A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate

Abstract

The present invention relates to a preparation method and application of a UV-curable methacrylate-containing silicone oil. First, a methacrylate structure organic compound containing a mercapto group structure, 3-mercaptopropionyloxyethyl methacrylate, is synthesized. ;Secondly, react with end-group epoxy-containing polymethylsiloxane, under the catalysis of organic base, mercapto group can perform ring-opening click chemical reaction on propylene oxide efficiently and quickly, without cross-linking side reaction, and the reaction is controllable , the grafting rate of methacrylate is as high as 95%, and the polymethylsiloxane (PSi-MMA) with methacrylate structure in the terminal group with excellent performance is prepared; the composite photoinitiator is used to coat the substrate Ultraviolet light curing on the material, rapid curing at room temperature to form a film, clean and pollution-free, the prepared film has excellent release effect: the residual adhesion rate of standard tape is higher than 92%, and the release force is stable at 15-30 g About /in, it is a solvent-free, metal-free catalyst, fast silicone light curing system that does not require high temperature curing.

Description

technical field

[0001] The invention belongs to the field of polymer material science, and in particular relates to a preparation method of an ultraviolet (UV) curable silicone oil material, which can be applied to photocurable release agent materials. Background technique

[0002] Polymethylsiloxane, referred to as silicone oil, the main chain structure is connected by silicon-oxygen bonds, has excellent flexibility, and at the same time shows high and low temperature resistance, and can be used in a wide temperature range, with both weather resistance and resistance High and low temperature characteristics, in addition, compared with conventional polymers, it has excellent barrier properties, low surface energy and surface tension, corrosion resistance, electrical insulation, ozone resistance, waterproof, flame retardancy, physiological inertness and other properties , Widely used in aerospace, release materials, electrical and electronic, chemical machinery, medical and h...

Examples

Example Embodiment

[0032] Example 1

[0033] Mercapto group-containing methacrylate compound, methacrylic acid-3-mercapto-propionyloxy ethyl, hydroxyethyl acrylate mercaptopropionic acid obtained by esterification with methacrylic acid, the reaction of equation [3]:

[0034]

[0035] [3] Synthesis of methacrylic acid, 3-mercapto-propionyloxy-ethyl ester

[0036] Methacrylate, 2-hydroxyethyl methacrylate (13.00 g; 0.10 mol), 3- mercaptopropionic acid (11.13 g; 0.105 mol), p-toluenesulfonic acid (1.00 g) as an esterification reaction catalyst, hydroquinone (0.12 g) as a polymerization inhibitor, benzene (15.00 mL) as a water, was gradually added to a 250 mL three-neck flask. After loading three bottles trap placed in an oil bath of slowly heated to reflux, the reaction temperature 8 h. After completion of the reaction product was cooled to, washed with a dilute solution of 3% sodium bicarbonate 3 times, washed with distilled water until neutral, dried over anhydrous sodium sulfate overnight. The sol...

Example Embodiment

[0037] Example 2

[0038] Synthesis of polymethyl methacrylate silicone material of the end structure (PSi-MMA) is.

[0039] Epoxy-terminated methoxy poly siloxane structural formula [2], made, Figure 4 Epoxy-terminated methoxy poly siloxane NMR spectrum, the structure of the one-NMR proton peak, by integration calculation, n = 14, molecular weight of 1300.

[0040] To 250 mL three-necked flask with a constant pressure funnel, and a bottom magnetic stir bar were added to epoxy-terminated methoxy poly siloxane (13.00 g, 0.01 mol), triethylamine (0.08 g, 0.0008 mol) and solvent of acetone (50 mL). Stirring at room temperature, methyl acrylate, 3-mercapto-propionyloxy-ethyl ester (4.36 g, 0.02 mol) in acetone (10 mL) was added dropwise to the reaction solution, and epoxy-terminated silicone with methoxy polyethylene the molar ratio of acrylate, 3-methyl-mercapto-propionyloxy-ethyl ester 1: 2, epoxy-terminated methoxy poly siloxane was added dropwise 10 min, the reaction was continued...

Example Embodiment

[0041] Example 3

[0042] Synthesis of polymethyl methacrylate silicone material of the end structure (PSi-MMA) is.

[0043] Example 2 except that the epoxy-terminated methoxy poly siloxane has a molecular weight 2500, n = 30.

[0044] In other embodiments without changing the conditions of Example 2, the preparation process epoxy-terminated siloxane and poly methoxy-yl methacrylate, 3-mercapto-propionyloxy-ethyl weights were: 25.0 g and 4.36 g , the same amount of solvent can be used tetrahydrofuran, ethyl acetate, toluene, xylene, acetone, methyl ethyl ketone and the like in place of, the same operation, characterized by IR and NMR spectra confirm the successful preparation of a PSi-MMA, molecular weight 2900, methacrylic acid ester grafted 97%. Reference numeral PSi-MMA02.

technical field

[0001] The invention belongs to the field of polymer material science, and in particular relates to a preparation method of an ultraviolet (UV) curable silicone oil material, which can be applied to photocurable release agent materials. Background technique

[0002] Polymethylsiloxane, referred to as silicone oil, the main chain structure is connected by silicon-oxygen bonds, has excellent flexibility, and at the same time shows high and low temperature resistance, and can be used in a wide temperature range, with both weather resistance and resistance High and low temperature characteristics, in addition, compared with conventional polymers, it has excellent barrier properties, low surface energy and surface tension, corrosion resistance, electrical insulation, ozone resistance, waterproof, flame retardancy, physiological inertness and other properties , Widely used in aerospace, release materials, electrical and electronic, chemical machinery, medical and h...

Examples

Example Embodiment

[0032] Example 1

[0033] Mercapto group-containing methacrylate compound, methacrylic acid-3-mercapto-propionyloxy ethyl, hydroxyethyl acrylate mercaptopropionic acid obtained by esterification with methacrylic acid, the reaction of equation [3]:

[0034]

[0035] [3] Synthesis of methacrylic acid, 3-mercapto-propionyloxy-ethyl ester

[0036] Methacrylate, 2-hydroxyethyl methacrylate (13.00 g; 0.10 mol), 3- mercaptopropionic acid (11.13 g; 0.105 mol), p-toluenesulfonic acid (1.00 g) as an esterification reaction catalyst, hydroquinone (0.12 g) as a polymerization inhibitor, benzene (15.00 mL) as a water, was gradually added to a 250 mL three-neck flask. After loading three bottles trap placed in an oil bath of slowly heated to reflux, the reaction temperature 8 h. After completion of the reaction product was cooled to, washed with a dilute solution of 3% sodium bicarbonate 3 times, washed with distilled water until neutral, dried over anhydrous sodium sulfate overnight. The sol...

Example Embodiment

[0037] Example 2

[0038] Synthesis of polymethyl methacrylate silicone material of the end structure (PSi-MMA) is.

[0039] Epoxy-terminated methoxy poly siloxane structural formula [2], made, Figure 4 Epoxy-terminated methoxy poly siloxane NMR spectrum, the structure of the one-NMR proton peak, by integration calculation, n = 14, molecular weight of 1300.

[0040] To 250 mL three-necked flask with a constant pressure funnel, and a bottom magnetic stir bar were added to epoxy-terminated methoxy poly siloxane (13.00 g, 0.01 mol), triethylamine (0.08 g, 0.0008 mol) and solvent of acetone (50 mL). Stirring at room temperature, methyl acrylate, 3-mercapto-propionyloxy-ethyl ester (4.36 g, 0.02 mol) in acetone (10 mL) was added dropwise to the reaction solution, and epoxy-terminated silicone with methoxy polyethylene the molar ratio of acrylate, 3-methyl-mercapto-propionyloxy-ethyl ester 1: 2, epoxy-terminated methoxy poly siloxane was added dropwise 10 min, the reaction was continued...

Example Embodiment

[0041] Example 3

[0042] Synthesis of polymethyl methacrylate silicone material of the end structure (PSi-MMA) is.

[0043] Example 2 except that the epoxy-terminated methoxy poly siloxane has a molecular weight 2500, n = 30.

[0044] In other embodiments without changing the conditions of Example 2, the preparation process epoxy-terminated siloxane and poly methoxy-yl methacrylate, 3-mercapto-propionyloxy-ethyl weights were: 25.0 g and 4.36 g , the same amount of solvent can be used tetrahydrofuran, ethyl acetate, toluene, xylene, acetone, methyl ethyl ketone and the like in place of, the same operation, characterized by IR and NMR spectra confirm the successful preparation of a PSi-MMA, molecular weight 2900, methacrylic acid ester grafted 97%. Reference numeral PSi-MMA02.

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