UV (ultraviolet) resin prepared from ethoxyquinoline polymer as well as preparation method and application of UV resin

Abstract

The invention discloses a UV (ultraviolet) resin prepared from an ethoxyquin polymer, which is prepared by the following steps: by taking butyl acetate as a reaction solvent, reacting the ethoxyquin polymer with succinic anhydride under the action of a catalyst to prepare a carboxyl modified ethoxyquin polymer; the preparation method comprises the following steps: reacting bisphenol A epoxy resin with acrylic acid under the action of a catalyst and a polymerization inhibitor to prepare a composition of an epoxy acrylate intermediate and bisphenol A epoxy diacrylate; n-butyl acetate is used as a reaction solvent, under the action of a catalyst and a polymerization inhibitor, a carboxyl-modified ethoxyquinoline polymer reacts with a composition of an epoxy acrylate intermediate and bisphenol A type epoxy diacrylate until the acid value is smaller than or equal to 3.0 mgKOH / g, n-butyl acetate is removed through reduced pressure distillation, a UV reactive diluent is added for dissolution, filtering is conducted, and the UV resin is prepared. The UV resin prepared by taking the ethoxyquinoline polymer as the raw material can be applied as a raw material of a UV coating, ink and an adhesive.

Description

Technical Field

[0001] The invention belongs to the field of materials and relates to a UV resin prepared by using ethoxyquinoline polymer and a preparation method and application thereof. Background Art

[0002] Ethoxyquin is a very economical and effective antioxidant, which is currently widely used. It is not only used for food preservation, but also can slow down rubber aging, inhibit vitamin oxidation, and prevent fruit skin from discoloring due to oxidation. However, for every ton of ethoxyquin crude oil produced, 0.2 to 0.25 tons of distillation heavy component polymers will be produced, that is, distillation kettle residue, which is solid at room temperature and begins to melt into a viscous liquid when heated to 90 to 100°C. It is a hazardous waste. Treating it as solid waste not only puts pressure on the ecological environment, but also requires capital costs to treat solid waste. The resource utilization of heavy component polymers has always been a technical problem that has plagued the development of the industry.

[0003] With the rapid development of science and technology and the strict restrictions on solvents by environmental protection laws and regulations, UV light-curing polymer materials are receiving more and more attention. UV light-curing materials have excellent properties such as fast curing, low energy consumption, less pollution, and high efficiency. Therefore, they are widely used in the fields of coatings, printing, and electronics industries, and have developed rapidly in recent years. Epoxy acrylate (EA) is prepared by ring-opening esterification of epoxy group-containing compounds and acrylic acid or methacrylic acid. It is an important light-curing oligomer with low irritation, fast curing speed, high transparency, high hardness and other excellent properties. It is widely used in light-curing inks, coatings, adhesives and other fields, and is widely used in the United States, Japan, and developed European countries. In recent years, with the rise of ultraviolet light curing technology in my country, new light-curing materials have become more and more widely used as raw materials for UV coatings, inks, and adhesives, and their usage is increasing year by year.

[0004] If UV technology can be combined with the heavy components of ethoxyquinoline distillation to achieve resource utilization of the heavy components of ethoxyquinoline distillation polymers, then the technical problems that have been plaguing the development of the industry will find a feasible solution. Summary of the invention

[0005] The object of the present invention is to provide a UV resin prepared by using ethoxyquinoline polymer in view of the above-mentioned deficiencies in the prior art.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A UV resin prepared from ethoxyquinoline polymer, comprising ethoxyquinoline polymer modified epoxy acrylate, bisphenol A type epoxy diacrylate, and UV active diluent, is prepared by the following method: using butyl acetate as a reaction solvent, under the action of a catalyst, the ethoxyquinoline polymer reacts with succinic anhydride to obtain a carboxyl-modified ethoxyquinoline polymer; under the action of a catalyst and an inhibitor, the bisphenol A type epoxy resin reacts with acrylic acid to obtain an epoxy acrylate intermediate shown in formula I and a The invention discloses a method for preparing a composition of bisphenol A epoxy diacrylate; using butyl acetate as a reaction solvent, in the presence of a catalyst and an inhibitor, reacting a composition of a carboxyl-modified ethoxyquinoline polymer with an epoxy acrylate intermediate and bisphenol A epoxy diacrylate until the acid value is ≤3.0 mgKOH / g, removing butyl acetate by reduced pressure distillation, adding a UV active diluent to dissolve, filtering, and obtaining a UV resin containing ethoxyquinoline polymer-modified epoxy acrylate, bisphenol A epoxy diacrylate and a UV active diluent.

[0008] Ethoxyquinoline is generally prepared by condensing p-aminophenyl ether with acetone under the action of p-toluenesulfonic acid as a catalyst, using toluene as a reaction solvent. After the reaction is completed, a Na2CO3 aqueous solution with a concentration of about 0.1 g / mL is added to stand for stratification, and the upper organic layer is taken. The organic layer enters a distillation kettle for distillation, and toluene, a fraction 1 with an ethoxyquinoline content of less than 78%, a fraction 2 with an ethoxyquinoline content of 78% or less and less than 88% (the distillation temperature is 190±5°C and the vacuum degree is -0.096MPa±0.001MPa), and a finished product with an ethoxyquinoline content of 88% or less (the distillation temperature is 190±5°C and the vacuum degree is -0.096MPa±0.001MPa) are distilled out in sequence, and the ethoxyquinoline distillation kettle residue is obtained in a distillation tower.

[0009] The ethoxyquinoline polymer is obtained by extraction using the residue of ethoxyquinoline distillation kettle as raw material and one selected from xylene or butyl acetate as extraction solvent.

[0010] Another object of the present invention is to provide a method for preparing a UV resin prepared from the ethoxyquinoline polymer, comprising:

[0011] Step (1), pretreatment of ethoxyquinoline still residue: mixing butyl acetate with ethoxyquinoline still residue, stirring and heating to 50-100° C., dissolving at 50-100° C. for 1-3 hours, cooling, filtering, and obtaining a butyl acetate solution of ethoxyquinoline polymer;

[0012] Step (2), in the presence of a catalyst, using butyl acetate as a reaction solvent, the ethoxyquinoline polymer reacts with succinic anhydride to obtain a carboxyl-modified ethoxyquinoline polymer;

[0013] Step (3), reacting bisphenol A epoxy resin with acrylic acid under the action of a catalyst and a polymerization inhibitor to obtain a composition of an epoxy acrylate intermediate represented by formula I and a bisphenol A epoxy diacrylate represented by formula II;

[0014]

[0015] Step (4), using butyl acetate as a reaction solvent, reacting a carboxyl-modified ethoxyquinoline polymer with a composition of an epoxy acrylate intermediate and bisphenol A epoxy diacrylate in the presence of a catalyst and an inhibitor until an acid value is ≤3.0 mgKOH / g, removing butyl acetate by distillation under reduced pressure, adding a UV active diluent to dissolve, and filtering to obtain a UV resin containing ethoxyquinoline polymer-modified epoxy acrylate, bisphenol A epoxy diacrylate and a UV active diluent.

[0016] In step (1), the mass ratio of butyl acetate to ethoxyquinoline distillation kettle residue is 1:0.5 to 1:2.0, preferably 1:1.0 to 1:1.6.

[0017] The amine value of the butyl acetate solution of the ethoxyquinoline polymer is 80-110 mgKOH / g. The theoretical amine value of ethoxyquinoline is 258 mgKOH / g.

[0018] Preferably, the pretreatment of the ethoxyquinoline still residue is as follows: butyl acetate and ethoxyquinoline still residue are mixed, heated to 60-90° C. with stirring, dissolved at 60-90° C. for 1-2 hours, cooled after uniform dissolution, and filtered to remove black solid particles formed by high-temperature carbonization of organic matter to obtain a butyl acetate solution of ethoxyquinoline polymer.

[0019] Preferably, the mixture is cooled to 40°C and filtered.

[0020] The filtration adopts filter paper with a pore size of 20 microns.

[0021] In step (2), It represents ethoxyquinoline polymer, and ethoxyquinoline polymer reacts with succinic anhydride, that is, the secondary amine group of ethoxyquinoline polymer reacts with succinic anhydride to undergo acylation reaction, and the carboxyl functional group is introduced into the ethoxyquinoline polymer to obtain the carboxyl-modified ethoxyquinoline polymer. The principle is as follows:

[0022]

[0023] The reaction temperature is 70-110° C., the end point of the reaction is when the acid value decreases to a constant value, and generally, the reaction time is 1-5 hours.

[0024] After the reaction is completed, the mixture is cooled to 40°C and discharged.

[0025] The mass ratio of the butyl acetate solution of the ethoxyquinoline polymer to succinic anhydride is (56.1×1000 / Av):100.07; wherein 100.07 is the relative molecular weight of succinic anhydride, 56.1 is the relative molecular weight of KOH, and Av is the amine value measured by the butyl acetate solution of the ethoxyquinoline polymer.

[0026] The catalyst is one of Lewis base catalysts, quaternary ammonium salt catalysts and quaternary phosphonium salt catalysts, or a mixture of two or more of them in any proportion.

[0027] The Lewis base catalysts include triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, tributylphosphine, etc.; the quaternary ammonium salt catalysts include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc.; the quaternary phosphonium salt catalysts include triphenylethylphosphonium bromide, tetrabutylphosphonium bromide, etc.

[0028] The dosage of the catalyst is 0.1wt% to 2wt% of the total mass of the butyl acetate solution of the ethoxyquinoline polymer and succinic anhydride.

[0029] In step (3), the epoxy group of the present invention is excessive to make the acrylic acid react completely. The mass ratio of the bisphenol A epoxy resin to the acrylic acid is (Eq×2):[(1.0-1.25)×72]; wherein Eq is the epoxy equivalent of the bisphenol A epoxy resin, i.e., the mass of the resin containing one epoxy group (g / equivalent), and 72 is the relative molecular weight of the acrylic acid.

[0030] The reaction temperature is 60-120°C, the end point of the reaction is when the acid value of the reaction system drops to ≤0.5 mgKOH / g, and the conversion rate of the acrylic acid addition reaction is above 99.5%. Generally, the reaction time is 1-8 hours.

[0031] After the reaction was completed, the mixture was cooled to below 50°C.

[0032] The catalyst is one of Lewis bases, quaternary ammonium salts and quaternary phosphonium salts, or a mixture of two or more of them in any proportion.

[0033] The Lewis base catalysts include triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, tributylphosphine, etc.; the quaternary ammonium salt catalysts include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc.; the quaternary phosphonium salt catalysts include triphenylethylphosphonium bromide, tetrabutylphosphonium bromide, etc.

[0034] The dosage of the catalyst is 0.1wt% to 2wt% of the total weight of the bisphenol A epoxy resin and acrylic acid.

[0035] The polymerization inhibitor is MEHQ (p-hydroxyanisole) or BHT (2,6-di-tert-butyl-4-methylphenol).

[0036] The dosage of the polymerization inhibitor is 100-5000ppm of the total mass of the bisphenol A epoxy resin and acrylic acid.

[0037] Under the action of catalyst and polymerization inhibitor, bisphenol A epoxy resin is ring-opened and reacts with acrylic acid to produce epoxy acrylate intermediate (I) with reserved epoxy group; at the same time, part of bisphenol A epoxy diacrylate (II) is generated. Although bisphenol A epoxy diacrylate (II) does not have reserved epoxy group, it is also an effective component and is a UV resin itself; epoxy acrylate intermediate (I) with reserved epoxy group and bisphenol A epoxy diacrylate (II) do not need to be separated and processed, and directly enter the next step of reaction as a composite. Bisphenol A epoxy diacrylate (II) itself is a UV resin, and as an effective component, it enters step (4) and becomes part of the target product UV resin.

[0038]

[0039]

[0040] In step (4), the mass ratio of the composition of the epoxy acrylate intermediate and bisphenol A epoxy diacrylate to the butyl acetate solution of the carboxyl-modified ethoxyquinoline polymer is [(Eq×2)+(1.0~1.25)×72]:[(56.1×1000 / Av+100.07)×(0.5~1.25)], preferably [(Eq×2)+(1.0~1.25)×72] :[(56.1×1000 / Av+100.07)×(0.6~1.0)]; wherein Eq is the epoxy equivalent of bisphenol A epoxy resin, that is, the mass of resin containing one epoxy group (g / equivalent), 72 is the relative molecular weight of acrylic acid, 56.1 is the relative molecular weight of KOH, Av is the amine value measured by the butyl acetate solution of ethoxyquinoline polymer, and 100.07 is the relative molecular weight of succinic anhydride.

[0041] The reaction temperature is 60° C. to 120° C., the end point of the reaction is an acid value ≤ 3.0 mgKOH / g, and generally, the reaction time is 1 to 10 hours, preferably 3 to 8 hours.

[0042] After the reaction of step (3) is completed, the intermediate does not need to be purified, and the butyl acetate solution of ethoxyquinoline polymer is directly added, and the catalyst and the inhibitor are added to react. The amount of the catalyst in step (3) is based on the total mass of the reactants bisphenol A epoxy resin and acrylic acid; the amount of the catalyst in step (4) (including the amount of the catalyst added in step (2), the catalyst added in step (3) and the amount of the catalyst added in step (4)) is based on the total mass of the composition obtained by the reaction in step (3) and the butyl acetate solution of ethoxyquinoline polymer in step (2). The inhibitor added in step (3) is also the same as the catalyst, and will enter step (4) to play a role. The amount of the inhibitor in step (4) is the sum of the amount of the inhibitor added in step (3) and the amount of the inhibitor added in step (4).

[0043] The catalyst is one of Lewis bases, quaternary ammonium salts and quaternary phosphonium salts, or a mixture of two or more of them in any proportion.

[0044] The Lewis base catalysts include triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, tributylphosphine, etc.; the quaternary ammonium salt catalysts include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, etc.; the quaternary phosphonium salt catalysts include triphenylethylphosphonium bromide, tetrabutylphosphonium bromide, etc.

[0045] The total amount of catalyst in step (2), step (3) and step (4) is 0.1wt% to 2wt% of the total mass of the butyl acetate solution of the composition of epoxy acrylate intermediate and bisphenol A epoxy diacrylate and carboxyl-modified ethoxyquinoline polymer.

[0046] The catalysts in step (2), step (3) and step (4) may be the same or different.

[0047] The polymerization inhibitor is MEHQ (p-hydroxyanisole) or BHT (2,6-di-tert-butyl-4-methylphenol), and the total amount of the polymerization inhibitor used in step (3) and step (4) is 100 to 5000 ppm of the total amount of the butyl acetate solution of the composition of the epoxy acrylate intermediate and bisphenol A epoxy diacrylate and the carboxyl-modified ethoxyquinoline polymer.

[0048] The polymerization inhibitors in step (3) and step (4) may be the same or different.

[0049] The epoxy group of the epoxy acrylate intermediate (I) obtained in step (3) reacts with the carboxyl group (-COOH) of the carboxyl-modified ethoxyquinoline polymer in step (2) according to the following principle:

[0050]

[0051] The conditions for removing butyl acetate by reduced pressure distillation are: vacuum degree -0.098MPa, temperature 120°C.

[0052] The UV active diluent accounts for 10-30% of the total mass of the target product UV resin, preferably 20-20.5%. The UV active diluent is also an effective component and becomes a part of the target product UV resin. The UV active diluent is tripropylene glycol diacrylate (TPGDA).

[0053] Specifically, after the reaction is completed, the temperature is lowered to 80° C., and butyl acetate is recovered by reduced pressure distillation to 120° C. Under the conditions of vacuum degree of -0.098 MPa and temperature of 120° C., no butyl acetate is distilled out for 10 minutes, and the distillation is terminated. The temperature is lowered to 100° C., and a UV active diluent accounting for 10 to 30% of the total mass of the target product UV resin, preferably 20 to 20.5% is added. The mixture is stirred and dissolved for 15 minutes, and the mixture is discharged and filtered to obtain a UV resin containing ethoxyquinoline polymer-modified epoxy acrylate, bisphenol A epoxy diacrylate and UV active diluent.

[0054] The filtration adopts 100 mesh gauze.

[0055] Another object of the present invention is to provide the use of the UV resin prepared from the ethoxyquinoline polymer in the preparation of UV coatings, inks or adhesives.

[0056] Compared with the prior art, the present invention has the following beneficial effects:

[0057] Ethoxyquinoline distillation kettle residue is a kind of chemical solid waste. The present invention firstly dissolves the ethoxyquinoline distillation kettle residue with butyl acetate, extracts organic molecules, filters out high-temperature carbides, and then acylates the secondary amine functional groups of the ethoxyquinoline polymer with succinic anhydride to introduce carboxyl groups, which are further used to modify epoxy acrylate, thereby realizing resource utilization and turning waste into treasure.

[0058] Due to the introduction of the rigid nitrogen-containing heteroatom quinoline ring structure, the UV resin prepared with ethoxyquinoline polymer as raw material has excellent properties such as high hardness, wear resistance, scratch resistance, heat resistance, and weather resistance after curing, and can be used as a raw material for UV coatings, inks, and adhesives. DETAILED DESCRIPTION

[0059] Determination of amine value by perchloric acid-acetic acid titration [1] :

[0060] Weigh about 0.2g (accurate to 0.0001g) of sample, place it in a 250mL conical flask, add about 25mL of glacial acetic acid solution, stir magnetically to fully dissolve, add 2 to 3 drops of crystal violet indicator (dissolve 0.5g of crystal violet in 100mL of glacial acetic acid), and titrate with the prepared calibrated 0.1mol / L perchloric acid standard solution until the solution changes from purple to pure blue, which is the titration end point. Titrate in parallel two or three times and take the average value.

[0061] The calculation formula of amine value is:

[0062]

[0063] Where:

[0064] C—concentration of perchloric acid standard solution, mol / L;

[0065] V—volume of perchloric acid standard solution consumed by the sample, mL;

[0066] m—mass of sample, g;

[0067] 56.1—The mass of potassium hydroxide per mole.

[0068] Example 1

[0069] The first step is to pretreat the ethoxyquinoline still residue: 2000 g of butyl acetate and 2000 g of ethoxyquinoline still residue are added to a 5L dissolving kettle, stirred and heated to 90°C, dissolved at 90°C for 2 hours, and after uniform dissolution, cooled to 40°C, filtered with a filter paper with a pore size of 20 μm, and black solid particles formed by high-temperature carbonization of organic matter are filtered out to obtain 3808 g of butyl acetate solution of ethoxyquinoline polymer, and the amine value is 93.1 mgKOH / g determined by perchloric acid-acetic acid titration method;

[0070] In the second step, 1205.16 g of butyl acetate solution of the ethoxyquinoline polymer obtained in the first step, 4 g of benzyltriethylammonium chloride, and 200.14 g of succinic anhydride were added to a 2L reactor, and the temperature was raised to 90-100° C. for reaction for 2 hours. The acid value of the sample was 81.8 mgKOH / g. After continuing the reaction for 0.5 hour, the acid value of the sample was 79.7 mgKOH / g. After continuing the reaction for another 0.5 hour, the acid value of the sample was 79.7 mgKOH / g. The acid value decreased to a constant value, the reaction was terminated, and the mixture was cooled to 40° C. The discharge was 1393.7 g (1409.3 g of the feed was added);

[0071] The mass ratio of the butyl acetate solution of ethoxyquinoline polymer to succinic anhydride is (56.1×1000 / Av):100.07; wherein 100.07 is the relative molecular weight of succinic anhydride, 56.1 is the relative molecular weight of KOH (in the amine value calculation formula), and Av is the amine value measured by the butyl acetate solution of ethoxyquinoline polymer.

[0072] The third step, in a 2L reactor, 370 grams of bisphenol A epoxy resin (epoxy equivalent 185), 1.5 grams of benzyltriethylammonium chloride, 0.15 grams of p-hydroxyanisole, 74 grams of acrylic acid were dropped, stirring was started, and the mixture was warmed to 70°C, incubated for 1 hour, then warmed to 80°C and incubated for 1 hour, then warmed to 110°C and incubated for 4 hours, and the acid value was ≤0.5mg / KOH at this time, and cooled to below 50°C to obtain a total of 445.65 grams of epoxy acrylate intermediate (I) and bisphenol A epoxy diacrylate (II) compositions of reserved epoxy groups. Without separation and purification, the next step reaction was directly carried out.

[0073] The fourth step is to put 680 grams of the product obtained in the second step, 0.1 grams of benzyltriethylammonium chloride and 0.1 grams of p-hydroxyanisole into the 2L reactor of the third step, heat it to 80°C, keep it warm for 1 hour, then heat it to 100°C and keep it warm for 1 hour, then heat it to 118°C and keep it warm for 5 hours, at this time, the acid value is ≤3.0mgKOH / g, cool it to 80°C, start vacuum distillation to recover butyl acetate to 120°C, when the vacuum degree is -0.098Mpa and the temperature is 120°C, continue for 10 After no butyl acetate was distilled out after 15 minutes, the distillation was terminated, the temperature was lowered to 100°C, 208.7 g of tripropylene glycol diacrylate (TPGDA) was added, and the mixture was stirred and dissolved for 15 minutes. The mixture was filtered with a 100-mesh gauze to obtain 1038.5 g of a clear, transparent viscous liquid, which was a UV resin prepared from ethoxyquinoline polymer (containing ethoxyquinoline polymer-modified epoxy acrylate, bisphenol A type epoxy diacrylate, and tripropylene glycol diacrylate), and 286 g of butyl acetate was recovered.

[0074] Example 2

[0075] raw materials

[0076] UV resin: UV resin prepared from ethoxyquinoline polymer in Example 1; difunctional aliphatic polyurethane acrylate (PH6630, Agenmon Group, with good toughness and flexibility).

[0077] UV monomers: ethoxylated pentaerythritol tetraacrylate (5EO-PETA, Jiangsu Litian Technology Co., Ltd. of Agenmon Group); 1,6-hexanediol diacrylate (HDDA, Jiangsu Litian Technology Co., Ltd. of Agenmon Group); tetrahydrofuran acrylate (THFA, Jiangsu Litian Technology Co., Ltd. of Agenmon Group).

[0078] Photoinitiator: 1173, Aigenmeng Anqing Technology Development Co., Ltd.

[0079] Additives: Tego432, Tego920, German Tego, add Tego432 and Tego920 into the coating in a mass ratio of 1:1.

[0080] Mixed solvent: Butyl acetate, toluene, and methyl isobutyl ketone are mixed in a mass ratio of 1:1:1.

[0081] Instruments and Equipment

[0082] LT-1002 UV curing machine, Lantian Special Light Development Co., Ltd.; QFZ paint film adhesion tester, Tianjin Kelian Material Testing Machine Factory; RCA paper tape abrasion tester, Shanghai Modern Environmental Engineering Technology Research Institute; water bath; hot and cold cycle equipment.

[0083] Coating preparation

[0084] Weigh a certain amount of UV resin, then add UV monomer, photoinitiator, and additives, stir evenly, and prepare the coating. The coating ratio is shown in Table 1.

[0085] Table 1: Coating ratio

[0086]

[0087]

[0088] Coating preparation and curing

[0089] A 10cm×10cm ABS plastic sheet was selected, and a layer of thermoplastic acrylic resin white primer was first sprayed on its surface and baked at 60℃ for 3h. Then, a UV topcoat was sprayed on its surface. The coating thickness was about 20μm. It was cured on a light curing machine to make the cured film surface dry. The dry-to-touch method was used to characterize it, and the curing time was recorded.

[0090] Performance Testing

[0091] Curing time: The experiment adopts the finger-touch drying method, which is to touch the surface of the paint film with your finger. If it does not feel sticky, it is considered that the surface of the paint film has been cured.

[0092] Pencil hardness: Determined according to GB 6739-86 coating pencil hardness method.

[0093] Adhesion: Determined according to GB / T 1720-88 coating adhesion test method. Divided into 7 levels, with 1 being the best and 7 being the worst.

[0094] Abrasion resistance: RCA test, 175g, 500±50 times.

[0095] Boiling water resistance: refer to the national standard GB / T 1733 "Determination of water resistance of paint films".

[0096] Resistant to hot and cold cycles:

[0097] (1) Scope and description: Plastic paints tend to crack due to moisture-heat cycles or loss of plasticizers, or both. Whether the paint film cracks and the extent of cracking can be determined by alternating exposure to a warm and cold box.

[0098] (2) Instruments: ① Humidity chamber, ② Freezing chamber, ③ Colorimeter, ④ Grid marker.

[0099] (3) Determination method: ① Place the test sample in a hot box with a relative humidity of 100% and a temperature of 38℃ for 24 hours. The sample should be placed at an angle of 0-30 degrees to the vertical direction, and the panels should not touch each other during the test. ② After 24 hours, immediately move the sample to a freezer at (-23±1.5)℃ for 20 hours. The transfer time should not exceed 30 seconds at most. ③ Take out the sample and place it at room temperature for 4 hours. In this way, a total of 48 hours is one cycle, during which stage evaluation can be carried out. ④ Carry out 15 cycles in total, and then test the appearance, color and adhesion of the sample.

[0100] (4) Result indication: The coating should be free of cracking, discoloration, decreased adhesion or other defects.

[0101] (5) Reference standard: American Standard AAMA 615-02 "Industry Specifications, Performance Requirements and Test Methods for High-Performance Organic Coatings on Plastic Profiles". [2]

[0102] Results and Discussion

[0103] UV resin is the main body of UV coating, and its performance basically determines the main properties of the cured coating. In this experiment, UV resin prepared by ethoxyquinoline polymer and difunctional aliphatic polyurethane acrylate resin were used to form coatings with different formulations. The coating properties are shown in Table 2.

[0104] Table 2: Effect of different ratios of UV resin prepared from ethoxyquinoline polymer and difunctional aliphatic polyurethane acrylate on coating properties

[0105]

[0106] Photoinitiator 1173 Description:

[0107] Manufacturer: Aijianmeng Anqing Technology Development Co., Ltd.;

[0108] Chemical name: 2-Hydroxy-2-methyl-1-phenyl-1-propanone;

[0109] English name: 2-Hydroxy-2-methyl-1-phenyl-propan-1-one;

[0110] CAS NO: 7473-98-5;

[0111] Molecular formula: C 10 H 12 O;

[0112] Relative molecular weight: 164.2;

[0113] Chemical structure:

[0114] Technical indicators:

[0115] Appearance: Colorless to light yellow transparent liquid;

[0116] Purity: ≥99.0%;

[0117] Boiling point: 80-81°C (degrees Celsius);

[0118] Light transmittance: 425nm ≥ 99.0%; 500nm ≥ 99.3%;

[0119] Volatile matter: ≤0.2%;

[0120] Ash content: ≤0.10%;

[0121] application:

[0122] 1173 is suitable for acrylic light-curing varnish systems, such as varnishes for wood, metal, paper, plastic, etc. 1173 is especially recommended for UV-curing coatings that need to withstand long-term sunlight and resist yellowing. Since 1173 is a liquid and very easy to blend, it is suitable for compounding with other photoinitiators. The recommended addition amount is 1-4% w / w.

[0123] References:

[0124] [1] Zhang Lanfen, Zhou Xiuli. Determination of amine value of epoxy curing agent [J]. Coatings Technology and Abstracts, 2004(1):40-41.

[0125] [2] Yu Yingying. Complete list of testing methods and instruments for coatings industry. Beijing: Chemical Industry Press, 2007: 525.

Claims

1. A UV resin prepared from an ethoxyquinoline polymer, characterized in that: The invention contains ethoxyquinoline polymer modified epoxy acrylate, bisphenol A type epoxy diacrylate and UV active diluent, and is prepared by the following method: using butyl acetate as a reaction solvent, under the action of a catalyst, the ethoxyquinoline polymer reacts with succinic anhydride to obtain a carboxyl-modified ethoxyquinoline polymer; under the action of a catalyst and an inhibitor, the bisphenol A type epoxy resin reacts with acrylic acid to obtain a composition of an epoxy acrylate intermediate shown in formula I and bisphenol A type epoxy diacrylate shown in formula II; using butyl acetate as a reaction solvent, under the action of a catalyst and an inhibitor, the carboxyl-modified ethoxyquinoline polymer reacts with the composition of the epoxy acrylate intermediate and bisphenol A type epoxy diacrylate to an acid value of ≤3.0 mgKOH / g, removing butyl acetate by reduced pressure distillation, adding a UV active diluent to dissolve, filtering, and obtaining a UV resin containing ethoxyquinoline polymer modified epoxy acrylate, bisphenol A type epoxy diacrylate and UV active diluent; 2. A method for preparing a UV resin prepared from the ethoxyquinoline polymer according to claim 1, characterized in that: include: Step (1), mixing butyl acetate and ethoxyquinoline distillation kettle residue, stirring and heating to 50-100° C., dissolving at 50-100° C. for 1-3 hours, cooling, filtering, and obtaining a butyl acetate solution of ethoxyquinoline polymer; Step (2), in the presence of a catalyst, using butyl acetate as a reaction solvent, the ethoxyquinoline polymer reacts with succinic anhydride to obtain a carboxyl-modified ethoxyquinoline polymer; Step (3), reacting bisphenol A epoxy resin with acrylic acid under the action of a catalyst and a polymerization inhibitor to obtain a composition of an epoxy acrylate intermediate represented by formula I and a bisphenol A epoxy diacrylate represented by formula II; Step (4), using butyl acetate as a reaction solvent, reacting a carboxyl-modified ethoxyquinoline polymer with a composition of an epoxy acrylate intermediate and bisphenol A epoxy diacrylate in the presence of a catalyst and an inhibitor until an acid value is ≤3.0 mgKOH / g, removing butyl acetate by distillation under reduced pressure, adding a UV active diluent to dissolve, and filtering to obtain a UV resin containing ethoxyquinoline polymer-modified epoxy acrylate, bisphenol A epoxy diacrylate and a UV active diluent.

3. The method for preparing UV resin according to claim 2, characterized in that: In step (1), the mass ratio of butyl acetate to ethoxyquinoline distillation kettle residue is 1:0.5 to 1:2.0, preferably 1:1.0 to 1:1.

6.

4. The method for preparing UV resin according to claim 2, characterized in that: In step (1), the amine value of the butyl acetate solution of the ethoxyquinoline polymer is 80 to 110 mgKOH / g.

5. The method for preparing UV resin according to claim 2, characterized in that: In step (2), the mass ratio of the butyl acetate solution of the ethoxyquinoline polymer to succinic anhydride is (56.1×1000 / Av):100.07; wherein Av is the amine value of the butyl acetate solution of the ethoxyquinoline polymer; The catalyst is one of Lewis base catalysts, quaternary ammonium salt catalysts, and quaternary phosphonium salt catalysts, or a mixture of two or more of them in any proportion; the Lewis base catalyst is triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, and tributylphosphine; the quaternary ammonium salt catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, and tetrabutylammonium bromide; the quaternary phosphonium salt catalyst is triphenylethylphosphonium bromide and tetrabutylphosphonium bromide; The amount of the catalyst is 0.1wt% to 2wt% of the total mass of the butyl acetate solution of the ethoxyquinoline polymer and succinic anhydride; The reaction temperature is 70-110° C., and the end point of the reaction is when the acid value decreases to a constant value.

6. The method for preparing UV resin according to claim 2, characterized in that: In step (3), the mass ratio of the bisphenol A epoxy resin to acrylic acid is (Eq×2):[(1.0-1.25)×72]; wherein Eq is the epoxy equivalent of the bisphenol A epoxy resin; The reaction temperature is 60-120°C, and the end point of the reaction is when the acid value of the reaction system drops to ≤0.5 mgKOH / g; The catalyst is one of Lewis bases, quaternary ammonium salts, and quaternary phosphonium salts, or a mixture of two or more of them in any proportion; the Lewis base catalyst is triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, and tributylphosphine; the quaternary ammonium salt catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, and tetrabutylammonium bromide; the quaternary phosphonium salt catalyst is triphenylethylphosphonium bromide and tetrabutylphosphonium bromide; The amount of the catalyst used is 0.1wt% to 2wt% of the total mass of bisphenol A epoxy resin and acrylic acid; The inhibitor is MEHQ or BHT; The dosage of the polymerization inhibitor is 100-5000ppm of the total mass of the bisphenol A epoxy resin and acrylic acid.

7. The method for preparing UV resin according to claim 2, characterized in that: In step (4), the mass ratio of the composition of the epoxy acrylate intermediate and bisphenol A epoxy diacrylate to the butyl acetate solution of the carboxyl-modified ethoxyquinoline polymer is [(Eq×2)+(1.0~1.25)×72]:[(56.1×1000 / Av+100.07)×(0.5~1.25)], preferably [(Eq×2)+(1.0~1.25)×72]:[(56.1×1000 / Av+100.07)×(0.6~1.0)]; wherein Eq is the epoxy equivalent of the bisphenol A epoxy resin, and Av is the amine value of the butyl acetate solution of the ethoxyquinoline polymer; The reaction temperature is 60°C to 120°C, and the end point of the reaction is an acid value ≤ 3.0 mgKOH / g; The catalyst is one of Lewis bases, quaternary ammonium salts, and quaternary phosphonium salts, or a mixture of two or more of them in any proportion; the Lewis base catalyst is triethylamine, N,N-dimethylbenzylamine, N,N-diethylbenzylamine, triphenylphosphine, and tributylphosphine; the quaternary ammonium salt catalyst is benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, and tetrabutylammonium bromide; the quaternary phosphonium salt catalyst is triphenylethylphosphonium bromide and tetrabutylphosphonium bromide; The total amount of the catalyst in step (2), step (3) and step (4) is 0.1 wt% to 2 wt% of the total mass of the butyl acetate solution of the composition of the epoxy acrylate intermediate and bisphenol A epoxy diacrylate and the carboxyl-modified ethoxyquinoline polymer; The inhibitor is MEHQ or BHT. The total amount of the inhibitor used in step (3) and step (4) is 100 to 5000 ppm of the total amount of the butyl acetate solution of the composition of the epoxy acrylate intermediate and bisphenol A epoxy diacrylate and the carboxyl-modified ethoxyquinoline polymer.

8. The method for preparing UV resin according to claim 2, characterized in that: In step (4), the conditions for removing butyl acetate by reduced pressure distillation are: vacuum degree -0.098MPa, temperature 120°C.

9. The method for preparing UV resin according to claim 2, characterized in that: In step (4), the UV active diluent accounts for 10-30% of the total mass of the target product UV resin, preferably 20-20.5%; the UV active diluent is tripropylene glycol diacrylate.

10. Use of the UV resin prepared from the ethoxyquinoline polymer according to claim 1 in the preparation of UV coatings, inks or adhesives.

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