High-performance photocurable FEVE fluorocarbon resin as well as synthesis method and application thereof

Abstract

The invention discloses a high-performance light-curable FEVE fluorocarbon resin and a synthesis method and application thereof.Fluorine olefin serves as a main monomer for synthesizing the fluorocarbon resin, meanwhile, alkyl vinyl monomers, epoxy vinyl monomers and fluorine-containing acrylate are introduced, fluorine atoms and fluorine-containing long side chains are introduced into a main chain of the obtained resin at the same time, and the fluorine-containing fluorine-containing fluorocarbon resin is obtained; the high-performance photocurable FEVE fluorocarbon resin is prepared from the fluorine-containing epoxy group and the epoxy group capable of reacting with acrylic acid to realize subsequent UV photocuring under the synergistic effect of all the components, and has the characteristics of good weather resistance, good mechanical properties, good hydrophobicity and high curing speed; the resin can be applied to the fields of repairing, packaging and the like with relatively high requirements on curing speed and corrosion resistance, so that the resin not only has high practicability, but also shows remarkable application value and potential in related application fields.

Description

Technical Field

[0001] The invention relates to a high-performance photocurable FEVE fluorocarbon resin and a synthesis method and application thereof. Background Art

[0002] FEVE type fluorocarbon resin has good weather resistance and stain resistance, and the introduction of other monomers also improves its processing performance. It can be prepared into coatings for use in heavy corrosion protection fields such as petrochemicals and bridge construction. Usually, in the process of preparing fluorocarbon resin into coatings, it is necessary to introduce groups that can be used for curing reactions into the structural system. The more common method is to introduce hydroxyl groups into the molecular chain. By adding a curing agent containing isocyanate, the isocyanate and the hydroxyl group are chemically combined to form a cross-linked structure in the molecular system, thereby achieving the purpose of enhancing the performance of the paint film. However, this process cannot be completed immediately in a short period of time. After the paint is applied, it is generally necessary to wait for a period of time before it can be used after the reactive groups are basically cross-linked. This limits the areas in which it can be applied. In addition, since organic solvents need to be added to adjust the viscosity during the preparation of the coating, most of these solvents are highly volatile and pose a great threat to humans and the environment.

[0003] Photocuring is the curing process of monomers, oligomers or polymer matrices under light induction. After adding photoinitiators to unsaturated polyester resins, the photoinitiators absorb the radiation energy of ultraviolet light and split into free radicals, which trigger polymerization and cross-linking reactions of prepolymers and solidify into network polymers in a very short time. As a result, coatings, inks, adhesives, etc. are converted from liquid to solid within seconds, which is efficient, economical, energy-saving and environmentally friendly. It is widely used in 3D printing, printing, circuit board painting, sign and label production, optical disc manufacturing, flat panel display, semiconductor lighting, electronic components, medical and other industries, and has huge market potential and application prospects.

[0004] At present, the common photocuring systems on the market mainly include epoxy acrylate, polyurethane acrylate resin, polyester acrylate resin, amino acrylate resin, polyether acrylate or vinyl resin, etc., and the most practically used are epoxy acrylate resin, polyurethane acrylate resin and polyester acrylate resin. Huang Qingxin et al. prepared a photocurable FEVE resin by directly reacting a commercial FEVE resin containing hydroxyl groups with acrylic acid. However, according to their experimental data, the acrylic acid conversion rate of this reaction system is slightly low, and multiple product purifications are required, and no specific performance research has been conducted. It can be seen that in the field of photocuring, there is still a huge gap in photocurable fluorocarbon resins, so the present invention has good market prospects and application value. Summary of the invention

[0005] The present invention aims at the synthesis of a photocurable FEVE type fluorocarbon resin and provides a photocurable fluorocarbon resin, a synthesis method and application thereof.

[0006] The technical solution adopted by the present invention is as follows:

[0007] A high-performance photocurable FEVE fluorocarbon resin, the components and molar content ratios are:

[0008] 1) The mole fraction is 30%-50% fluoroolefin;

[0009] 2) a mole fraction of 20% to 30% alkyl vinyl monomer;

[0010] 3) The molar fraction of epoxy vinyl monomer is 20%-30%;

[0011] 4) 0% to 10% fluorinated acrylate by mole fraction;

[0012] 5) The molar fraction of acrylic acid is 5%-20%.

[0013] The present invention uses fluoroolefin as the first monomer for synthesizing fluorocarbon resin, introduces fluorine atoms into the main chain, and endows the resin with good weather resistance, chemical corrosion resistance and other properties. The fluoroolefin is selected from chlorotrifluoroethylene or tetrafluoroethylene.

[0014] Alkyl vinyl monomers are used to reduce the crystallinity of the resin, improve the solubility of the resin in organic solvents, and give the resin good transparency, gloss, hardness and flexibility. The alkyl vinyl monomers that can be used include one or more of ethyl vinyl ether, isobutyl vinyl ether, cycloethyl vinyl ether, glycidyl vinyl ether, hydroxybutyl vinyl ether, vinyl acetate, vinyl butyrate, vinyl caproate or vinyl versatate.

[0015] The role of epoxy vinyl monomer is to introduce epoxy groups into the molecular chain. By adding a catalyst, the epoxy groups undergo a ring-opening reaction and polymerize with acrylic acid to achieve the introduction of unsaturated double bonds. At the same time, it can also improve the mobility of the molecular chain segments. The epoxy vinyl monomers selected are allyl glycidyl ether and glycidyl methacrylate.

[0016] The role of fluorinated acrylate is to introduce fluorinated long side chains into the molecular chain, which increases the flexibility of the main molecular chain and enhances the mechanical properties while increasing the fluorine content of the resin. The fluorinated acrylate monomers that can be used are one of perfluorobutyl acrylate, perfluorohexyl acrylate, perfluorodecyl acrylate, dodecafluoroheptyl acrylate, tridecafluorooctyl acrylate, tridecafluorooctyl methacrylate, and perfluorocyclohexyl methyl acrylate.

[0017] The role of acrylic acid is to introduce double bond groups into the molecular chain to facilitate subsequent UV light curing.

[0018] Furthermore, in the process of synthesizing the FEVE fluorocarbon resin in the present invention, a solvent and an initiator are also added, wherein the molar fraction of the initiator is 0.5-2.5%, and the initiator is selected from one or more of azo or organic peroxide, preferably azobisisobutyronitrile or benzoyl peroxide.

[0019] Furthermore, when introducing photocurable reactive groups into FEVE fluorocarbon resin, the present invention also needs to add polymerization inhibitor and catalyst, wherein the dosage of the polymerization inhibitor is 0.5%-2.5% of the acrylic acid; the dosage of the catalyst is 1%-5% of the total reactants.

[0020] As a preferred embodiment of the present invention, the polymerization inhibitor is 4-methoxyphenol.

[0021] The catalyst is selected from one of an amine nucleophilic reagent or a phosphine nucleophilic reagent, including triphenylphosphine, triethylamine, tetrabutylammonium bromide, tetramethylammonium bromide, and NN dimethylbenzylamine.

[0022] The solvent is selected from one or more of aromatic benzenes and aliphatic acetates, preferably xylene or butyl acetate or a mixture of the two.

[0023] Another object of the present invention is to claim a method for synthesizing the above-mentioned high-performance photocurable FEVE fluorocarbon resin, comprising the following steps:

[0024] a. Stir the reaction monomers fluoroolefin, alkyl vinyl monomer, epoxy vinyl monomer, fluorinated acrylate, solvent and initiator uniformly according to the ratio;

[0025] b. Add the liquid obtained in step a into a high pressure reactor and start heating the reaction; the reaction temperature is 60-80 ° C, the reaction time is 8-12 hours, and the pressure is 0.4-0.9 MPa;

[0026] c. After the reaction is completed, the product is collected, and the resin, acrylic acid, solvent, catalyst, and inhibitor obtained in step b are weighed and stirred evenly according to the ratio;

[0027] d. The mixture of step c is reacted at 90-110° C. for 2-6 hours. When the acid value no longer decreases, the reaction is considered to be complete, and the product is poured out to obtain a photocurable FEVE fluorocarbon resin.

[0028] The present invention also requests protection for the application of the above-mentioned high-performance photocurable FEVE fluorocarbon resin in the field of coatings. The specific method is: before spraying, add a photoinitiator with a molar fraction of 0.5%-5% and an active diluent with a molar fraction of 0%-20% to the high-performance photocurable FEVE fluorocarbon resin, and then spray it for photocuring.

[0029] The active diluent can be selected from IBOA, ACMO, HDDA, and PHEA.

[0030] The photoinitiator is selected from photoinitiator 184, photoinitiator 1173, and TPO.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The method of the present invention can be used to prepare high-performance photocurable FEVE fluorocarbon resin, which has the characteristics of good weather resistance, good mechanical properties, good hydrophobicity and fast curing speed. The resin can be used in the fields of repair, packaging and the like which have high requirements for curing speed and corrosion resistance. Therefore, the resin not only has high practicality, but also shows significant application value and potential in related application fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram of the synthesis principle of high-performance photocurable FEVE fluorocarbon resin. DETAILED DESCRIPTION

[0034] The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but should not be construed as limiting the present invention.

[0035] It should be understood that the terms or words used in the specification and claims should not be understood as having the meaning defined in the dictionary, but should be understood as having the meaning consistent with their meaning in the context of the present invention based on the following principle: the concept of the term can be appropriately defined by the inventor for the best explanation of the present invention.

[0036] The photoinitiator 184 in the present invention is 1-hydroxycyclohexyl phenyl ketone.

[0037] Photoinitiator 1173 is 2-hydroxy-2-methyl-1-phenyl-1-propanone.

[0038] The preparation process of high-performance photocurable FEVE fluorocarbon resin includes:

[0039] a. Stir the reaction monomers fluoroolefin, alkyl vinyl monomer, epoxy vinyl monomer, fluorinated acrylate, solvent and initiator uniformly according to the ratio;

[0040] b. Add the liquid obtained in step a into a high pressure reactor and start heating the reaction; the reaction temperature is 60-80°C, preferably 70-75°C, the reaction time is 8-12 hours, and the pressure is 0.4-0.9MPa;

[0041] c. After the reaction is completed, the product is collected, and the resin, acrylic acid, solvent, catalyst, and inhibitor obtained in step b are weighed and stirred evenly according to the ratio;

[0042] d. The mixture of step c is reacted at 90-110° C. for 2-4 hours. When the acid value no longer decreases, the reaction is considered to be complete, and the product is poured out to obtain a high-performance photocurable FEVE fluorocarbon resin.

[0043] Its principle is as follows Figure 1 shown.

[0044] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0045] Example 1

[0046] Take a mixed solvent of 50% chlorotrifluoroethylene, 30% vinyl acetate, 20% allyl glycidyl ether, 1.5% azobisisobutyronitrile, 50% butyl acetate and xylene by mass, add it into a closed reactor, stir and heat it to 70°C for 8 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 100% butyl acetate solution to the fluorocarbon resin, stir and heat it to 90°C, add 20% acrylic acid by mole fraction and 2% NN dimethylbenzylamine by mass after the materials are mixed, react at 90°C until the acid value is unchanged, pour out the reaction product, and obtain a photocurable FEVE fluorocarbon resin.

[0047] Example 2

[0048] Take a mixed solvent of 50% chlorotrifluoroethylene, 25% vinyl acetate, 20% allyl glycidyl ether, 5% octyl tridecafluoroacrylate, 1.5% azobisisobutyronitrile, 50% butyl acetate and xylene by mass, add it into a closed reactor, stir and heat it to 70°C for 8 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 100% butyl acetate solution to the fluorocarbon resin, stir and heat it to 90°C, add 20% acrylic acid by mole fraction and 2% NN dimethylbenzylamine by mass after the materials are mixed, react at 90°C until the acid value is unchanged, pour out the reaction product, and obtain a photocurable FEVE fluorocarbon resin.

[0049] Example 3

[0050] Take a mixed solvent of 40% chlorotrifluoroethylene, 30% vinyl acetate, 25% allyl glycidyl ether, 5% octyl tridecafluorooctyl acrylate, 1.5% azobisisobutyronitrile, 40% butyl acetate and xylene by mass, add it into a closed reactor, stir and heat it to 70°C for 8 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 100% butyl acetate solution to the fluorocarbon resin, stir and heat it to 90°C, add 25% acrylic acid by mole fraction and 2% NN dimethylbenzylamine by mass after the materials are mixed, react at 90°C until the acid value is unchanged, pour out the reaction product, and obtain a photocurable FEVE fluorocarbon resin.

[0051] Example 4

[0052] Take a mixed solvent of 40% chlorotrifluoroethylene, 30% vinyl acetate, 25% allyl glycidyl ether, 5% octyl tridecafluoroacrylate, 1.5% azobisisobutyronitrile, 40% butyl acetate and xylene by mass, add it into a closed reactor, stir and heat it to 60°C for 10 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 100% butyl acetate solution to the fluorocarbon resin and stir and heat it to 100°C. After the materials are mixed, add 25% acrylic acid by mole fraction and 2% NN dimethylbenzylamine by mass fraction, react at 100°C until the acid value is unchanged, pour out the reaction product, and obtain a photocurable FEVE fluorocarbon resin.

[0053] Example 5

[0054] Take a mixed solvent of 40% chlorotrifluoroethylene, 30% isobutyl vinyl ether, 25% allyl glycidyl ether, 5% octadecafluorooctyl acrylate, 1.5% azobisisobutyronitrile, 40% butyl acetate and xylene by mass, add it into a closed reactor, stir and heat it to 60°C for 10 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 100% butyl acetate solution to the fluorocarbon resin and stir and heat it to 100°C. After the materials are mixed, add 25% acrylic acid by mole fraction and 2% NN dimethylbenzylamine by mass fraction, react at 100°C until the acid value is unchanged, pour out the reaction product, and obtain a high-performance photocurable FEVE fluorocarbon resin.

[0055] Example 6

[0056] Take a mixed solvent of 40% chlorotrifluoroethylene, 25% isobutyl vinyl ether, 25% allyl glycidyl ether, 10% octadecafluorooctyl acrylate, 1.5% azobisisobutyronitrile, 40% butyl acetate and xylene, add it into a closed reactor, stir and heat it to 60°C for 10 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 100% butyl acetate solution to the fluorocarbon resin, stir and heat it to 100°C, add 25% acrylic acid and 2% NN dimethylbenzylamine after the materials are mixed, react at 100°C until the acid value is unchanged, pour out the reaction product, and obtain a high-performance photocurable FEVE fluorocarbon resin.

[0057] Example 7

[0058] Take a mixed solvent of 40% chlorotrifluoroethylene, 30% isobutyl vinyl ether, 25% allyl glycidyl ether, 5% octadecafluorooctyl acrylate, 1.5% azobisisobutyronitrile, 40% butyl acetate and xylene by mass, add it into a closed reactor, stir and heat it to 60°C for 12 hours to obtain a fluorocarbon resin. Add 0.5% 4-methoxyphenol and 30% butyl acetate solution to the fluorocarbon resin, stir and heat it to 110°C, add 25% acrylic acid by mole fraction and 2% NN dimethylbenzylamine by mass after the materials are mixed, react at 110°C until the acid value is unchanged, pour out the reaction product, and obtain a high-performance photocurable FEVE fluorocarbon resin.

[0059] Application Examples

[0060] As an application example of the present invention, the photocurable FEVE fluorocarbon resin prepared in Examples 1-7 is added with a photoinitiator having a molar fraction of 0.5%-5% and an active diluent having a molar fraction of 0%-20%, sprayed on an iron plate and photocured to obtain a fluorocarbon coating, and its mechanical properties, hydrophobic properties and acid and alkali resistance are tested according to GB / T6739-2006, GB / T1732-1993, GB / T9286-1998, GB / T6742-1986, and GB / T30693-2014 standards. The test results are shown in Table 1 below:

[0061] Table 1 Test results of the photocurable FEVE fluorocarbon resin obtained in each example

[0062]

[0063] At the same time, the high-performance photocurable FEVE fluorocarbon resin prepared in the embodiment of the present invention can be quickly cured when sprayed on an iron plate.

[0064] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. All equivalent embodiments or changes made without departing from the concept of the present invention should be included in the scope of protection of the present invention.

Claims

1. A high-performance photocurable FEVE fluorocarbon resin, characterized in that: The components and molar content ratios are: 1) The mole fraction is 30%-50% fluoroolefin; 2) a mole fraction of 20% to 30% alkyl vinyl monomer; 3) The molar fraction of epoxy vinyl monomer is 20%-30%; 4) 0% to 10% fluorinated acrylate by mole fraction; 5) The molar fraction of acrylic acid is 5%-20%.

2. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: The alkyl vinyl monomer is one or more of ethyl vinyl ether, isobutyl vinyl ether, cycloethyl vinyl ether, glycidyl vinyl ether, hydroxybutyl vinyl ether, vinyl acetate, vinyl butyrate, vinyl caproate or vinyl versatate.

3. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: Epoxy vinyl monomers include allyl glycidyl ether and glycidyl methacrylate.

4. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: The fluorine-containing acrylate monomer is one of perfluorobutyl acrylate, perfluorohexyl acrylate, perfluorodecyl acrylate, dodecafluoroheptyl acrylate, tridecafluorooctyl acrylate, tridecafluorooctyl methacrylate and perfluorocyclohexyl methyl acrylate.

5. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: Solvents and initiators are also added during the synthesis of FEVE fluorocarbon resins; the molar fraction of the initiator is 0.5-2.5%; the initiator is selected from one or more of azo or organic peroxides; and the solvent is selected from one or more of aromatic benzene and aliphatic acetate.

6. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: When introducing photocurable reactive groups into FEVE fluorocarbon resin, it is also necessary to add inhibitors and catalysts, wherein the amount of the inhibitor is 0.5%-2.5% of the acrylic acid; the amount of the catalyst is 1%-5% of the total reactants; the catalyst is selected from an amine nucleophilic reagent or a phosphine nucleophilic reagent.

7. The method for synthesizing the high-performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: The steps include: a. Stir the reaction monomers fluoroolefin, alkyl vinyl monomer, epoxy vinyl monomer, fluorinated acrylate, solvent and initiator uniformly according to the ratio; b. Add the liquid obtained in step a into a high pressure reactor and start heating the reaction; the reaction temperature is 60-80 ° C, the reaction time is 8-12 hours, and the pressure is 0.4-0.9MPa; c. After the reaction is completed, the product is collected, and the resin, acrylic acid, solvent, catalyst, and inhibitor obtained in step b are weighed and stirred evenly according to the ratio; d. The mixture of step c is reacted at 90-110° C. for 2-4 hours. When the acid value no longer decreases, the reaction is considered to be complete, and the product is poured out to obtain a photocurable FEVE fluorocarbon resin.

8. The use of the high-performance photocurable FEVE fluorocarbon resin according to claim 1 in the field of coatings, characterized in that: Before spraying, 0.5%-5% of a photoinitiator and 0%-20% of an active diluent are added to the high-performance photocurable FEVE fluorocarbon resin, and then the resin can be sprayed for photocuring.

9. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: Active diluents include IBOA, ACMO, HDDA, PHEA.

10. The high performance photocurable FEVE fluorocarbon resin according to claim 1, characterized in that: The photoinitiators selected are photoinitiator 184, photoinitiator 1173, and TPO.

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