Isosorbide bio-based epoxy acrylate and preparation method and application thereof

Abstract

This invention discloses an isosorbide-based bio-based epoxy acrylate, which is prepared from bio-based isosorbide and bio-based glycerol-derived epichlorohydrin as raw materials to obtain isosorbide glycidyl ether; using bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid as raw materials, an esterification reaction and a vacuum polycondensation reaction are carried out sequentially to obtain a bio-based carboxyl-terminated polyester; the bio-based carboxyl-terminated polyester reacts with isosorbide glycidyl ether to obtain a bio-based epoxy resin; the bio-based epoxy resin reacts with acrylic acid to obtain a UV-curable isosorbide-based bio-based epoxy acrylate. This invention also discloses an isosorbide-based bio-based epoxy acrylate UV resin, which is obtained by mixing isosorbide-based bio-based epoxy acrylate with UV monomers. This invention further discloses the application of isosorbide-based bio-based epoxy acrylate or isosorbide-based bio-based epoxy acrylate UV resin in the preparation of UV coatings, inks, and adhesives.

Description

Technical Field

[0001] This invention belongs to the field of materials and relates to an isosorbide bio-based epoxy acrylate, its preparation method and application. Background Technology

[0002] As is well known, petrochemical resources such as oil, natural gas, and coal are widely used and non-renewable resources, and are also the main raw materials for producing polymer resin materials. Against the backdrop of reducing the over-exploitation and use of fossil resources and achieving sustainable development, the conversion and utilization of bio-based raw materials and their derivatives have become a new research hotspot. Among them, bio-based coating resins are a class of polymeric compounds prepared from renewable biomass. Compared with traditional petrochemical coating resins, they have the characteristics of environmental friendliness and sustainability, thus attracting widespread attention and applied research in various fields.

[0003] Among various renewable resources (such as solar and wind energy), biomass is the only renewable organic carbon resource in nature. Sorbitol, as one of the top ten biomass platform chemicals, has broad application prospects as isosorbide, a product obtained through acid-catalyzed dehydration.

[0004] With the rapid development of science and technology and the strict restrictions on solvents imposed by environmental protection regulations, ultraviolet (UV) curable polymer materials are receiving increasing attention. UV curable materials possess excellent properties such as rapid curing, low energy consumption, low pollution, and high efficiency, and are therefore widely used in coatings, printing, and electronics industries, experiencing rapid development in recent years. With the rise of UV curing technology, new UV-curable materials are being used more and more extensively as raw materials for UV coatings, inks, and adhesives, with usage increasing year by year.

[0005] There are few reports on technologies that use renewable plant resources to synthesize coating resins and apply them to the field of photocuring.

[0006] If UV technology can be combined with renewable plant resources to achieve the application of bio-based UV resins and bio-based UV coatings, then the carbon emission problem that has been troubling the industry will find a feasible solution, and the pollution of the environment caused by chemical synthesis processes will be greatly reduced. Summary of the Invention

[0007] The purpose of this invention is to address the above-mentioned shortcomings of the prior art by providing an isosorbide-based bio-based epoxy acrylate.

[0008] Another object of the present invention is to provide a method for preparing the isosorbide bio-based epoxy acrylate.

[0009] Another object of the present invention is to provide the application of the isosorbide bio-based epoxy acrylate.

[0010] The objective of this invention can be achieved through the following technical solutions:

[0011] A bio-based isosorbide epoxy acrylate is prepared by using bio-based isosorbide and bio-based glycerol-derived epichlorohydrin as raw materials to obtain isosorbide glycidyl ether; and by using bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid as raw materials to undergo esterification and vacuum polycondensation reactions in sequence to prepare a bio-based carboxyl-terminated polyester; the bio-based carboxyl-terminated polyester reacts with isosorbide glycidyl ether to obtain a bio-based epoxy resin; and the bio-based epoxy resin reacts with acrylic acid to obtain a UV-curable isosorbide bio-based epoxy acrylate.

[0012] The structural formula of bio-based isosorbide is shown below:

[0013]

[0014] The structural formula of bio-based 1,2-pentanediol is shown below:

[0015]

[0016] The structural formula of bio-based 1,5-pentanediol is shown below:

[0017]

[0018] The structural formula of bio-based succinic acid is shown below:

[0019]

[0020] A method for preparing the isosorbide bio-based epoxy acrylate includes the following steps:

[0021] Step (1): Isosorbide glycidyl ether is prepared by reacting bio-based isosorbide with bio-based glycerol via epichlorohydrin.

[0022]

[0023] Step (2): Using bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and bio-based succinic acid as raw materials, under N2 protection, the esterification reaction is carried out first in the presence of a catalyst, and then an antioxidant is added to carry out a vacuum polycondensation reaction to prepare bio-based end-carboxyl polyester.

[0024] Step (3): Under the action of a catalyst, bio-based terminal carboxyl polyester reacts with isosorbide glycidyl ether to obtain bio-based epoxy resin.

[0025] Step (4): In the presence of a catalyst and a polymerization inhibitor, bio-based epoxy resin reacts with acrylic acid to prepare UV-curable isosorbide bio-based epoxy acrylate.

[0026] In step (1), the isosorbide glycidyl ether is prepared by the following method: a catalyst is used to catalyze the ring-opening etherification reaction of bio-based isosorbide and bio-based glycerol epichlorohydrin; then sodium hydroxide solid is added, and a ring-closing reaction occurs under the action of a strong base to obtain isosorbide glycidyl ether.

[0027] Preferably, the isosorbide glycidyl ether is prepared by the following method: Bio-based isosorbide, bio-based glycerol-derived epichlorohydrin, and a catalyst are added to a reactor for a ring-opening etherification reaction; then, solid sodium hydroxide is added in 3-10 batches for a ring-closing reaction; after the reaction is complete, the solid is filtered, epichlorohydrin is removed by vacuum distillation, then dissolved in ethyl acetate, washed with water, ethyl acetate is removed by vacuum distillation, and filtered to obtain isosorbide glycidyl ether. The epoxy equivalent (mass of resin containing 1 mol of epoxy groups) is determined according to GB / T 4612-2008. The epoxy equivalent of the isosorbide glycidyl ether is 130-200 g / mol.

[0028] The mass ratio of the bio-based isosorbide to the bio-based glycerol-derived epichlorohydrin is [1.0×146.14]:[(2.0~30)×92.52], preferably [1.0×146.14]:[(2.0~6.0)×92.52].

[0029] Specifically, the mass ratio of the bio-based isosorbide to the bio-based glycerol-derived epichlorohydrin can be (1.0×146.14):(6.0×92.52).

[0030] The catalyst is one or a mixture of two or more quaternary ammonium salt catalysts or quaternary phosphonium salt catalysts in any proportion.

[0031] The quaternary ammonium salt catalysts are benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc.; the quaternary phosphonium salt catalysts are triphenylethylphosphonium bromide, tetrabutylphosphonium bromide, etc.

[0032] The amount of catalyst used is 0.05wt% to 3wt% of the total mass of bio-based isosorbide and bio-based glycerol-based epichlorohydrin, preferably 0.2wt% to 0.5wt%.

[0033] The ring-opening etherification reaction is carried out at a temperature of 115℃ to 120℃ and for a time of 2 to 6 hours.

[0034] Preferably, bio-based isosorbide, bio-based glycerol-based epichlorohydrin, and catalyst are added to a reactor, stirred until homogeneous, and then the temperature is slowly increased to 115°C over 0.5 to 2 hours. The ring-opening etherification reaction is carried out at a temperature of 115°C to 120°C for 2 to 6 hours.

[0035] The mass ratio of the bio-based isosorbide to sodium hydroxide is [1.0×146.14]:[(2.0~2.5)×40.01].

[0036] Specifically, the mass ratio of the bio-based isosorbide to sodium hydroxide can be (1.0×146.14):(2.1×40.01).

[0037] The closed-loop reaction is carried out at a temperature of 50–55°C for 2–8 hours.

[0038] Conditions for removing excess epichlorohydrin by vacuum distillation: vacuum conditions of -0.085 MPa to -0.1 MPa and temperature of 117 to 120 °C.

[0039] Specifically, the conditions for removing excess epichlorohydrin by vacuum distillation are: vacuum conditions of -0.090 MPa and temperature of 117–120 °C.

[0040] The filtration process uses a 100-mesh filter.

[0041] In step (2), the bio-based carboxyl-terminated polyester is prepared by the following method: First, bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and catalyst are added to a reactor equipped with a distillation column, condenser and water separator, heated and melted and the material temperature is raised to 110°C; then bio-based succinic acid is added, and under N2 protection, an esterification reaction is carried out at a temperature of 210-250°C. During the esterification reaction, the temperature at the top of the distillation column does not exceed 100°C. When the temperature at the top of the distillation column is below 60°C and the material is clear and transparent, an antioxidant is added, and a vacuum polycondensation reaction is carried out at a temperature of 210-250°C and a vacuum condition of -0.088 to -0.098 MPa (gauge pressure) until no water is distilled out; after the polycondensation reaction is completed, the mixture is filtered to obtain the bio-based carboxyl-terminated polyester.

[0042] The mass ratio of the bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid is [1.5×146.14]:[(0.8~1.2)×2.1×104.15]:[(0.8~1.2)×1.05×104.15]:[(0.8~1.2)×5.65×118.09], preferably [1.5×146.14]:[1×2.1×104.15]:[1×1.05×104.15]:[1×5.65×118.09].

[0043] The catalyst is one or a mixture of two or more of the following in any proportion: antimony glycolate, antimony triacetate, isopropyl titanate, n-butyl titanate, tin isooctanoate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin oxide, bismuth isooctanoate, and lanthanum isooctanoate; further selected from one or a mixture of two or more of the following in any proportion: isopropyl titanate, n-butyl titanate, antimony glycolate, and bismuth isooctanoate; the amount of the catalyst is 0.01 wt% to 1 wt% of the total mass of bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid, preferably 0.05 wt% to 0.085 wt%.

[0044] The antioxidant is triphenyl phosphite; the amount of the antioxidant is 0.01wt% to 1wt% of the total mass of bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and bio-based succinic acid, preferably 0.05wt% to 0.085wt%.

[0045] Preferably, the pressure of the vacuum polycondensation reaction is -0.090 MPa (gauge pressure).

[0046] The vacuum polycondensation reaction takes 1 to 8 hours.

[0047] Under the reaction conditions of this invention, polyols and polyacids undergo esterification and polycondensation reactions, generating small molecule water which is then distilled off. When no water is distilled off from the reaction system, the polycondensation reaction is considered to be complete.

[0048] The filtration process uses a 100-mesh filter.

[0049] In step (3), the bio-based epoxy resin is prepared by the following method: isosorbide glycidyl ether, bio-based carboxyl-terminated polyester and catalyst are added to a reactor, stirred evenly, and the temperature is slowly raised to 80°C in 0.5 to 1 hour, and then slowly raised to 100°C in 1 to 3 hours. The reaction is carried out at a temperature of 100 to 105°C until the acid value of the reaction system is ≤2.0 mgKOH / g, and the bio-based epoxy resin is obtained.

[0050] The mass ratio of isosorbide glycidyl ether to bio-based carboxyl-terminated polyester is [(4.0~5.0)×epoxy equivalent of isosorbide glycidyl ether]:1000.

[0051] The catalyst is one or a mixture of two or more Lewis base catalysts, quaternary ammonium salt catalysts or quaternary phosphonium salt catalysts in any proportion.

[0052] The Lewis base catalysts are triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, tributylphosphine, etc.; the quaternary ammonium salt catalysts are benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc.; the quaternary phosphonium salt catalysts are triphenylethylphosphonium bromide, tetrabutylphosphonium bromide, etc.

[0053] The amount of the catalyst used is 0.1wt% to 3wt% of the total mass of isosorbide glycidyl ether and bio-based carboxyl-terminated polyester, preferably 0.1wt% to 0.5wt%.

[0054] Generally, the total reaction time is 1 to 6 hours. When the acid value of the reaction system is ≤2.0 mg KOH / g, the reaction is terminated by cooling to below 60°C.

[0055] In step (4), the isosorbide bio-based epoxy acrylate is prepared by the following method: adding acrylic acid, catalyst and polymerization inhibitor to bio-based epoxy resin, stirring evenly, slowly raising the temperature to 100°C over 1 to 3 hours, reacting at 100 to 105°C for 1 to 2 hours, slowly raising the temperature to 115°C over 1 to 3 hours, reacting at 115 to 120°C for 1 to 6 hours until the acid value of the reaction system is ≤2.0 mgKOH / g, cooling to 80°C, and terminating the reaction.

[0056] The mass ratio of the acrylic acid and the bio-based carboxyl-terminated polyester is [(1.8~3.3)×72.06]:1000, preferably [(1.8~2.2)×72.06]:1000.

[0057] The catalyst is one or a mixture of two or more Lewis base catalysts, quaternary ammonium salt catalysts or quaternary phosphonium salt catalysts in any proportion.

[0058] The Lewis base catalysts are triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, tributylphosphine, etc.; the quaternary ammonium salt catalysts are benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc.; the quaternary phosphonium salt catalysts are triphenylethylphosphonium bromide, tetrabutylphosphonium bromide, etc.

[0059] The catalyst is used in an amount of 0.1 wt% to 3 wt% of the total mass of bio-based isosorbide glycidyl ether, bio-based carboxyl-terminated polyester and acrylic acid.

[0060] The polymerization inhibitor is one or a mixture of two of p-hydroxyanisole (MEHQ) and 2,6-di-tert-butyl-4-methylphenol (BHT) in any proportion; the amount of polymerization inhibitor used is 0.01 wt% to 1 wt% of the total mass of isosorbide glycidyl ether, bio-based carboxyl-terminated polyester and acrylic acid.

[0061] An isosorbide-based bio-based epoxy acrylate UV resin is obtained by mixing the isosorbide-based bio-based epoxy acrylate with an appropriate amount of UV monomer, stirring evenly, and removing air bubbles under vacuum to obtain a clear and transparent isosorbide-based bio-based epoxy acrylate UV resin.

[0062] Preferably, one method for obtaining the isosorbide-based bio-based epoxy acrylate UV resin involves adding a UV monomer to the isosorbide-based bio-based epoxy acrylate, stirring at 70–85°C for 0.5–1 hour, removing air bubbles under vacuum until the resin solution is clear and transparent, stopping the vacuum, cooling to 70°C, and filtering through a 100-mesh filter to obtain a clear and transparent isosorbide-based bio-based epoxy acrylate UV resin.

[0063] The viscosity of the isosorbide bio-based epoxy acrylate UV resin is 4000-9000 cps@60℃.

[0064] The UV monomer is one or more of TPGDA, DPGDA, HDDA, and GPTA in any proportion.

[0065] The amount of the UV monomer used is 5 wt% to 30 wt% of the total mass of isosorbide glycidyl ether, carboxyl-terminated polyester and acrylic acid.

[0066] The vacuum conditions for degassing are -0.050MPa to -0.090MPa, and the time is 1 to 5 hours.

[0067] The isosorbide bio-based epoxy acrylate or the isosorbide bio-based epoxy acrylate UV resin described in this invention is used in the preparation of UV coatings, inks, and adhesives.

[0068] The beneficial effects of this invention are:

[0069] 1,5-Pentanediol has a straight-chain structure. Its introduction increases the flexibility of the main chain and reduces viscosity. 1,2-Pentanediol has a branched-chain structure. The introduction of branches can disrupt the symmetry of the main chain structure, increasing the distance between molecular chain segments, reducing the polymer's crystallinity and melting point, and affecting the application properties of the polymer product, such as hardness, impact resistance, flexural strength, and tensile strength. Introducing hydrophobic alkyl side groups protects the main chain functional groups, improving the water resistance and heat resistance of the main chain structure. Isosorbide is a bicyclic ether alcohol, synthesized through the dehydration reaction of D-sorbitol. As a bio-based product already produced on a large industrial scale, it has low production costs, is non-toxic, and has high rigidity, and it possesses two independent secondary hydroxyl groups. Compared with other bio-based monomers, isosorbide has high rigidity, which can significantly improve the hardness of bio-based polymers. This invention optimizes the ratio of the three alcohols, adjusts the crystallinity and melting point of the main chain, achieves moderate viscosity, and balances hardness and flexibility, thereby improving the overall performance of UV-cured coatings.

[0070] This invention prepares isosorbide glycidyl ether by reacting epichlorohydrin with isosorbide, introducing epoxy groups. The isosorbide glycidyl ether containing epoxy groups at both ends serves as a functional monomer, which can connect to the carboxyl groups of terminal carboxyl polyesters or the carboxyl groups of acrylic acid, thereby introducing a UV-curable photosensitive group—acryloyloxy—into the polymer molecular chain.

[0071] The isosorbide bio-based epoxy acrylate of this invention can be used as a raw material for UV coatings, inks, and adhesives. After curing, it has excellent properties such as high hardness, wear resistance, scratch resistance, heat resistance, and weather resistance. Detailed Implementation

[0072] Bio-based isosorbide (IS) is a novel, green, non-toxic bio-based material with excellent properties such as chirality. It is also the only sugar diol that has achieved large-scale industrial production. The main raw material for isosorbide is sorbitol. Due to the wide availability and low price of raw materials, as well as its outstanding environmental performance, isosorbide is hailed as the second most important bio-based chemical raw material after polylactic acid.

[0073] Bio-based isosorbide (98.5% purity), manufacturer: Hubei Qibajiu Chemical Co., Ltd.

[0074] Epichlorohydrin, manufactured by Shandong Binhua Group, is produced using the bio-based glycerol method.

[0075] Bio-based 1,2-pentanediol, manufactured by Shandong Yinuo Biotechnology Group, is produced using non-grain bio-based furfural as raw material.

[0076] Bio-based 1,5-pentanediol, manufactured by Shandong Yinuo Biotechnology Group, is produced using non-grain bio-based furfural as raw material.

[0077] Bio-based succinic acid, manufactured by Shandong Landian Biotechnology Co., Ltd., is produced using microbial fermentation. Compared with petrochemical synthesis, microbial fermentation produces succinic acid that is purely natural, pollution-free, and food-grade without further processing. It is also fully biodegradable, utilizing renewable plant resources as raw materials, thus reducing the environmental pollution caused by chemical synthesis processes.

[0078] Example 1

[0079] Step (1), Preparation of isosorbide glycidyl ether: 1460 g of bio-based isosorbide (relative molecular weight 146.14), 5550 g of bio-based glycerol-derived epichlorohydrin, and 19 g of benzyltriethylammonium chloride were added to a reactor. The mixture was stirred until homogeneous, and then the temperature was slowly increased from room temperature to 115°C over 1.5 hours. The ring-opening etherification reaction was carried out under reflux conditions (temperature 115°C-120°C) for 4 hours. The temperature was then lowered to 50°C, and 841 g of sodium hydroxide solid was added in 6 batches. Under the action of a strong alkali, the ring-closing reaction occurred at a temperature of 50-55°C for 5 hours. After the reaction was completed, the solid in the reaction system was removed by filtration, and excess epichlorohydrin was removed by vacuum distillation. The vacuum distillation conditions were: vacuum condition -0.090. The pressure was increased slowly from room temperature to 117°C over 3 hours, and vacuum distilled at 117-120°C for 3 hours. No epichlorohydrin distilled off at this point. The vacuum was stopped, and the temperature was lowered to 55°C. 260 g of ethyl acetate was added to dissolve the ethyl acetate. The mixture was washed three times with 200 g of water added each time. The washed organic phase was then subjected to vacuum distillation to remove the ethyl acetate. The vacuum distillation was carried out under a vacuum of -0.090 MPa, slowly increased from room temperature to 117°C over 3 hours, and vacuum distilled at 117-120°C for 3 hours. No ethyl acetate distilled off at this point. The vacuum was stopped, and the temperature was lowered to 55°C. The mixture was filtered through a 100-mesh filter to obtain isosorbide glycidyl ether. The epoxy equivalent was determined to be 130.5 g / mol according to GB / T 4612-2008.

[0080] Step (2), Preparation of bio-based carboxyl-terminated polyester: 2192.1 g of bio-based isosorbide, 2187.15 g of bio-based 1,2-pentanediol (relative molecular weight 104.15), 1093.58 g of bio-based 1,5-pentanediol (relative molecular weight 104.15), and 10 g of isopropyl titanate were first put into a reactor equipped with a distillation column, condenser, and water separator, and heated to melt and the material temperature was raised to 110℃;

[0081] Then, 6672.1 grams of bio-based succinic acid (relative molecular weight 118.09) was added to the reactor, and N2 was introduced. Under N2 protection, the temperature was slowly raised to 210°C to carry out the esterification reaction, during which the temperature at the top of the distillation column did not exceed 100°C. When the temperature at the top of the distillation column was below 60°C and the material was clear and transparent, 10 grams of antioxidant triphenyl phosphite was added, and a vacuum was started to carry out the vacuum polycondensation reaction: the vacuum conditions were -0.088MPa to -0.090MPa, maintained for 6 hours, and the reaction temperature was slowly raised from 210°C to 250°C until no water was distilled out, indicating that the polycondensation reaction was completed.

[0082] The material was cooled to 80°C, the vacuum was ended, and it was filtered through a 100-mesh filter to obtain a bio-based carboxyl-terminated polyester.

[0083] Step (3), preparation of bio-based epoxy resin: 522 g of isosorbide glycidyl ether obtained in step (1), 1000 g of bio-based carboxyl-terminated polyester obtained in step (2), and 7.5 g of benzyltriethylammonium chloride were put into the reactor, the stirrer was turned on and stirred evenly, and then the temperature was slowly raised from room temperature to 80°C in 1 hour, and then slowly raised to 100°C in 2 hours. The reaction was carried out at 100-105°C for 3.5 hours. At this time, the acid value of the reaction system was ≤2.0 mgKOH / g, and the bio-based epoxy resin was obtained. The temperature was then lowered to below 60°C.

[0084] Step (4) Preparation of isosorbide bio-based epoxy acrylate: Add 147 g of acrylic acid, 7.5 g of benzyltriethylammonium chloride and 15 g of MEHQ to the bio-based epoxy resin obtained in step (3), turn on the stirrer and stir evenly, slowly raise the temperature from room temperature to 100°C within 2 hours, react at 100-105°C for 1.5 hours, then slowly raise the temperature to 115°C within 2 hours, react at 115-120°C for 4 hours until the acid value of the reaction system is ≤2.0 mgKOH / g, and obtain isosorbide bio-based epoxy acrylate. Cool down to 80°C to terminate the reaction;

[0085] Step (5) Preparation of isosorbide bio-based epoxy acrylate UV resin: Add 420 g of TPGDA to the isosorbide bio-based epoxy acrylate obtained in step (4), stir at 70-85℃ for 0.5 hours, then remove bubbles under vacuum (vacuum condition is -0.080 MPa), maintain for 3 hours until the resin liquid is clear and transparent, stop the vacuum, filter with a 100 mesh filter at 70℃ to obtain clear and transparent isosorbide bio-based epoxy acrylate UV resin with a viscosity of 6700 cps@60℃.

[0086] Example 2

[0087] raw materials

[0088] UV resin: Isosorbide bio-based epoxy acrylate UV resin prepared in Example 1; trifunctional polyurethane acrylate Photomer 6008 (IGM Resins).

[0089] UV monomers: propoxylated glycerol triacrylate (GPTA, Jiangsu Litian Technology Co., Ltd.); dipropylene glycol diacrylate (DPGDA, Jiangsu Litian Technology Co., Ltd.); phenolic ethoxyacrylate (Photomer 4039, IGMresins).

[0090] Photoinitiator 1173 (Aijianmeng Anqing Technology Development Co., Ltd.)

[0091] Additives: The mass ratio of Tego432 (Germany) and Tego920 (Germany) is 1:1.

[0092] Solvent: A mixed solvent of butyl acetate and methyl isobutyl ketone in a mass ratio of 1:1.

[0093] Instruments and equipment: LT-1002 UV curing machine, Lantian Special Lamp Development Co., Ltd.; QFZ paint film adhesion tester, Tianjin Kelian Materials Testing Machine Factory; RCA paper tape abrasion tester, Shanghai Modern Environmental Engineering Technology Research Institute; water bath; hot and cold circulation equipment.

[0094] Coating preparation: The coating ratio is shown in Table 1. Weigh a certain amount of UV resin, then add UV monomer, photoinitiator, additives, and solvent, stir evenly, and prepare the coating.

[0095] Table 1: Coating Proportions

[0096]

[0097] Coating preparation and curing: A 10cm × 10cm ABS plastic sheet was selected. First, a layer of thermoplastic acrylic resin white primer was sprayed onto its surface and baked at 60℃ for 3 hours. Then, a coating was sprayed onto its surface, with a coating thickness of approximately 20μm. The film was then cured on a UV curing machine (curing conditions: wavelength 365 nm, light intensity 600mW / cm²). 2 The curing process was carried out until the film was surface dry, and the curing time was recorded using the touch-drying method.

[0098] Performance testing

[0099] Curing time: The experiment used the finger-touch dry method. If the surface of the paint film does not feel sticky when lightly touched with a finger, it is considered that the surface of the paint film has been cured.

[0100] Pencil hardness: Determined according to GB 6739-86 Coated pencil hardness method.

[0101] Adhesion: Determined according to GB / T 1720-88, Test Method for Coating Adhesion. It is divided into 7 levels, with level 1 being the best and level 7 the worst.

[0102] Abrasion resistance: RCA test, 175g, 500±50 cycles.

[0103] Water resistance: Refer to national standard GB / T 1733 "Determination of water resistance of paint film".

[0104] Resistance to thermal cycling:

[0105] (1) Scope and description: Coatings may crack due to damp heat cycling or plasticizer loss, or both. Alternating exposure to a hot and cold chamber can be used to determine whether the coating is cracked and the degree of cracking.

[0106] (2) Instruments: ① Humidity chamber, ② Freezing chamber, ③ Colorimeter, ④ Cross-section instrument.

[0107] (3) Test method: ① Place the test sample in a humid heat chamber at 38℃ with a relative humidity of 100% for 24 hours. The sample should be placed at an angle of 0-30 degrees to the vertical direction, and the samples should not touch each other during the test. ② After 24 hours, immediately transfer the sample to a freezer at (-23±1.5)℃ for 20 hours. The transfer time should not exceed 30 seconds. ③ Take out the sample and place it at room temperature for 4 hours. This totals 48 hours as one cycle, during which a phase evaluation can be carried out. ④ Perform 15 cycles in total, and then test the appearance, color, and adhesion of the sample.

[0108] (4) Results indicate that the coating should be free from cracking, discoloration, decreased adhesion or other defects.

[0109] (5) Reference standard: American Standard AAMA 615-02, "Industry specifications, performance requirements and test methods for high-performance organic coatings on plastic profiles". [1] .

[0110] Results and Discussion

[0111] UV resin is the main component of UV coatings, and its performance largely determines the main properties of the cured coating film. In this experiment, trifunctional polyurethane acrylate Photomer 6008 and the isosorbide bio-based epoxy acrylate UV resin prepared in Example 1 were used to compose coatings with different formulations. The coating film properties are shown in Table 2.

[0112] Table 2: Effects of different ratios of Photomer 6008 and isosorbide-based bio-based epoxy acrylate UV resin on coating performance

[0113]

[0114] References:

[0115] 1. Yu Yingying. A Comprehensive Guide to Testing Methods and Instruments for the Coatings Industry. Beijing: Chemical Industry Press, 2007: 525.

[0116] Photoinitiator 1173 Description:

[0117] Manufacturer: Aijianmeng Anqing Technology Development Co., Ltd.;

[0118] Chemical name: 2-hydroxy-2-methyl-1-phenyl-1-propanone;

[0119] English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one;

[0120] CAS NO: 7473-98-5;

[0121] Molecular formula: C 10 H 12 O;

[0122] Molecular weight: 164.2

[0123] Chemical structural formula: ;

[0124] Technical Specifications:

[0125] Appearance: Colorless to pale yellow transparent liquid;

[0126] Purity: ≥99.0%;

[0127] Boiling point: 80-81℃;

[0128] Light transmittance: 425nm ≥ 99.0%; 500nm ≥ 99.3%;

[0129] Volatile matter: ≤0.2%;

[0130] Ash content: ≤0.10%;

[0131] Applications: 1173 is suitable for acrylic UV-cured varnish systems, such as varnishes for wood, metal, paper, and plastics. 1173 is particularly recommended for UV-cured coatings that require long-term exposure to sunlight and resistance to yellowing. Because 1173 is a liquid, it is very easy to blend, making it suitable for use in combination with other photoinitiators. The recommended addition level is 1-4% w / w.

Claims

1. An isosorbide-based bio-based epoxy acrylate, characterized in that: It is prepared from bio-based isosorbide and bio-based glycerol-based epichlorohydrin to obtain isosorbide glycidyl ether; bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid are used as raw materials to carry out esterification and vacuum polycondensation reactions in sequence to prepare bio-based carboxyl-terminated polyester; bio-based carboxyl-terminated polyester reacts with isosorbide glycidyl ether to obtain bio-based epoxy resin; bio-based epoxy resin reacts with acrylic acid to obtain UV-curable isosorbide bio-based epoxy acrylate.

2. A method for preparing isosorbide bio-based epoxy acrylate according to claim 1, characterized in that: Includes the following steps: Step (1): Isosorbide glycidyl ether is prepared by reacting bio-based isosorbide with bio-based glycerol via epichlorohydrin. Step (2): Using bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and bio-based succinic acid as raw materials, under N2 protection, the esterification reaction is carried out first in the presence of a catalyst, and then an antioxidant is added to carry out a vacuum polycondensation reaction to prepare bio-based end-carboxyl polyester. Step (3): Under the action of a catalyst, bio-based terminal carboxyl polyester reacts with isosorbide glycidyl ether to obtain bio-based epoxy resin. Step (4): In the presence of a catalyst and a polymerization inhibitor, bio-based epoxy resin reacts with acrylic acid to prepare UV-curable isosorbide bio-based epoxy acrylate.

3. The method for preparing isosorbide bio-based epoxy acrylate according to claim 2, characterized in that: In step (1), isosorbide glycidyl ether is prepared by the following method: bio-based isosorbide, bio-based glycerol-based epichlorohydrin and catalyst are added to a reactor to carry out a ring-opening etherification reaction; then sodium hydroxide solid is added in 3 to 10 batches to carry out a ring-closing reaction; after the reaction is completed, the solid is filtered, epichlorohydrin is removed by vacuum distillation, then dissolved in ethyl acetate, washed with water, ethyl acetate is removed by vacuum distillation, filtered, and isosorbide glycidyl ether is obtained. The mass ratio of the bio-based isosorbide to the bio-based glycerol-derived epichlorohydrin is [1.0×146.14]:[(2.0~30)×92.52]; the mass ratio of the bio-based isosorbide to sodium hydroxide is [1.0×146.14]:[(2.0~2.5)×40.01]; The catalyst is one or more of quaternary ammonium salt catalysts or quaternary phosphonium salt catalysts in any proportion; the quaternary ammonium salt catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, or tetrabutylammonium bromide; the quaternary phosphonium salt catalyst is triphenylethylphosphonium bromide or tetrabutylphosphonium bromide; the amount of catalyst used is 0.05wt% to 3wt% of the total mass of bio-based isosorbide and bio-based glycerol-based epichlorohydrin.

4. The method for preparing isosorbide bio-based epoxy acrylate according to claim 3, characterized in that: In step (1), the mass ratio of bio-based isosorbide to bio-based glycerol epichlorohydrin is [1.0×146.14]:[(2.0~6.0)×92.52]; the amount of catalyst used is 0.2~0.5wt% of the total mass of bio-based isosorbide and bio-based glycerol epichlorohydrin.

5. The method for preparing isosorbide bio-based epoxy acrylate according to claim 2, characterized in that: In step (2), the bio-based carboxyl-terminated polyester is prepared by the following method: First, bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and catalyst are added to a reactor equipped with a distillation column, condenser and water separator, heated to melt and the material temperature is raised to 110℃; then bio-based succinic acid is added, and under N2 protection, an esterification reaction is carried out at a temperature of 210~250℃. During the esterification reaction, the temperature at the top of the distillation column does not exceed 100℃. When the temperature at the top of the distillation column is lower than 60℃ and the material is clear and transparent, an antioxidant is added, and a vacuum polycondensation reaction is carried out at a temperature of 210~250℃ and a vacuum condition of -0.088~-0.098MPa; after the polycondensation reaction is completed, the mixture is filtered to obtain the bio-based carboxyl-terminated polyester. The mass ratio of the bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid is [1.5×146.14]:[(0.8~1.2)×2.1×104.15]:[(0.8~1.2)×1.05×104.15]:[(0.8~1.2)×5.65×118.09]; The catalyst is one or more of the following in any proportion: antimony glycolate, antimony triacetate, isopropyl titanate, n-butyl titanate, tin isooctanoate, dibutyltin dilaurate, dibutyltin oxide, monobutyltin oxide, bismuth isooctanoate, and lanthanum isooctanoate; the amount of the catalyst used is 0.01 wt% to 1 wt% of the total mass of bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid. The antioxidant is triphenyl phosphite; the amount of the antioxidant is 0.01 wt% to 1 wt% of the total mass of bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and bio-based succinic acid.

6. The method for preparing isosorbide bio-based epoxy acrylate according to claim 3, characterized in that: In step (2), the mass ratio of the bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid is [1.5×146.14]:[1×2.1×104.15]:[1×1.05×104.15]:[1×5.65×118.09]; The catalyst is one or more of isopropyl titanate, n-butyl titanate, antimony glycolate, and bismuth isooctanoate in any proportion; the amount of the catalyst used is 0.05 wt% to 0.085 wt% of the total mass of bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol, and bio-based succinic acid. The antioxidant is used in an amount of 0.05 wt% to 0.085 wt% of the total mass of bio-based isosorbide, bio-based 1,2-pentanediol, bio-based 1,5-pentanediol and bio-based succinic acid.

7. The method for preparing isosorbide bio-based epoxy acrylate according to claim 2, characterized in that: In step (3), the bio-based epoxy resin is prepared by the following method, including: adding isosorbide glycidyl ether, bio-based carboxyl-terminated polyester and catalyst into a reactor, stirring evenly, slowly raising the temperature to 80°C in 0.5 to 1 hour, and then slowly raising the temperature to 100°C in 1 to 3 hours, and reacting at a temperature of 100 to 105°C until the acid value of the reaction system is ≤2.0 mgKOH / g, to obtain the bio-based epoxy resin; The mass ratio of isosorbide glycidyl ether to bio-based carboxyl-terminated polyester is [(4.0~5.0)×epoxy equivalent of isosorbide glycidyl ether]:1000; The catalyst is one or a mixture of two or more Lewis base catalysts, quaternary ammonium salt catalysts, or quaternary phosphonium salt catalysts in any proportion; the Lewis base catalyst is triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, or tributylphosphine; the quaternary ammonium salt catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, or tetrabutylammonium bromide; the quaternary phosphonium salt catalyst is triphenylethylphosphonium bromide or tetrabutylphosphonium bromide; the amount of the catalyst is 0.1wt% to 3wt% of the total mass of isosorbide glycidyl ether and bio-based carboxyl-terminated polyester, preferably 0.1wt% to 0.5wt%.

8. The method for preparing isosorbide bio-based epoxy acrylate according to claim 2, characterized in that: In step (4), isosorbide bio-based epoxy acrylate is prepared by the following method: adding acrylic acid, catalyst and polymerization inhibitor to bio-based epoxy resin, stirring evenly, slowly raising the temperature to 100°C over 1 to 3 hours, reacting at 100 to 105°C for 1 to 2 hours, slowly raising the temperature to 115°C over 1 to 3 hours, and reacting at 115 to 120°C until the acid value of the reaction system is ≤2.0 mgKOH / g, to obtain isosorbide bio-based epoxy acrylate; The mass ratio of the acrylic acid and the bio-based carboxyl-terminated polyester is [(1.8~3.3)×72.06]:1000, preferably [(1.8~2.2)×72.06]:1000; The catalyst is one or a mixture of two or more Lewis base catalysts, quaternary ammonium salt catalysts, or quaternary phosphonium salt catalysts in any proportion; the Lewis base catalyst is triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, or tributylphosphine; the quaternary ammonium salt catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, or tetrabutylammonium bromide; the quaternary phosphonium salt catalyst is triphenylethylphosphonium bromide or tetrabutylphosphonium bromide; the amount of catalyst used is 0.1wt% to 3wt% of the total mass of bio-based isosorbide glycidyl ether, bio-based carboxyl-terminated polyester, and acrylic acid. The polymerization inhibitor is one or a mixture of two of p-hydroxyanisole and 2,6-di-tert-butyl-4-methylphenol in any proportion; the amount of polymerization inhibitor used is 0.01 wt% to 1 wt% of the total mass of isosorbide glycidyl ether, bio-based carboxyl-terminated polyester and acrylic acid.

9. An isosorbide-based bio-based epoxy acrylate UV resin, characterized in that: It is obtained by mixing isosorbide bio-based epoxy acrylate as described in claim 1 with UV monomers, stirring evenly, and removing bubbles under vacuum to obtain a clear and transparent isosorbide bio-based epoxy acrylate UV resin. The UV monomer is one or more of TPGDA, DPGDA, HDDA, and GPTA in any proportion; the amount of the UV monomer is 5wt% to 30wt% of the total mass of isosorbide glycidyl ether, carboxyl-terminated polyester, and acrylic acid.

10. The application of the isosorbide bio-based epoxy acrylate of claim 1 or the isosorbide bio-based epoxy acrylate UV resin of claim 9 in the preparation of UV coatings, inks, and adhesives.

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