Polyurethane acrylate oligomer as well as preparation method and application thereof

Abstract

The invention provides a polyurethane acrylate oligomer as well as a preparation method and application thereof. The polyurethane acrylate oligomer provided by the invention is prepared from the following raw materials: isocyanate, polyester polyol, hydroxyl-containing silicone oil, hydroxyl monoacrylate and hydroxyl multi-acrylate according to a molar ratio of 6 to (4.1 to 5.5) to (0.9 to 1.2) to (0.9 to 1.1) to (0.03 to 0.05). The polyurethane acrylate oligomer provided by the invention is optimized from multiple aspects such as raw materials and proportions thereof, and can be cured by adopting an ultraviolet curing process; excellent elasticity and tensile strength are realized; according to the present invention, the organic silicon group is contained in the structure, and during film forming, the organic silicon group is grafted into the film forming substance, such that the surface tension of the paint film can be reduced, and the continuous and durable skin feeling and the oil stain resistance of the paint film can be obtained; the polyurethane acrylate oligomer provided by the invention can be used for leather coatings, a formed paint film can have lasting skin feeling and oil stain resistance effects, and the polyurethane acrylate oligomer can be further used for wood veneer protective coatings, plastic skin feeling coatings, other skin feeling coatings and the like.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a polyurethane acrylate oligomer and a preparation method and application thereof. Background Art

[0002] Leather coating is a general term for a class of materials used for leather surface finishing, protection and beautification. It plays a very important role in the leather manufacturing industry. It can increase the beauty of leather, extend the service life of leather, significantly improve the quality and grade of leather products, and increase commercial value. With the change of consumer concepts and the emergence of environmental protection issues, people have put forward higher requirements for leather coatings. Leather coatings are composed of film-forming materials, coloring materials, diluents and additives in a certain proportion, among which film-forming materials are the basis of leather coatings. Traditional leather coatings are mainly made of thermoplastic organic solvent-based resins as film-forming materials, and also made of thermoplastic water-based resins as the main film-forming materials. Most of the methods to increase skin feel and anti-fouling are obtained by adding silicone-fluorine additives in the late stage of coating manufacturing. This solvent-based coating has great fire hazards both in the manufacturing process and in the use process, and the volatilization of a large amount of organic solvents is harmful to the environment; while the water-based coating film is not full enough, not beautiful, and has poor water resistance. The comprehensive effect is difficult to meet people's growing requirements, and the actual drying time is generally more than 24 hours, and the construction efficiency is relatively low; the skin feel and anti-fouling effect of the paint film formed by this physical addition of skin feel additives cannot last long. After a period of use, the physical properties of silicone-fluorine additives disappear and the skin feel and anti-fouling properties are no longer maintained. UV curing technology has the characteristics of high efficiency, energy saving, and environmental protection. Especially in recent years, since the country has vigorously advocated the application of environmentally friendly and safe materials, it has been widely used in the fields of coatings, inks, and adhesives. Therefore, the global development in recent years has been quite rapid, especially in the field of UV curing coatings, which has made great progress.

[0003] In order to improve the efficiency, environmental protection, safety, fullness and beauty, long-lasting anti-fouling and long-lasting skin feel of leather coatings, these properties have become a special requirement for the characteristics of leather coating materials in recent years.

[0004] The most beneficial feature of UV curing is its high efficiency. Due to the extremely short curing time (generally within a few seconds), the drying efficiency is improved. The diluent used is an active diluent, which participates in the reaction during the film-forming process and becomes part of the basic material. It no longer evaporates into the atmosphere, reducing pollution to the environment. Since the materials used, including the active diluent, are substances with high flash points, they are not easy to catch fire and burn, which greatly guarantees the safety of firefighting. The solid content of traditional coatings is generally only about 30%, and it is difficult to achieve fullness after drying, lacking fullness, while the solid content of light-cured leather coatings can be close to 100%, so the paint film can achieve good fullness and gloss. The skin feel and stain resistance of traditional leather coatings are obtained by adding silicon-fluorine additives in the later stage of coating manufacturing. As the silicon-fluorine additives gradually float up, they are gradually eliminated by external mechanical friction or volatilization, and the skin feel disappears, and the anti-oil effect disappears. There is also a way to add silicon-fluorine-containing active diluents later, but the silicon-fluorine content of such monomers and other performance defects of such monomers affect the performance of film-forming substances, and it is also difficult to achieve a lasting skin feel and good stain resistance.

[0005] The Chinese patent application with publication number CN113999367A discloses a stain-resistant UV-curable waterborne polyurethane acrylate dispersion, which includes the following components in weight fractions: 2-3 parts of acrylate monomer, 1.5-2 parts of hydroxy acid monomer, 10-13 parts of isocyanate, 2-5 parts of silicon-containing polyol, 0.8-3 parts of polyol, 0.02-0.06 parts of catalyst, 0.007-0.01 parts of inhibitor, 5-10 parts of solvent, 15-20 parts of hydroxy acrylate, 1-3 parts of neutralizer, 1-2 parts of chain extender, and 52-68 parts of deionized water. However, after the polyurethane acrylate dispersion prepared by the method is formed into a film, its skin feel and anti-oil stain ability need to be improved. Summary of the invention

[0006] In order to overcome the technical problem that the skin feel and oil resistance of the UV-curable polyurethane acrylate obtained in the prior art need to be improved after film formation, the present invention provides a polyurethane acrylate oligomer that can be cured by ultraviolet light irradiation, and the paint film after film formation has good elasticity and tensile strength, and can have a lasting skin feel and oil resistance effect.

[0007] The first aspect of the present invention provides a polyurethane acrylate oligomer, wherein the raw materials include isocyanate, polyester polyol, hydroxyl-containing silicone oil, hydroxyl monoacrylate and hydroxyl polyacrylate in a molar ratio of 6: (4.1-5.5): (0.9-1.2): (0.9-1.1): (0.03-0.05).

[0008] The polyurethane acrylate oligomer provided by the present invention optimizes the raw materials and the ratio, so that the finally obtained polyurethane acrylate has a -C=C- structure / group, an urethane structure / group, and a silane structure / group; during light curing, the -C=C- structure / group can undergo an addition reaction to form a continuously cured paint film, so that an ultraviolet light curing process can be used for curing, which improves the drying efficiency, and the solid content can reach 100% after drying, and the paint film can achieve good fullness and gloss; during film formation, the silane structure / group can be grafted into the film-forming material through a chemical reaction, which can reduce the surface tension of the paint film, and can also enable the paint film to obtain a continuous and durable skin feel and anti-oil and anti-water stain capabilities. In summary, the polyurethane acrylate oligomer provided by the present invention can be cured by ultraviolet light, and the paint film after film formation can have a lasting skin feel and anti-fouling effect.

[0009] In some embodiments of the present invention, the polyurethane acrylate oligomer provided by the present invention comprises raw materials including isocyanate, polyester polyol, hydroxyl-containing silicone oil, hydroxyl monoacrylate, and hydroxyl polyacrylate in a molar ratio of 6: (4.1-5.5): (0.9-1.1): (0.9-1.0): (0.03-0.04). By further optimizing the ratio of each raw material, the polyurethane acrylate oligomer obtained by the present invention can obtain a more lasting skin feel and anti-fouling effect after film formation.

[0010] In some embodiments of the present invention, the hydroxyl-containing silicone oil has the structural formula HO[(CH 3 ) 2 SiO] n OH; preferably, n is an integer of 11-14, and / or, the hydroxyl-containing silicone oil has a molecular weight of 900-1000. The present invention adopts a silicone oil having a structural formula of HO[(CH 3 ) 2 SiO] n The bi-terminal hydroxyl silicone oil containing OH can react with isocyanate to graft the hydroxyl group in the hydroxyl silicone oil to the polyurethane acrylate oligomer, and in the subsequent film-forming process, improve the lasting skin feel and lasting anti-fouling effect of the paint film (such as the paint film on the leather surface). In particular, when n in the structural formula is an integer of 11-14, and / or the hydroxyl silicone oil has a molecular weight of 900-1000, the obtained polyurethane acrylate oligomer performs better in improving the lasting skin feel and lasting anti-fouling effect of the paint film (such as the paint film on the leather surface).

[0011] In some embodiments of the present invention, the hydroxy monoacrylate refers to an acrylate containing one hydroxyl group and one unsaturated double bond. Preferably, the hydroxy monoacrylate is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and polyester acrylate containing one hydroxyl group and an unsaturated double bond.

[0012] The present invention adopts the above-mentioned hydroxy monopropionate to realize the photocuring film formation of the polyurethane acrylate and improve the flexibility, so that the obtained paint film has better mechanical properties.

[0013] In some embodiments of the present invention, the hydroxyl multiacrylate is selected from at least one of pentaerythritol triacrylate, trimethylolpropane diacrylate, and dipentaerythritol pentaacrylate.

[0014] The present invention adopts the above-mentioned hydroxyl multiacrylate to realize the photocuring film formation of the polyurethane acrylate and provide higher hardness, thereby improving the mechanical properties of the obtained paint film.

[0015] In some embodiments of the present invention, the isocyanate is selected from H 12 At least one of MDI, MDI, TDI, IPDI, and HDI.

[0016] The present invention adopts the above isocyanate to achieve that the paint film obtained after the polyurethane acrylate is photocured into a film has high hardness, elastic modulus, tensile strength, paint film gloss and excellent adhesion to the substrate.

[0017] In some embodiments of the present invention, the polyester polyol is at least one of polyester diols with a molecular weight of 1500 to 2000. The present invention uses polyester diols with a molecular weight of 1500-2000, so that the paint film obtained after the polyurethane acrylate oligomer is photocured to form a film has a good elastic modulus and elongation.

[0018] In some embodiments of the present invention, the raw materials of the polyurethane acrylate oligomer also include an antioxidant, and the antioxidant is selected from at least one of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, zinc dialkyl dithiophosphate, N-phenyl-α-naphthylamine, and benzotriazole derivatives, and the total amount thereof is 170-200 ppm of the total formula.

[0019] The present invention adopts the above-mentioned antioxidant to make the polyurethane acrylate oligomer lighter in color and the paint film has excellent aging resistance. In particular, the antioxidant adopts 2,6-di-tert-butyl-4-methylphenol to make the polyurethane acrylate oligomer lighter in color, more beautiful, and the paint film has better aging resistance.

[0020] In some embodiments of the present invention, the raw materials of the polyurethane acrylate oligomer also include a diluent, and the function of the diluent is to reduce the viscosity of the coating, facilitate construction, and adjust the flexibility of the coating film. Preferably, the diluent is an active diluent, which means that the active diluent participates in the reaction during the film formation process, becomes a part of the base material, and no longer volatilizes into the atmosphere, thereby reducing pollution to the environment.

[0021] In some embodiments of the present invention, the reactive diluent is selected from at least one of dicyclopentenyl acrylate (such as EM2051) and lauric acid acrylate (such as EM215). Dicyclopentenyl acrylate (such as EM2051) and lauric acid acrylate (such as EM215) are substances with high flash points, are not easy to catch fire, and play a great role in ensuring the safety of fire fighting.

[0022] In some embodiments of the present invention, the raw materials of the polyurethane acrylate oligomer further include a polymerization inhibitor, and the polymerization inhibitor is selected from at least one of p-hydroxyanisole, hydroquinone, and 2,5-dimethylhydroquinone, and the total amount thereof is 300-350 ppm of the total mass of the formula. The present invention adopts the above-mentioned polymerization inhibitor to inhibit the occurrence of the addition reaction of the polyurethane acrylate oligomer during the synthesis process.

[0023] In some embodiments of the present invention, the raw materials of the polyurethane acrylate oligomer further include a catalyst, preferably the catalyst is selected from at least one of the environmentally friendly catalyst organic bismuth, dibutyltin dilaurate, triethylamine, tetrabutylammonium hydrogensulfate, tetrabutylammonium bromide, and triethylbenzylammonium chloride, and the total amount thereof is 100-150ppm of the total mass of the formula. The present invention uses the above catalyst to shorten the synthesis time of the polyurethane acrylate oligomer.

[0024] The second aspect of the present invention provides a method for preparing the polyurethane acrylate oligomer, comprising the following steps: (1) Dissolve the polyester polyol, diluent, inhibitor and antioxidant and stir evenly; (2) After adding hydroxyl-containing silicone oil and stirring evenly, add isocyanate and react; (3) Then, a catalyst, hydroxy monoacrylate and hydroxy polyacrylate are added and reacted until the NCO value of the system is less than 0.1%, and the reaction is stopped to obtain the polyurethane acrylate oligomer.

[0025] In some embodiments of the present invention, the reaction conditions in step (2) are: reacting at 50-55° C. for 4 to 4.5 hours while stirring.

[0026] In some embodiments of the present invention, the reaction conditions in step (3) are: reacting at 70-75° C. for 2 to 2.5 hours while stirring.

[0027] The present invention adopts the above special process, and on the basis of optimizing raw materials and proportions, further ensures that the obtained polyurethane acrylate oligomer can graft silicone into the film-forming material when forming a film, greatly prolonging the skin feel and anti-fouling effect retention time of the leather coating.

[0028] The third aspect of the present invention provides the use of the aforementioned polyurethane acrylate oligomer and / or the polyurethane acrylate oligomer obtained by the preparation method in a coating. Preferably, the coating is at least one of a veneer protective coating, a waterproof coating, and a skin-feel coating. The skin-feel coating is selected from at least one of a plastic skin-feel coating and a leather coating, and can also be used for other skin-feel coatings.

[0029] The fourth aspect of the present invention provides a leather coating, comprising the aforementioned polyurethane acrylate oligomer or the polyurethane acrylate oligomer obtained by the preparation method. The leather coating provided by the present invention adopts the polyurethane acrylate oligomer provided by the present invention, and after curing into a film, the obtained paint film has a high elongation at break, a high tensile strength, a moderate elastic modulus, and has a lasting skin feel and anti-fouling effect.

[0030] The present invention optimizes the raw materials, raw material ratios and other aspects, so that the obtained polyurethane acrylate oligomer not only has the characteristics of being photocurable and can increase the drying speed of the leather coating, but also the paint film obtained after the polyurethane acrylate oligomer is cured and film-formed has good mechanical properties, and the polyurethane acrylate oligomer can graft the silane structure / group into the film-forming substance when it is cured and film-formed, which greatly prolongs the skin feel and anti-fouling effect of the paint film (especially the leather coating), and can greatly improve the finishing effect on the substrate (especially the leather products). On the basis of optimizing the raw materials and their ratios, the present invention further optimizes the preparation process, further ensures that the polyurethane acrylate oligomer has a silane structure / group, and can graft the silane structure / group into the film-forming substance during the curing and film-forming process, thereby further improving the skin feel and durability of the anti-fouling effect of the paint film (especially the leather coating).

[0031] The polyurethane acrylate oligomer provided by the present invention is a green, environmentally friendly, safe and efficient ultraviolet light curing material, which can be applied to skin-feel coatings such as leather coatings and plastic skin-feel coatings, and can also be used in the fields of veneer protective coatings and waterproof coatings, thereby expanding the application of ultraviolet light curing and being able to be conveniently and flexibly used in ultraviolet light curing materials. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] The polyurethane acrylate oligomer provided by the present invention adopts raw materials: isocyanate I, polyester polyol II, hydroxyl-containing silicone oil III, hydroxyl monoacrylate IV, and hydroxyl polyacrylate V, and the molar ratio of the raw materials is 6: (4.1-5.5): (0.9-1.1): (0.9-1.0): (0.03-0.04), preferably 6: (4.1-4.5): (0.9-0.95): (0.9-1.0): (0.03-0.04)

[0034] The method for preparing the polyurethane acrylate oligomer provided by the present invention comprises the following steps: (1) Put polyester polyol, diluent, inhibitor and antioxidant into a reactor, heat to 40°C to completely melt, and stir for 15 minutes until uniform; (2) Add hydroxyl silicone oil and continue stirring for 5 minutes until uniform; (3) While stirring, quickly add isocyanate, continue stirring and heating, and after reacting at 50-55°C for 4 hours, add catalyst, hydroxy monoacrylate and hydroxy polyacrylate, react at 70-75°C for 2 hours, and then measure the NCO value of the system until the NCO value is less than 0.1%.

[0035] The following examples are given to specifically describe the present invention, but it is worth pointing out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by technical personnel skilled in the art based on the above-mentioned content of the present invention still fall within the scope of protection of the present invention.

[0036] In the following examples, the preparations used are all commercially available conventional products as long as the molecular structure and molecular weight of the materials meet the requirements and are qualified industrial products.

[0037] The meanings of some terms in this invention are as follows:

[0038] Example 1 Synthesis of oligomers

[0039] In this embodiment, a polyurethane acrylate oligomer is provided, and its preparation method is as follows: 448g of Yantai Huada polyester polyol CMA-44, 200g of EM2051, 200g of EM215, 1g of BHT, and 0.2g of MEHQ are added to a 1000mL reaction bottle, slowly heated to 40°C to completely dissolve the polyester polyol, stirred for 15 minutes, and after stirring evenly, 50g of double-terminal hydroxypropyl silicone oil Wss-140 is added and stirred for 5 minutes. After stirring evenly, 85g of isocyanate H is quickly added. 12MDI, after reacting at 50-55℃ for 4 hours, add 0.05g catalyst BICAT8108, 3g HEA, 2g PETA and 13g Ketian polyester acrylate 2102, react at 70-75℃ for 2 hours, measure the system NCO until the NCO value is less than 0.1% to obtain the oligomer, which is recorded as PU1.

[0040] The polyurethane acrylate oligomer obtained in this example is liquid, slightly yellow and transparent at 25° C., and the measured NCO value is 0.05%.

[0041] Example 2 Synthesis of oligomers

[0042] In this embodiment, a polyurethane acrylate oligomer is provided, and its preparation method is as follows: 448g Qingdao Yutian polyester polyol POL-356, 200g EM2051, 200g EM215, 1g BHT, and 0.15g MEHQ are added to a 1000mL reaction bottle, slowly heated to 40°C to completely dissolve the polyester polyol, stirred for 15 minutes, and after stirring evenly, 50g of double-terminal hydroxypropyl silicone oil Wss-140 is added and stirred for 5 minutes. After stirring evenly, 85g of isocyanate H is quickly added. 12 MDI, after reacting at 50-55℃ for 4 hours, add 0.05g catalyst BICAT8108, 3g HEA, 2g PETA and 13g Ketian 2102 polyester acrylate, react at 70-75℃ for 2 hours, measure the system NCO until the NCO value is less than 0.1% to obtain the oligomer, which is recorded as PU2.

[0043] The polyurethane acrylate oligomer obtained in this example is liquid, slightly yellow and transparent at 25° C., and the measured NCO value is 0.03%.

[0044] Example 3 Synthesis of oligomers

[0045] In this embodiment, a polyurethane acrylate oligomer is provided, and its preparation method is as follows: 448g of Zhejiang Huafeng Group polyester polyol PE-3020, 180g EM2051, 220g EM215, 1g BHT, and 0.2g MEHQ are added to a 1000mL reaction bottle, slowly heated to 40°C to completely dissolve the polyester polyol, stirred for 15 minutes, and after stirring evenly, 50g of double-terminal hydroxypropyl silicone oil Wss-140 is added and stirred for 5 minutes. After stirring evenly, 85g of isocyanate H is quickly added. 12 MDI, after reacting at 50-55℃ for 4 hours, add 0.05g catalyst BICAT8108, 3g HEA, 2g PETA and 13g Jiangmen Hengguang polyester acrylate 0206, react at 70-75℃ for 2 hours, measure the system NCO until the NCO value is less than 0.1% to obtain the oligomer, which is recorded as PU3.

[0046] The polyurethane acrylate oligomer obtained in this example is in a liquid, slightly yellow and transparent state at 25° C., and its NCO value is measured to be 0.04%.

[0047] Example 4 Synthesis of oligomers

[0048] In this embodiment, a polyurethane acrylate oligomer is provided, and its preparation method is as follows: 223g Zhejiang Huafeng Group polyester polyol PE-3020, 224g Qingdao Yutian polyester polyol POL-356, 210g EM2051, 190g EM215, 1g BHT, 0.15g MEHQ are added to a 1000mL reaction bottle, slowly heated to 40°C to completely dissolve the polyester polyol, stirred for 15 minutes, and after stirring evenly, 50g of double-terminal hydroxypropyl silicone oil Wss-140 is added and stirred for 5 minutes. After stirring evenly, 85g of isocyanate H is quickly added. 12 MDI, after reacting at 50-55℃ for 4 hours, add 0.05g catalyst BICAT8108, 4g HPA, 2g PETA and 13g Guangdong Haohui polyester acrylate CR90475, react at 70-75℃ for 2 hours, measure the system NCO value until the NCO value is less than 0.1% to obtain the oligomer, which is recorded as PU4.

[0049] The polyurethane acrylate oligomer obtained in this example is liquid, slightly yellow and transparent at 25° C., and the measured NCO value is 0.05%.

[0050] Example 5 Preparation of UV Curing Coating

[0051] In this embodiment, a UV curing coating is provided, which is prepared according to the formula in Table 1 below.

[0052] Table 1

[0053] The above groups A and B were made into coatings respectively, and the relevant indicators were measured as follows: viscosity 1000--2000mpa.s / 25°, fineness: <5um.

[0054] Example 6 Preparation of UV Curing Coating

[0055] In this embodiment, a UV curing coating is provided, which is prepared according to the formula in Table 2 below.

[0056] Table 2

[0057] The above groups C, D and E were made into coatings respectively, and the relevant indicators were measured as follows: viscosity 1000--2000mpa.s / 25°, fineness: <5um.

[0058] Test example

[0059] Test subjects: UV curing coatings obtained in Examples 5 and 6.

[0060] Test method: Roll the UV curing coating on the PU leather to make a 10 micron film, 1000mj / cm 2 Cured under UV light, the adhesion (Baige method), dyne value, skin feel and stain resistance of the paint film after curing were tested respectively; then the paint was made into a film according to GB / T1040-2006, and after UV curing, the elongation at break, tensile strength and elastic modulus were tested.

[0061] Test results: The test results are shown in Table 3.

[0062] Table 3

[0063] It can be seen from the above table that the curing degrees of the several polyurethane acrylate oligomers synthesized in the above embodiments are relatively high, indicating fast curing; the adhesion is good; the elongation at break, elastic modulus, and tensile strength are all high; after dry cotton gauze is rubbed under load, the dyne value is high, the skin feel is softer, the stain resistance is good, and the designed performance is achieved.

[0064] Group B uses the existing anti-fouling polyurethane acrylate oligomer B / 828 on the market to replace the polyurethane acrylate oligomer provided by the present invention in equal amounts, and the mechanical strengths such as elongation at break, tensile strength, and elastic modulus of the obtained paint film are significantly worse; and the skin feel of the paint film after 2000 times of a 500-gram load-bearing wear tester (dry cotton gauze), the dyne value after 2000 times of a 500-gram load-bearing wear tester (dry cotton gauze), and the result of scribbling on the paint film with an oily pen after friction and wiping again after 10 minutes are all significantly worse. Therefore, it is shown that the polyurethane acrylate oligomer provided by the present invention is used for the preparation of the paint film, and after light curing, the elongation at break, tensile strength, and elastic modulus of the paint film are improved, and a lasting skin feel and anti-fouling property are provided.

[0065] In the above embodiments, unless otherwise specified, known conventional options may be selected. For example, in Embodiments 5 and 6, the preparation of the coating is mentioned, but the method for preparing the coating is not specifically described. In this case, those skilled in the art may select a known method to prepare the coating; for example, the determination of the NCO value is mentioned in the above embodiments, but the specific determination method is not described. Therefore, those skilled in the art may select a known conventional method for determination; and so on.

[0066] The UV curing coating provided in the above implementation can be used in the field of skin-feel coatings such as leather coatings and plastic skin-feel coatings, and can also be used in the fields of waterproof coatings and veneer protective coatings, expanding the application of UV curing and being able to be conveniently and flexibly used in UV curing materials.

[0067] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyurethane acrylate oligomer, characterized in that: The raw materials include isocyanate, polyester polyol, hydroxyl-containing silicone oil, hydroxyl monoacrylate and hydroxyl polyacrylate in a molar ratio of 6: (4.1-5.5): (0.9-1.2): (0.9-1.1): (0.03-0.05).

2. The polyurethane acrylate oligomer according to claim 1, characterized in that: The raw materials include isocyanate, polyester polyol, hydroxyl-containing silicone oil, hydroxyl monoacrylate and hydroxyl polyacrylate in a molar ratio of 6: (4.1-4.5): (0.9-1.1): (0.9-1.0): (0.03-0.04).

3. The polyurethane acrylate oligomer according to claim 1 or 2, characterized in that: The hydroxyl-containing silicone oil has the structural formula HO[(CH3)2SiO] n OH; Preferably, n is an integer of 11-14, and / or the hydroxyl-containing silicone oil has a molecular weight of 900-1000.

4. The polyurethane acrylate oligomer according to any one of claims 1 to 3, characterized in that: The hydroxy monopropionate is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and polyester acrylate containing one hydroxyl group and an unsaturated double bond; And / or, the hydroxy polyacrylate is selected from at least one of pentaerythritol triacrylate, trimethylolpropane diacrylate and dipentaerythritol pentaacrylate; And / or, the isocyanate is selected from H 12 At least one of MDI, MDI, TDI, IPDI, and HDI; And / or, the polyester polyol is at least one of polyester diols having a molecular weight of 1500 to 2000.

5. The polyurethane acrylate oligomer according to any one of claims 1 to 4, characterized in that: The raw materials also include an antioxidant, which is selected from at least one of 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis (β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, zinc dialkyl dithiophosphate, N-phenyl-α-naphthylamine, and benzotriazole derivatives, and the total amount of the antioxidant is 170-200ppm of the total amount of the formula; And / or, the raw material further includes a diluent, and the diluent is a reactive diluent, preferably, the reactive diluent is selected from at least one of dicyclopentenyl acrylate and lauric acid acrylate; And / or, the raw materials further include a polymerization inhibitor, the polymerization inhibitor is selected from at least one of p-hydroxyanisole, hydroquinone, and 2,5-dimethylhydroquinone, and the total amount thereof is 300-350 ppm of the total mass of the formula; And / or, the raw materials also include a catalyst, the catalyst is at least one of organic bismuth, dibutyltin dilaurate, triethylamine, tetrabutylammonium hydrogen sulfate, tetrabutylammonium bromide, and triethylbenzylammonium chloride, and the total amount thereof is 100-150ppm of the total mass of the formula.

6. The method for preparing the polyurethane acrylate oligomer according to any one of claims 1 to 5, characterized in that: The following steps are involved: (1) Dissolve the polyester polyol, diluent, inhibitor and antioxidant and stir evenly; (2) After adding hydroxyl-containing silicone oil and stirring evenly, add isocyanate and react; (3) Then, a catalyst, hydroxy monoacrylate and hydroxy polyacrylate are added and reacted until the NCO value of the system is less than 0.1%, and the reaction is stopped to obtain the polyurethane acrylate oligomer.

7. The preparation method according to claim 6, characterized in that: The reaction conditions in step (2) are: reacting at 50-55° C. for 4 to 4.5 hours while stirring; And / or, the reaction conditions in step (3) are: reacting at 70-75° C. for 2 to 2.5 hours while stirring.

8. Use of the polyurethane acrylate oligomer obtained according to any one of claims 1 to 5 and / or the polyurethane acrylate oligomer obtained by the preparation method according to claim 6 or 7 in coatings.

9. The use according to claim 8, characterized in that: The coating is selected from at least one of veneer protective coating, waterproof coating, and skin-feel coating; Preferably, the skin-feel coating is selected from at least one of leather coating and plastic skin-feel coating.

10. A leather coating, characterized in that: The raw materials include the polyurethane acrylate oligomer obtained according to any one of claims 1 to 5 and / or the polyurethane acrylate oligomer obtained by the preparation method described in claim 6 or 7.

Images