CN102924662A - Anti-fog type ultraviolet light curing polyacrylate copolymer preparation method - Google Patents

Abstract

The invention discloses a preparation method of an anti-fog type ultraviolet light curing polyacrylate copolymer, which belongs to the technical field of ultraviolet light curing and polymerization. In the present invention, 2-acrylamide-2 methyl propane sulfonic acid, hydroxy acrylate and other monomers are used to prepare the sulfonic acid group-containing hydroxy acrylate copolymer (A1) through solution free radical polymerization; then polyisocyanate and mono The reaction of hydroxy acrylate produces unsaturated group-containing monoisocyanate (A2); finally, the unsaturated group-containing monoisocyanate (A2) is grafted to the sulfonic acid group-containing hydroxy acrylate copolymer (A1), and finally the anti- Fog-type UV-curable polyacrylate copolymer. The copolymer has simple synthesis process conditions and excellent hydrophilic anti-fog performance, and can be used as a main component of anti-fog paint to increase the anti-fog performance of the paint.

Description

A kind of preparation method of anti-fog type ultraviolet light curing polyacrylate copolymer

technical field

The invention relates to a preparation method of an anti-fog type ultraviolet light curing polyacrylate copolymer, belongs to the technical field of ultraviolet light curing and polymerization, and particularly relates to acrylate solution copolymerization. the

Background technique

When the glass surface enters a high-temperature environment from a low-temperature environment, due to the condensation of water vapor, fog droplets will be generated on the surface, which hinders the transmission of light. This is the mechanism of fog generation. the

At present, the mechanism of anti-fog coating can be divided into hydrophobic anti-fog mechanism and hydrophilic anti-fog mechanism. The hydrophobic anti-fog mechanism is to use the low surface energy of the coating to make water form freely rolling water droplets on the surface of the coating, so that the water droplets can leave the surface to achieve the anti-fog effect. The mechanism of hydrophilic anti-fog is to use water to fully spread on the surface of the coating to form a spreading water layer to achieve the anti-fog effect. the

The patent literature with application number 200910040585.9 discloses a UV-curable anti-fog coating composition and its preparation method, that is, water-based polyurethane acrylate is prepared by using polyethylene glycol, diisocyanate and hydroxyl-terminated acrylate, and then compounded with hydrophobic Resin, photoinitiator and reactive diluent to prepare photocurable anti-fog coating. the

The patent document with application number 200910088318.9 discloses an anti-fog coating, a special anti-fog coating composition and a method for preparing anti-fog products. It uses polyacrylic acid/methacrylic acid as the main hydrophilic monomer, supplemented by 2-acrylamide-2-methylpropanesulfonic acid (AMPS), glycidyl acrylate, polyvinyl alcohol and other monomers for aqueous polymerization, and then added The cross-linking agent or coupling agent is heated and cured to prepare a coating with anti-fog effect. the

Contents of the invention

Although AMPS has been used as an anti-fog performance monomer, there is no copolymerization method to prepare photocurable polyacrylate containing AMPS. Aiming at the existing technical problems, the present invention uses DMF as a solvent so that it can be dissolved in the system as a comonomer, thereby preparing the polyacrylate anti-fog coating resin containing AMPS. the

The technical scheme of the present invention is as follows: by reacting the compound (A2) that has 1 isocyanate group and 1 or above ethylenically unsaturated groups in 1 molecule by the hydroxyl acrylate copolymer (A1) containing sulfonic acid group Obtain an anti-fog type UV-curable polyacrylate copolymer;

The hydroxy acrylate copolymer (A1) containing sulfonic acid group is to obtain acrylate copolymer by free radical polymerization of 2-acrylamide-2 methyl propane sulfonic acid, hydroxy acrylate and other monomers; Hydroxyacrylate monomers include one or more of 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate; The other monomers mentioned include one or more of 2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate, tert-butyl methacrylate, and styrene;

The compound (A2) having one isocyanate group and one or more ethylenically unsaturated groups in one molecule is obtained by reacting polyisocyanates containing isocyanate groups with different degrees of activity and monohydroxy acrylate monomers Monoisocyanate containing unsaturated groups; the isocyanate includes one or more of isophorone diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; the monohydroxy type acrylate monomer used includes acrylic acid-2 One or more of -hydroxyethyl ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate;

The anti-fog type UV-curable polyacrylate copolymer is grafted by the compound (A2) having one isocyanate group and one or more ethylenically unsaturated groups in one molecule through the reaction of the isocyanate group contained in it and the hydroxyl group. Prepared on the hydroxyacrylate copolymer (A1) containing sulfonic acid groups;

A kind of synthetic steps of anti-fog type ultraviolet light curing polyacrylate copolymer comprises the following steps:

(1) Preparation of sulfonic acid-containing hydroxyacrylate copolymer (A1): 2-acrylamide-2-methylpropanesulfonic acid, hydroxyacrylate, other monomers and free radical polymerization initiators are dissolved in a polymerization solvent dropwise into a reaction vessel preheated to 70-90°C with a polymerization solvent, and react for 6-8 hours until the end of the reaction; the free radical initiator includes azobisisobutyronitrile, dibenzoyl peroxide One or more of them; the solvent is N, N-dimethylformamide; the 2-acrylamide-2 methylpropanesulfonic acid content of the hydroxyacrylate copolymer (A1) containing sulfonic acid groups The ratio is 1-30%;

(2) Preparation of compound (A2) having 1 isocyanate group and 1 or more ethylenically unsaturated groups in 1 molecule: Add the mixture of polyisocyanate and polymerization inhibitor into the reaction vessel under stirring , warming up to 30-50°C, drop the mixture of hydroxyacrylate, catalyst and solvent into the reaction vessel drop by drop, control the drop rate, finish dropping within 2-3h, react for 3-5h, until the reaction ends; the catalyst It is one or more of dibutyltin dilaurate, triethylamine, and stannous octoate, and the dosage is 0.01-0.05% of the mass sum of polyisocyanate and monohydroxy acrylate; the polymerization inhibitor includes 4-methoxy One or more of phenol, hydroquinone, and resorcinol, the dosage is 0.1% to 0.5% of the mass of monohydroxy acrylate;

(3) Preparation of anti-fog polyacrylate copolymer: under stirring, the product obtained in step (1) is heated up to 70°C, and the product obtained in step (2) is dropped into the reaction vessel drop by drop , Control the dropping rate, finish dropping within 1~2h, and then react for 3~5h until the end of the reaction. the

Technical effect of the present invention is as follows:

In the preparation method of the present invention, AMPS is used as a hydrophilic monomer to improve surface energy, styrene, 2-hydroxyethyl methacrylate and isooctyl acrylate are used as polymer main monomers, and DMF is used as a polymerization solvent , Using AIBN as a free radical polymerization initiator to prepare polyacrylate containing AMPS. By adjusting the feeding amount of AMPS, the hydrophilic monomer content of the obtained polymer and the anti-fog performance of the film-formed product are adjusted. The invention has mild polymerization conditions, controllable polymer structure and performance, excellent polymer product performance, convenient preparation and operation, and good product application performance. the

Figure 1 is the infrared spectrum of the anti-fog UV-curable polyacrylate copolymer. the

Fig. 2 is the nuclear magnetic resonance spectrum of the anti-fog type UV-curable polyacrylate copolymer. the

Figure 3 is the water contact angle of anti-fog UV-curable polyacrylate copolymer. the

Figure 4 is an anti-fog photo of an anti-fog type UV-curable polyacrylate copolymer. the

Specific implementation method

Below in conjunction with example the present invention is described in further detail, but the present invention is not limited thereto. the

Example 1:

Add 10g of solvent to a four-necked flask equipped with a magnetic stirrer, a thermometer, and a spherical condenser, and mix 2.500g of 2-acrylamide-2 methylpropanesulfonic acid, 10.974g of hydroxyethyl methacrylate, and 10.363g of isoacrylate Octyl ester, 5.622g methyl methacrylate, 0.821g initiator azobisisobutyronitrile and 15g solvent were added to the dropping funnel. Raise the temperature to 90°C, drop in the comonomer drop by drop with a dropping funnel, control the dropping speed, and finish dropping within 2 to 3 hours. Reaction to 6 ~ 8h, until the end of the reaction. the

22.229g (0.10mol) of isophorone diisocyanate and 0.07g (0.2%) of the polymerization inhibitor p-hydroxyanisole were added to a three-necked flask equipped with a magnetic stirrer and a thermometer, and the temperature was raised to 40°C. A mixture of 14.315 g (0.11 mol) of hydroxyethyl methacrylate and 0.004 g (0.02%) of dibutyltin dilaurate as a catalyst was dropped into the funnel drop by drop, and the drop rate was controlled to complete the drop within 2 to 3 hours. After the dropwise reaction, the NCO content reaches the predetermined value, and the reaction ends. Produces isocyanate-containing unsaturated monomers. the

Add the unsaturated monomer containing isocyanate group dropwise to the copolymerization product heated to 70°C through the dropping funnel, drop it within 2 hours, and react until the NCO content reaches the predetermined value, and the reaction ends. the

Example 2:

Add 10g of solvent to a four-necked flask equipped with a magnetic stirrer, a thermometer, and a spherical condenser, and mix 1.500g of 2-acrylamide-2 methylpropanesulfonic acid, 10.974g of hydroxyethyl methacrylate, and 11.363g of isoacrylate Octyl ester, 5.622g methyl methacrylate, 0.821g initiator azobisisobutyronitrile and 15g solvent were added to the dropping funnel. Raise the temperature to 90°C, drop the comonomer drop by drop with a dropping funnel, control the dropping speed, and finish dropping within 2 to 3 hours. Reaction to 6 ~ 8h, until the end of the reaction. the

22.229g (0.10mol) of isophorone diisocyanate and 0.07g (0.2%) of the polymerization inhibitor p-hydroxyanisole were added to a three-necked flask equipped with a magnetic stirrer and a thermometer, and the temperature was raised to 40°C. A mixture of 14.315 g (0.11 mol) of hydroxyethyl methacrylate and 0.004 g (0.02%) of dibutyltin dilaurate as a catalyst was dropped into the funnel drop by drop, and the drop rate was controlled to complete the drop within 2 to 3 hours. After the dropwise reaction, the NCO content reaches the predetermined value, and the reaction ends. Produces isocyanate-containing unsaturated monomers. the

Add the unsaturated monomer containing isocyanate group dropwise to the copolymerization product heated to 70°C through the dropping funnel, drop it within 2 hours, and react until the NCO content reaches the predetermined value, and the reaction ends. the

Example 3:

Add 10g of solvent to a four-necked flask equipped with a magnetic stirrer, a thermometer, and a spherical condenser, and mix 0.500g of 2-acrylamide-2 methylpropanesulfonic acid, 10.974g of hydroxyethyl methacrylate, and 12.363g of isoacrylate Octyl ester, 5.622g methyl methacrylate, 0.821g initiator azobisisobutyronitrile and 15g solvent were added to the dropping funnel. Raise the temperature to 90°C, drop in the comonomer drop by drop with a dropping funnel, control the dropping speed, and finish dropping within 2 to 3 hours. Reaction to 6 ~ 8h, until the end of the reaction. the

22.229g (0.10mol) of isophorone diisocyanate and 0.07g (0.2%) of the polymerization inhibitor p-hydroxyanisole were added to a three-necked flask equipped with a magnetic stirrer and a thermometer, and the temperature was raised to 40°C. A mixture of 14.315 g (0.11 mol) of hydroxyethyl methacrylate and 0.004 g (0.02%) of dibutyltin dilaurate as a catalyst was dropped into the funnel drop by drop, and the drop rate was controlled to complete the drop within 2 to 3 hours. After the dropwise reaction, the NCO content reaches the predetermined value, and the reaction ends. Produces isocyanate-containing unsaturated monomers. the

Add the unsaturated monomer containing isocyanate group dropwise to the copolymerization product heated to 70°C through the dropping funnel, drop it within 2 hours, and react until the NCO content reaches the predetermined value, and the reaction ends. the

Example 4:

Add 10g solvent, 10.974g hydroxyethyl methacrylate, 12.863g isooctyl acrylate, 5.622g methyl methacrylate, 0.821g initiator couple Azodiisobutyronitrile and 15 g of solvent were added to the dropping funnel. Raise the temperature to 90°C, drop in the comonomer drop by drop with a dropping funnel, control the dropping speed, and finish dropping within 2 to 3 hours. Reaction to 6 ~ 8h, until the end of the reaction. the

22.229g (0.10mol) of isophorone diisocyanate and 0.07g (0.2%) of the polymerization inhibitor p-hydroxyanisole were added to a three-necked flask equipped with a magnetic stirrer and a thermometer, and the temperature was raised to 40°C. Add the mixture of 14.315g (0.11mol) hydroxyethyl methacrylate and catalyst dibutyltin dilaurate 0.004g (0.02%) drop by drop into the funnel, control the drop rate, and finish the drop within 2-3h. After the dropwise reaction, the NCO content reaches the predetermined value, and the reaction ends. Produces isocyanate-containing unsaturated monomers. the

Add the unsaturated monomer containing isocyanate group dropwise to the copolymerization product heated to 70°C through the dropping funnel, drop it within 2 hours, and react until the NCO content reaches the predetermined value, and the reaction ends. the

Embodiment 5:

Add 10g of solvent to a four-necked flask equipped with a magnetic stirrer, a thermometer, and a spherical condenser, and mix 1.000g of 2-acrylamide-2 methylpropanesulfonic acid, 10.974g of hydroxyethyl methacrylate, and 11.863g of isoacrylate Octyl ester, 5.622g methyl methacrylate, 0.821g initiator azobisisobutyronitrile and 15g solvent were added to the dropping funnel. Raise the temperature to 90°C, drop in the comonomer drop by drop with a dropping funnel, control the dropping speed, and finish dropping within 2 to 3 hours. Reaction to 6 ~ 8h, until the end of the reaction. the

22.229g (0.10mol) of isophorone diisocyanate and 0.07g (0.2%) of the polymerization inhibitor p-hydroxyanisole were added to a three-necked flask equipped with a magnetic stirrer and a thermometer, and the temperature was raised to 40°C. A mixture of 14.315 g (0.11 mol) of hydroxyethyl methacrylate and 0.004 g (0.02%) of dibutyltin dilaurate as a catalyst was dropped into the funnel drop by drop, and the drop rate was controlled to complete the drop within 2 to 3 hours. After the dropwise reaction, the NCO content reaches the predetermined value, and the reaction ends. Produces isocyanate-containing unsaturated monomers. the

Add the unsaturated monomer containing isocyanate group dropwise to the copolymerization product heated to 70°C through the dropping funnel, drop it within 2 hours, and react until the NCO content reaches the predetermined value, and the reaction ends. the

After making the polyacrylate copolymer obtained in Example 1 into a photocuring formula, the contact angle test results of the photocured film are shown in the figure; . Through the test of the contact angle of the polyacrylate copolymer UV-cured film, it can be seen that the water contact angle of the cured film is only about 10 degrees, which has excellent hydrophilicity, that is, has a good anti-fog effect. the

The above-mentioned embodiments are used to illustrate the present invention, rather than to limit the present invention. Within the spirit of the present invention and the protection scope of the claims, any modification and change made to the present invention will fall into the protection scope of the present invention. the

Claims (8)

1. a kind of preparation method of anti-fog type ultraviolet-curable polyacrylate copolymer, it is characterized in that have 1 isocyanate group and 1 or 1 by the hydroxyl acrylate copolymer (A1) containing sulfonic acid group and 1 molecule A novel copolymer with anti-fog effect obtained by reacting a compound (A2) with more than one ethylenically unsaturated group. 2. anti-fogging type UV-curable polyacrylate copolymer according to claim 1, is characterized in that, the hydroxyacrylate copolymer (A1) that contains sulfonic acid group is made of 2-acrylamide-2 methyl Propanesulfonic acid, hydroxy acrylate and other monomers are prepared by free radical polymerization of acrylate copolymers; the hydroxy acrylate monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid One or more of -2-hydroxypropyl ester and -2-hydroxypropyl methacrylate; the other monomers include -2-ethylhexyl acrylate, butyl acrylate, methyl methacrylate, methyl One or more of tert-butyl acrylate and styrene. 3. The anti-fog type UV-curable polyacrylate copolymer according to claim 1, characterized in that, the compound having 1 isocyanate group and 1 or more ethylenically unsaturated groups in said 1 molecule (A2) is a monoisocyanate containing unsaturated groups obtained by reacting polyisocyanates containing isocyanate groups with different degrees of activity and monohydroxy type acrylate monomers; the isocyanates include isophorone diisocyanate, toluene diisocyanate, diphenyl One or more of methyl methane diisocyanates; the monohydroxy acrylate monomers used include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, methyl One or more of 2-hydroxypropyl acrylate. 4. anti-fog type ultraviolet light-curable polyacrylate copolymer according to claim 1, is characterized in that, anti-fog type ultraviolet light-curable polyacrylate copolymer is to have 1 isocyanate group and 1 or The compound (A2) having more than one ethylenically unsaturated group is prepared by reacting the isocyanate group contained therein with the hydroxyl group and grafting onto the sulfonic acid group-containing hydroxyacrylate copolymer (A1). 5. anti-fogging type UV-curable polyacrylate copolymer according to claim 1, is characterized in that, the used initiator of the free radical polymerization of the hydroxyl acrylate copolymer (A1) containing sulfonic acid group comprises azo One or more of diisobutyronitrile and dibenzoyl peroxide, the solvent used is N,N-dimethylformamide, and the reaction temperature is 70-90°C. 6. The anti-fog type UV-curable polyacrylate copolymer according to claim 1, wherein the compound having one isocyanate group and one or more ethylenically unsaturated groups in one molecule The catalyst used in the nucleophilic addition reaction of (A2) is one or more of dibutyltin dilaurate, triethylamine, and stannous octoate, and the consumption is 0.01% to 0.05% of the mass sum of polyisocyanate and monohydroxy acrylate; The polymerization inhibitor used includes one or more of 4-methoxyphenol, hydroquinone, and resorcinol, the dosage is 0.1% to 0.5% of the mass of monohydroxy acrylate, and the reaction temperature is 30 ~ 50°C. 7. anti-fogging type UV-curable polyacrylate copolymer according to claim 1, is characterized in that, the 2-acrylamide-2 methylpropane of the hydroxyacrylate copolymer (A1) of described sulfonic acid group The proportion of sulfonic acid content is 1-30%. 8. The anti-fog type UV-curable polyacrylate copolymer according to claims 1-6, which is used as a main component of an anti-fog coating formulation to enhance the anti-fog property of the coating formulation.

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