is terminated when the NCO value is reduced to 50% to 60% of the initial value.
8. The method of claim 3, wherein the catalyst in the step 2 comprises dibutyltin dilaurate; the temperature is 50-90 ℃.
9. The method of claim 3, wherein the diisocyanate in step 2 is represented by the following formula 3
OCN-R5-NCO
General formula 3
Wherein R is5Is composed ofOne kind of (1);
the acrylate having a hydroxyl group in the step 2 is represented by the following general formula 4
R6-OH
General formula 4
10. The method of claim 3, wherein the catalyst in step 3 comprises dibutyltin dilaurate, the reaction temperature is 60-90 ℃, and when the NCO content of the reaction system is 0, the semi-terminated polyurethane prepolymer in step 2 is added in a certain proportion.
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