Method for modifying urethane acrylate by triazine naphthalene compound, urethane acrylate polymer and application thereof

Abstract

The invention provides a method for modifying polyurethane acrylate with a triazine naphthalene compound, a polyurethane acrylate polymer and application of the polyurethane acrylate polymer. The method comprises the following steps: (1) adding isocyanate and polyol in a molar ratio of (1.8-2.2): 1 into a reaction kettle, then adding an organic solvent of which the mass is the same as the total mass of the isocyanate and the polyol, and uniformly mixing to obtain an initial solution; the isocyanate is prepared from a triazine naphthalene compound with an isocyanate group and diisocyanate; the polyhydric alcohol comprises a triazine naphthalene compound with a hydroxyl group and dihydric alcohol; (2) under protective gas, dropwise adding a catalyst into the initial solution, and carrying out heating reaction to obtain a reaction solution; (3) keeping the temperature unchanged, and continuously adding hydroxyl acrylate and a polymerization inhibitor into the reaction solution for blocking until the content of isocyanate functional groups is lower than 0.1%; and cooling, neutralizing to be neutral, carrying out reduced pressure distillation to remove the solvent, carrying out immersion cleaning with deionized water, filtering and drying to obtain the polyurethane acrylate polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of polyurethane acrylate preparation, more particularly, to a method for modifying polyurethane acrylate with triazine naphthalene compounds, polyurethane acrylate polymer and its application. BACKGROUND

[0002] At present, polyurethane acrylate resin is a resin that has developed rapidly in recent years, which has good flexibility, elasticity, wear resistance and adhesion, and has been widely used in topcoat and adhesive fields. However, the polyurethane acrylate resin has poor water resistance, mechanical strength, aging resistance and high temperature resistance, so it is a technical direction in the field to study the method for modifying the polyurethane acrylate in order to improve the comprehensive performance of the polyurethane acrylate. SUMMARY

[0003] The purpose of the present application is to provide a method for modifying polyurethane acrylate with triazine naphthalene compounds, which successfully participates in the polymerization reaction of polyurethane acrylate with three functional groups of triazine naphthalene compounds, so that the modified polyurethane acrylate has improved adhesion, boiling resistance, aging resistance, mechanical strength and volume stability, and has good low dielectric properties. Therefore, the modification method expands the application range of polyurethane acrylate polymer, and is suitable for electronic field.

[0004] In order to achieve the above purpose, the present application provides a method for modifying polyurethane acrylate with triazine naphthalene compounds, which comprises the following steps:

[0005] (1) adding isocyanate and polyol with a molar ratio of 1.8-2.2:1 into a reaction kettle, adding organic solvent with the same mass as the total mass of isocyanate and polyol, and mixing uniformly to obtain a primary solution; the isocyanate comprises triazine naphthalene compounds with isocyanate groups and diisocyanate; the polyol comprises triazine naphthalene compounds with hydroxyl groups and dihydric alcohol;

[0006] (2) adding catalyst dropwise into the primary solution under protective gas, and heating to obtain a reaction solution;

[0007] (3) keeping the temperature unchanged, continuously adding hydroxy acrylate and polymerization inhibitor into the reaction solution for end-capping until the content of isocyanate functional groups is less than 0.1%, cooling, neutralizing to neutral, removing the solvent by reduced pressure distillation, and then immersing in deionized water, filtering and drying to obtain polyurethane acrylate polymer.

[0008] Further, the hydroxyl group bearing triazine naphthalene compound is 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine, and / or the isocyanate group bearing triazine naphthalene compound is 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine.

[0009] Further, the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate and hexamethylene diisocyanate.

[0010] Further, the dihydric alcohol is one or a combination of polytetrahydrofuran, polypropylene glycol, neopentyl glycol, polyethylene glycol and polycaprolactone diol.

[0011] Further, the catalyst is one or a combination of stannous octoate, dibutyl tin dilaurate and triethanolamine; and / or, the polymerization inhibitor is hydroquinone or tert-butyl hydroquinone; and / or, the organic solvent is one of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, cyclohexane, ethyl acetate, pentane, heptane and hexane.

[0012] Further, the hydroxyl acrylate monomer is one or a combination of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

[0013] The present application also provides a polyurethane acrylate polymer obtained according to the above method.

[0014] The present application also provides a topcoat comprising the above polyurethane acrylate polymer.

[0015] The present application also provides an adhesive comprising the above polyurethane acrylate polymer.

[0016] The present application also provides an application of the above polyurethane acrylate polymer, which can be used in electronics, electrical appliances, machinery, furniture, buildings or road surfaces.

[0017] The present application has the following advantages:

[0018] The present application utilizes 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine and 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine as polyols and isocyanates respectively to participate in the polymerization reaction of polyurethane acrylate, so that the modified polyurethane acrylate body exhibits improved adhesion, boiling water resistance, aging resistance, mechanical strength and volume stability during use, and also has good low dielectric properties. Therefore, the body modification method expands the use range of polyurethane acrylate polymers and is suitable for the electronic field.

[0019] Other features and advantages of the present application will be apparent in the detailed description section below. DETAILED DESCRIPTION

[0020] In order to make the above-mentioned objectives, features and advantages of the present application more apparent and comprehensible, the specific embodiments of the present application are described in detail below.

[0021] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the spirit of the present application, so the present application is not limited to the specific embodiments disclosed below.

[0022] In a first aspect, a method for modifying a triazine naphthalene compound polyurethane acrylate according to the present application comprises the following steps:

[0023] (1) adding isocyanate and polyol in a molar ratio of 1.8-2.2:1 into a reaction kettle, then adding an organic solvent with the same mass as the total mass of the isocyanate and polyol, and mixing uniformly to obtain a primary solution; the isocyanate comprises a triazine naphthalene compound with isocyanate groups and diisocyanate; the polyol comprises a triazine naphthalene compound with hydroxyl groups and dihydric alcohol;

[0024] (2) flushing the reaction kettle by vacuumizing and filling with inert gas 2-4 times respectively, then adding a catalyst drop by drop into the primary solution through a feeder under stirring after sealing, heating to 70-90℃, and keeping the reaction time for 2-4h to obtain a reaction solution; the amount of catalyst is 0.05-0.08% of the total mass of isocyanate and dihydric alcohol;

[0025] (3) keeping the temperature unchanged, continuously adding hydroxy acrylate and a polymerization inhibitor to the reaction solution for end-capping until the content of isocyanate functional groups is less than 0.1%, then cooling to room temperature, adding a neutralizing agent triethylamine to neutralize to neutral, removing the solvent by reduced pressure distillation, and obtaining the polyurethane acrylate polymer by deionized water immersion, filtration and drying; the molar ratio of hydroxy acrylate to isocyanate is 0.8-1.2:1.

[0026] In an embodiment, the triazine naphthalene compound with hydroxyl groups is 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine, and the preparation method comprises the following steps: dissolving 6-hydroxy-naphthalene-1-carbonitrile in diphenyl sulfone in a reaction container according to a molar ratio, adding methanesulfonic acid dropwise under argon protection and 0℃, continuously stirring until the liquid phase is uniform, then slowly warming to room temperature for 12h, adding ammonia water to adjust the pH value to neutral, filtering, washing with deionized water and drying to obtain 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine.

[0027] In one embodiment, the isocyanate group-containing triazine naphthalene compound is 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine, and the preparation method thereof comprises the following steps: dissolving 1 mol of 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine in DNF, controlling the reaction temperature at 95°C under argon protection, adding 0.35 mol of hexamethylene diisocyanate drop by drop, keeping the reaction for 4 h, and distilling off the DNF solvent to obtain 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine.

[0028] In one embodiment, the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate, and hexamethylene diisocyanate.

[0029] In one embodiment, the diol is one or a combination of polytetrahydrofuran, polypropylene glycol, neopentyl glycol, polyethylene glycol, and polycaprolactone diol.

[0030] In one embodiment, the catalyst is one or a combination of stannous octoate, dibutyl tin dilaurate, and triethanolamine.

[0031] In one embodiment, the polymerization inhibitor is hydroquinone or tert-butyl hydroquinone. In one embodiment, the organic solvent is one of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, cyclohexane, ethyl acetate, pentane, heptane, and hexane.

[0032] In one embodiment, the hydroxy acrylate monomer is one or a combination of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.

[0033] In a second aspect, a polyurethane acrylate polymer obtained according to the above method is provided.

[0034] In a third aspect, a topcoat comprising the above polyurethane acrylate polymer is provided.

[0035] In a fourth aspect, an adhesive comprising the above polyurethane acrylate polymer is provided.

[0036] In a fifth aspect, the above polyurethane acrylate polymer is used in electronics, electrical appliances, machinery, furniture, buildings, or road surfaces.

[0037] The method for modifying a triazine naphthalene compound polyurethane acrylate, the polyurethane acrylate polymer, and the application thereof are described in detail below with reference to specific embodiments.

[0038] Preparation Example

[0039] (1) Preparation of 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine

[0040] Dissolve 6-hydroxy-naphthalene-1-carbonitrile in diphenyl sulfone in a reaction vessel in a molar ratio, drop 6-hydroxy-naphthalene-1-carbonitrile in methanesulfonic acid under argon protection and 0℃, continue stirring until the liquid phase is uniform, then slowly warm to room temperature for 12h, adjust the pH value to neutral by droping ammonia water, filter, wash with deionized water and dry to obtain 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine.

[0041] (2) Preparation of 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine

[0042] Dissolve 1 mol of 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine in DNF, control the reaction temperature at 95℃ under argon protection, drop 0.35 mol of hexamethylene diisocyanate, keep the reaction for 4h, remove the DNF solvent by distillation to obtain 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine.

[0043] Example 1

[0044] (1) Add isocyanate and polyol in a molar ratio of 1.8:1 in a reaction kettle, then add N,N-dimethylformamide with the same mass as the total mass of isocyanate and polyol, mix uniformly to obtain a primary solution; the isocyanate is 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine and toluene diisocyanate with a molar ratio of 1:1; the polyol is 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine and polytetrahydrofuran with a molar ratio of 1:1;

[0045] (2) The reaction kettle is purged twice by vacuum and inert gas respectively, then after being sealed, stannous octoate is added dropwise into the primary solution through a feeder under stirring, heated to 70℃, and kept for 2h to obtain a reaction solution; the amount of stannous octoate is 0.05% of the total mass of isocyanate and polyol;

[0046] (3) Continue to add hydroxyethyl acrylate and hydroquinone (0.05% of hydroxyethyl acrylate) into the reaction solution for capping until the content of isocyanate functional groups is less than 0.1%, then cool to room temperature, neutralize to neutral by adding neutralizing agent triethylamine, remove the solvent by distillation under reduced pressure, and obtain polyurethane acrylate polymer by deionized water immersion, filtration and drying; the molar ratio of hydroxyethyl acrylate to isocyanate is 0.9:1.

[0047] Example 2

[0048] (1) In the reaction kettle, isocyanate and polyol with a molar ratio of 2:1 were added, and the same mass of acetone as the total mass of isocyanate and polyol was added, and mixed uniformly to obtain a primary solution; the isocyanate was 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine and isophorone diisocyanate with a molar ratio of 1:1; the polyol was 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine and neopentyl glycol with a molar ratio of 1:1;

[0049] (2) The reaction kettle was rinsed by vacuumizing and filling with inert gas 4 times respectively, and then after being sealed, dibutyltin dilaurate was added dropwise into the primary solution through the feeder under stirring, heated to 90℃, and kept for 4h to obtain a reaction solution; the amount of dibutyltin dilaurate was 0.05-0.08% of the total mass of isocyanate and polyol;

[0050] (3) The temperature was kept unchanged, and the reaction solution was continuously capped by adding hydroxyethyl methacrylate and tert-butyl catechol (0.05% of hydroxyethyl methacrylate) until the content of isocyanate functional group was less than 0.1%; cooled to room temperature, neutralized to neutral by adding neutralizing agent triethylamine, removed the solvent by reduced pressure distillation, and then immersed in deionized water, filtered and dried to obtain a polyurethane acrylate polymer; the molar ratio of hydroxyethyl methacrylate to isocyanate was 1:1.

[0051] Example 3

[0052] (1) In the reaction kettle, isocyanate and polyol with a molar ratio of 2.2:1 were added, and the same mass of ethyl acetate as the total mass of isocyanate and polyol was added, and mixed uniformly to obtain a primary solution; the isocyanate was 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine and diphenylmethane diisocyanate with a molar ratio of 1:1; the polyol was 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine and polycaprolactone diol with a molar ratio of 1:1;

[0053] (2) The reaction kettle was rinsed by vacuumizing and filling with inert gas 3 times respectively, and then after being sealed, dibutyltin dilaurate was added dropwise into the primary solution through the feeder under stirring, heated to 80℃, and kept for 3h to obtain a reaction solution; the amount of dibutyltin dilaurate was 0.05-0.08% of the total mass of isocyanate and polyol;

[0054] (3) keeping the temperature unchanged, continue to add hydroxyethyl acrylate and tert-butyl catechol (0.05% of hydroxyethyl acrylate) to the reaction solution for capping until the isocyanate functional group content is less than 0.1%; cool to room temperature, add neutralizer triethylamine to neutralize to neutral, remove the solvent by vacuum distillation, and then immerse in deionized water, filter and dry to obtain a polyurethane acrylate polymer; the molar ratio of the hydroxyethyl acrylate to the isocyanate is 1.1:1.

[0055] Comparative Example 1

[0056] The same as Example 3 except that the isocyanate does not comprise 2,4,6-tris(6'-isocyanatophenyl)-1,3,5-triazine.

[0057] Comparative Example 2

[0058] The same as Example 3 except that the polyol does not comprise 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine compound.

[0059] Comparative Example 3

[0060] The same as Example 3 except that 1,5-naphthalene diisocyanate is used instead of 2,4,6-tris(6'-isocyanatophenyl)-1,3,5-triazine compound.

[0061] Performance Test

[0062] 1. Coating

[0063] (1) Sample

[0064] According to the mass fraction, 20 parts of the polyurethane acrylate polymer of each example and comparative example, 30 parts of trimethylolpropane triacrylate, 3 parts of benzophenone, 0.2 parts of leveling agent (BYK373), 0.5 parts of dispersant (AFCONA4010) and 10 parts of talc are weighed and uniformly mixed, vacuum defoaming, and then coated on the glass sheet subjected to electrostatic dust removal, and then irradiated with 700 mJ / cm 2 of ultraviolet light at 45℃ to obtain a film sample with a film thickness of 0.5 mm.

[0065] (2) Test

[0066] Adhesion: crosshatch method (3M600, 3 times).

[0067] Water boiling resistance: the sample is placed in 100℃ water and soaked for 2 hours, and the appearance is observed.

[0068] Wear resistance: tested according to the standard "Determination of Abrasion Resistance of Pigment and Varnish-Rotary Rubber Sand Wheel Method" (GB / T1768-2006).

[0069] 2. Film

[0070] (1) Sample

[0071] According to the mass fraction, 20 parts of polyurethane acrylate polymer of each example and comparative example, 30 parts of trimethylolpropane triacrylate, 3 parts of benzophenone, 0.2 parts of leveling agent (BYK373), 0.5 parts of dispersant (AFCONA4010) and 10 parts of talc were weighed and uniformly mixed, vacuum defoaming, then poured into a mold coated with a release agent, and cured by irradiation of 700 mJ / cm 2 of ultraviolet light at 60℃ to obtain a 1mm thick film.

[0072] (2) Test

[0073] Mechanical strength: test the tensile strength of the film, the tensile speed is 1m / min.

[0074] Heat aging resistance: place in a 200℃ oven for 24h, test the change rate % of mechanical strength.

[0075] Volume stability: in compression mode, the heating rate is 5℃ / min, use a thermal mechanical analyzer to measure the sample linear expansion coefficient (CTE).

[0076] Dielectric properties: dielectric tester Keysight E5071C and precision impedance analyzer Agilent 4294A, respectively test the dielectric constant (1GHz).

[0077] Data test results, see Table 1.

[0078] Table 1 test results

[0079]

[0080] As can be seen from the above examples, using 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine and 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine as polyols and isocyanates respectively to participate in the polymerization reaction of polyurethane acrylate, the modified polyurethane acrylate body exhibits improved adhesion, boiling water resistance, wear resistance, aging resistance, mechanical strength and volume stability during use, and also has good low dielectric properties. Therefore, this body modification method expands the use range of polyurethane acrylate polymer and is suitable for the electronic field.

[0081] While certain specific embodiments of the application have been described in detail herein for the purposes of exemplification, numerous other variations and modifications will be apparent to persons skilled in the art. Any and all such variations and modifications are within the scope of this application as defined in the appended claims.

Claims

1. A method of modifying a urethane acrylate with a triazine naphthalene compound, characterized by, comprising the steps of: (1) adding isocyanate and polyol in a molar ratio of 1.8-2.2:1 into a reaction kettle, adding organic solvent with the same mass as the total mass of isocyanate and polyol, mixing uniformly to obtain a primary solution; the isocyanate comprises triazine naphthalene compound with isocyanate group and diisocyanate; the polyol comprises triazine naphthalene compound with hydroxyl group and dihydric alcohol; (2) adding catalyst dropwise into the primary solution under protective gas, heating to obtain a reaction solution; (3) keeping the temperature unchanged, continuously adding hydroxy acrylate and polymerization inhibitor into the reaction solution for end-capping until the content of isocyanate functional group is less than 0.1%, cooling, neutralizing to neutral, removing solvent by distillation under reduced pressure, immersing in deionized water, filtering and drying to obtain polyurethane acrylate polymer.

2. The method of claim 1, wherein, the triazine naphthalene compound with hydroxyl group is 2,4,6-tris(6'-hydroxynaphthyl)-1,3,5-triazine, and / or the triazine naphthalene compound with isocyanate group is 2,4,6-tris(6'-isocyanate naphthyl)-1,3,5-triazine.

3. The method of claim 1, wherein, the diisocyanate is one or a combination of toluene diisocyanate, isophorone diisocyanate, diphenyl methane diisocyanate, dicyclohexyl methane diisocyanate and hexamethylene diisocyanate.

4. The method of claim 1, wherein, the dihydric alcohol is one or a combination of polytetrahydrofuran, polypropylene glycol, neopentyl glycol, polyethylene glycol and polycaprolactone diol.

5. The method of claim 1, wherein, the catalyst is one or a combination of stannous octoate, dibutyl tin dilaurate and triethanolamine; and / or, the polymerization inhibitor is hydroquinone or tert-butyl hydroquinone; and / or, the organic solvent is one of acetone, N,N-dimethylformamide, N,N-dimethylacetamide, cyclohexane, ethyl acetate, pentane, heptane and hexane.

6. The method of claim 4, wherein, the hydroxy acrylate monomer is one or a combination of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

7. A polyurethane acrylate polymer obtained by the method according to any one of claims 1-6.

8. A topcoat characterized by, comprising the polyurethane acrylate polymer according to claim 7.

9. An adhesive, characterized by comprising the polyurethane acrylate polymer according to claim 7.

10. Use of the polyurethane acrylate polymer according to claim 7, characterized in that, which can be used in electronics, electrical appliances, machinery, furniture, buildings or road surfaces. which can be used in electronics, electrical appliances, machinery, furniture, buildings or road surfaces.

Images