CN114133572B - Photosensitive organic silicon resin, preparation method and application - Google Patents
Photosensitive organic silicon resin, preparation method and application Download PDFInfo
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- CN114133572B CN114133572B CN202210008733.4A CN202210008733A CN114133572B CN 114133572 B CN114133572 B CN 114133572B CN 202210008733 A CN202210008733 A CN 202210008733A CN 114133572 B CN114133572 B CN 114133572B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
The invention provides a photosensitive organic silicon resin, a preparation method and application, and belongs to the technical field of photosensitive molecular materials. Dissolving a photoinitiator and a catalyst I in a solvent I, adding isocyanate siloxane, heating, stirring for reaction, washing n-hexane, and distilling under reduced pressure to obtain a siloxane photoinitiator; mixing hydroxyl-terminated PDMS, isocyanate siloxane, a catalyst I and a solvent II, heating, stirring, reacting, washing with acetonitrile, and distilling under reduced pressure to obtain siloxane PDMS; mixing a siloxane photoinitiator, siloxane PDMS, alkyl siloxane and a solvent III, heating to 40-60 ℃, adding a mixture of a catalyst II and deionized water, adding hexamethyldisiloxane, standing for layering, taking down the layer, and carrying out reduced pressure distillation to obtain the photosensitive organic silicon resin. The preparation method is simple and easy to control, and the photosensitive organic silicon resin has low surface energy and high hardness, and is used for preparing coatings, antifouling and fingerprint resistance.
Description
Technical Field
The invention belongs to the technical field of photosensitive molecular materials, and particularly relates to photosensitive organic silicon resin, a preparation method and application thereof.
Background
The ultraviolet curing technology has more and more attention due to the unique advantages of room temperature curing, wide adaptability, low energy consumption, high efficiency, environmental protection and the like, and is widely applied to the fields of coatings, printing ink, adhesives, microelectronics, tooth restoration and the like.
Ultraviolet light cured coatings often have poor antifouling performance, are easily contaminated by aqueous and oily stains, and are difficult to clean. Fluorine-or silicon-containing components are often grafted into the polymer to improve the stain resistance durability of the coating. Although the fluorine-containing component has an excellent antifouling effect, the application of the fluorine-containing component is limited by the high cost, high toxicity and biological accumulation, and an antifouling coating prepared by combining low-surface-energy, non-toxic and low-cost Polydimethylsiloxane (PDMS) and a polymer matrix has the characteristics of high light transmittance, excellent hydrophobic and oleophobic properties and the like, so that the fluorine-containing component is more suitable for practical application. The molecular chains of PDMS have very good flexibility, but the hardness of the resulting coatings after curing is often not very high.
The silicone resin prepared by the acid hydrolysis condensation method has many excellent physical and chemical properties such as high hardness, high and low temperature resistance, oxidation resistance, weather resistance and the like, and the silicone resin has more excellent wear resistance compared with polyurethane resin, epoxy resin and acrylate resin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides the photosensitive organic silicon resin, the preparation method and the application, the preparation method is simple and easy to control, the prepared photosensitive organic silicon resin has the characteristics of low surface energy and high hardness, and a coating prepared by compounding the photosensitive organic silicon resin with the multifunctional acrylate resin has high hardness and also has the characteristics of antifouling and fingerprint resistance.
The invention provides a preparation method of photosensitive organic silicon resin, which solves the technical problem of how to prepare photosensitive organic silicon resin capable of being applied to coating technology, and the preparation method is simple and easy to control and comprises the following steps:
(1) preparation of siloxane photoinitiators
The photoinitiator and the catalyst I are dissolved in the solvent I, and then the isocyanate siloxane is added dropwise. Raising the temperature to 40-60 ℃, continuously stirring and reacting for 5-8 hours, washing by using n-hexane, and carrying out reduced pressure distillation to obtain a siloxane photoinitiator;
(2) preparation of siloxane PDMS
Mixing hydroxyl-terminated PDMS, isocyanate siloxane, a catalyst I and a solvent II, heating to 50-70 ℃, stirring for reaction for 5-10 hours, washing with acetonitrile, and carrying out reduced pressure distillation to obtain siloxane PDMS;
(3) preparation of photosensitive organic silicon resin
Mixing a siloxane photoinitiator, siloxane PDMS, alkyl siloxane and a solvent III, heating to 40-60 ℃, dropwise adding a mixture of a catalyst II and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-60 ℃, stirring for 5-10 hours, adding hexamethyldisiloxane, heating to 60-80 ℃, stirring for 1-3 hours, standing for layering, taking down a layer, and carrying out reduced pressure distillation to obtain photosensitive organic silicon resin;
wherein, the catalyst I is one or more of dibutyltin dilaurate, stannous octoate and butyltin diacetate; the solvent I is one or more of chloroform, tetrahydrofuran and methyl ethyl ketone; the solvent II is one or more of methyl ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; the catalyst II is one or more of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; the solvent III is one or more of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran;
in one or more embodiments, the siloxane photoinitiator of step (1) has the following structure:
wherein X is a micromolecular photoinitiator with hydroxyl or amino, namely benzoin with hydroxyl or amino and derivatives thereof, benzil, alkyl benzophenones, benzophenones and thioxanthone compounds, and R is 1 is-CH 3 or-CH 2 CH 3 。
In one or more embodiments, the molar ratio of the photoinitiator to the isocyanate siloxane in the step (1) is 1: 1 to 1.5; the dosage of the catalyst I is 0.1-3% of the total mass of the photoinitiator and the isocyanate siloxane.
In one or more embodiments, the siliconized PDMS of step (2) has the following structure:
wherein R is 1 is-CH 3 or-CH 2 CH 3 ，R 3 Is composed of
the weight average molecular weight of the hydroxyl-terminated PDMS in the step (2) is 1000-5000 g/mol;
the molar ratio of the hydroxyl-terminated PDMS to the isocyanate siloxane in the step (2) is 1: 1-5; the dosage of the catalyst I is 0.1-3% of the total mass of the hydroxyl-terminated PDMS and the isocyanate siloxane.
In one or more embodiments, the alkanyl siloxane in step (3) has the structure:
R 3 -Si(OR 1 ) 3
wherein R is 1 is-CH 3 or-CH 2 CH 3 ，R 3 is-CH 3 、-CH 2 CH 3 or-CH 2 CH 2 CH 3 。
In one or more embodiments, the molar amount of the deionized water in the step (3) is 3 to 9 times of the total molar number of the siloxane photoinitiator, the siloxane containing long-chain PDMS and the alkyl siloxane;
the amount of the catalyst II used in the step (3) is 0.1-5% of the mass of the water;
the molar ratio of the siloxane photoinitiator, the siloxane PDMS, the alkyl siloxane and the hexamethyldisiloxane in the step (3) is 1: 0.01-1: 1-5: 0.5-2.
In one or more embodiments, the isocyanate siloxane in steps (1) and (2) is one or more of 3-isocyanatopropyl trimethoxy silane and 3-isocyanatopropyl triethoxy silane.
As a second aspect of the present invention, there is provided a photosensitive silicone resin prepared as described above, having the following structure:
wherein X is a micromolecular photoinitiator with hydroxyl or amino, R 1 is-CH 3 or-CH 2 CH 3 ，R 2 Is composed of
The third aspect of the invention provides an application of photosensitive organic silicon resin, wherein the photosensitive organic silicon resin, the multifunctional acrylate resin and the photoinitiator are mixed, and then coated on a substrate, and then irradiated by ultraviolet light to be cured to form a film;
wherein the photoinitiator is selected from one or more of 2,4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide;
the dosage of the photoinitiator is 1 to 5 percent of the total mass of the multifunctional acrylate resin and the silicon-containing resin capable of being photoinitiated and polymerized;
the multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin;
the base material is selected from one or more of a PC plate, a PMMA plate, a wood plate, a steel plate and a glass plate.
In one or more embodiments, the photosensitive silicone resin is used in an amount of 1% to 15% by weight of the multifunctional acrylate resin.
The invention at least comprises the following beneficial effects:
the invention firstly utilizes isocyanate siloxane to react with micromolecular photoinitiator and PDMS respectively to prepare siloxane photoinitiator and siloxane PDMS, and then the siloxane photoinitiator and the siloxane PDMS are hydrolyzed and condensed with alkyl siloxane and hexamethyldisiloxane to synthesize the photosensitive organic silicon resin. Siliconized PDMS is used to provide excellent high contact angle and low sliding angle to obtain excellent antifouling properties; the siloxane photoinitiator can be cracked to generate free radicals under the irradiation of ultraviolet light, and can react with multifunctional acrylate, and the PDMS component with low surface energy in the photosensitive organic silicon resin can be subjected to surface migration in the ultraviolet curing process, so that the concentration of the free radicals on the surface of the coating is improved, and oxygen inhibition can be reduced to a certain extent. After the photosensitive organic silicon resin and the multifunctional acrylate resin are compounded, the coating prepared by ultraviolet curing has excellent wear resistance, and the pencil hardness can reach 4H; the anti-fingerprint and easy-to-wipe performance is good, the durability is good, and the effect is good after the friction cycle test is 5000 times; the curing film has good hydrophobic and oleophobic performances, the water contact angle can reach more than 110 degrees, and the hexadecane contact angle can reach more than 37 degrees; the conversion rate of double bonds is more than 94%.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to specific embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The application of the photo-initiation polymerizable silicon-containing resin in the coating of the invention is tested and evaluated with reference to table 1 for the basic properties of the coating:
TABLE 1 coating Performance test method
The raw materials and sources used in examples 1 to 5 and comparative examples 1 to 3 of the present invention are shown in Table 2:
TABLE 2 raw materials and sources for examples and comparative examples
| Name of raw materials | Source of raw materials |
| Photoinitiator 2959 | Mecline reagent |
| Catalyst I: dibutyl tin dilaurate | Chemical Co Ltd of the national drug group |
| 3-isocyanatopropyltrimethoxysilane | Aladdin Ltd |
| Solvent I: methyl ethyl ketone | Aladdin Ltd |
| Monohydroxy terminated PDMS (M) w ＝1000) | Shanghai Mairuier Chemical Technology Co., Ltd. |
| N-hexane | Chemical Co Ltd of the national drug group |
| Acetonitrile | Chemical Co Ltd of the national drug group |
| Propyl trimethoxy silane | Mecanlin reagent |
| And (2) solvent II: isopropyl alcohol | Chemical Co Ltd of the national drug group |
| Catalyst II: hydrochloric acid | Chemical Co Ltd of the national drug group |
| Hexamethyldisiloxane | Chemical Co Ltd of the national drug group |
| Urethane acrylate resin | JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |
| Epoxy acrylate resin | JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |
| Polyester acrylate resin | JIANGSU LITIAN TECHNOLOGY Co.,Ltd. |
| 3-isocyanatopropyltriethoxysilane | Mecline reagent |
| Catalyst I: stannous octoate | Chemical Co Ltd of the national drug group |
| Dihydroxy terminated PDMS (M) w ＝1000) | Shanghai Mairuier Chemical Technology Co., Ltd. |
| Ethyl trimethoxysilane | Mecline reagent |
| Catalyst II: oxalic acid | Chemical Co Ltd of the national drug group |
| Monohydroxy terminated PDMS (M) w ＝2000) | Shanghai Mairuier Chemical Technology Co., Ltd. |
| Photoinitiator 1173 | Mecline reagent |
| Photoinitiator 184 | Mecline reagent |
| Propyl trimethoxy silane | Chemical Co Ltd of the national drug group |
| And (2) solvent II: acetone (II) | Chemical Co Ltd of the national drug group |
| Photoinitiator HMBP | Mecline reagent |
| Methyltrimethoxysilane | Mecline reagent |
| Photoinitiator ABP | Mecline reagent |
| Ethyl triethoxysilane | Aladdin Ltd |
Example 1
(1) Preparation of the siloxane photoinitiator 2959-IPTES
11.21g (0.05mol)2959 (2-hydroxy-2-methyl-p-hydroxyethyl etherylphenyl-1-propanone) and 0.15g dibutyltin dilaurate were dissolved in 4g methyl ethyl ketone, and 10.27g (0.05mol) IPTS (3-isocyanatopropyltrimethoxysilane) were added dropwise. The temperature was raised to 50 ℃ and the reaction was continued with stirring for 6 hours, after washing with n-hexane, distillation under reduced pressure gave the siloxane photoinitiator 2959-IPTES.
(2) Preparation of siloxane PDMS-1-1000-IPTES
Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer were charged 16.422g (0.08mol) of IPTES, 50g (0.05mol) of monohydroxy-terminated PDMS (M) w 1000), 0.061g of dibutyltin dilaurate, and 10g of methyl ethyl ketone were stirred in a 70 ℃ oil bath to react for 6 hours. Then washing with acetonitrile for three times, and distilling under reduced pressure to obtain siloxane PDMS-1-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.30g (0.01mol) of 2959-IPTES, 6.03g (0.005mol) of PDMS-1-1000-IPTES, 6.57g (0.04mol) of propyltrimethoxysilane and 5g of isopropanol were mixed, stirred well and warmed to 50 ℃. A mixture of 0.041g concentrated hydrochloric acid and 2.97g (0.165mol) deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 6 hours. Thereafter, 1.461g (0.009mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 3 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a1,
wherein X is
R 1 is-CH 3 ，R 2 Is composed of
，R 3 is-CH 2 CH 2 CH 3 )。
(4) Curing of photosensitive silicone resins
Mixing 100 parts by mass of urethane acrylate resin, 1 part by mass of photosensitive organic silicon resin (A1) and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, coating a film on a PMMA plate, and then irradiating by ultraviolet light to cure and form the film.
Example 2
(1) Preparation of siloxane photoinitiator 1173-IPTMS
8.21g (0.05mol) of 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone) and 0.14g of stannous octoate were dissolved in 4g of chloroform, and 12.35g (0.05mol) of IPTMS (3-isocyanatopropyltriethoxysilane) were added dropwise. The temperature is raised to 55 ℃, the reaction is continued for 5 hours under stirring, and after washing by n-hexane, reduced pressure distillation is carried out to obtain the siloxane photoinitiator 1173-IPTMS.
(2) Preparation of siloxane PDMS-2-1000-IPTMS
To a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer were added 39.52g (0.16mol) of IPTMS, 50g (0.05mol) of bishydroxy-terminated PDMS (M) w 1000), stannous octoate 0.063g and toluene 10g, and the reaction was stirred in an oil bath at 70 ℃ for 8 hours. Then washing with acetonitrile for three times, and distilling under reduced pressure to obtain siloxane PDMS-2-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.12g (0.01mol)1173-IPTMS, 4.48g (0.003mol) PDMS-1-1000-IPTMS, 3.76g (0.025mol) ethyltrimethoxysilane and 5g of toluene were mixed, stirred well and warmed to 45 ℃. A mixture of 0.043g of oxalic acid and 2.05g (0.114mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 55 ℃ for 8 hours. Then, 1.79g (0.011mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 2 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand to layer, and then the solvent and the low-boiling point residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a2,
wherein X is
R 1 is-CH 3 and-CH 2 CH 3 ，R 2 Is composed of
，R 3 is-CH 2 CH 3 )。
(4) Curing of photosensitive silicone resins
100 parts by mass of polyester acrylate resin, 1.5 parts by mass of photosensitive silicone resin (A2) and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone were mixed, and then a film was coated on a PC board, followed by ultraviolet irradiation and curing to form a film.
Example 3
(1) Preparation of the siloxane photoinitiator 184-IPTMS
10.22g (0.05mol)184 (1-hydroxy-cyclohexyl-phenyl-methanone) and 0.14g dibutyltin dilaurate were dissolved in 7g methyl ethyl ketone, and 14.82g (0.06mol) IPTMS was added dropwise. The temperature is raised to 60 ℃, the reaction is continued for 6 hours under stirring, and after the n-hexane is washed, the siloxane photoinitiator 184-IPTMS is obtained by reduced pressure distillation.
(2) Preparation of siloxane PDMS-2-1000-IPTMS
Into a four-necked flask equipped with a stirrer, a reflux condenser and a thermometer were charged 24.70g (0.10mol) of IPTMS, 100g (0.05mol) of monohydroxy-terminated PDMS (M) w 2000), 0.081g of stannous octoate and 20g of xylene, and the reaction was stirred in an oil bath at 70 ℃ for 10 hours. Then washing with acetonitrile for three times, and distilling under reduced pressure to obtain siloxane PDMS-1-2000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.51g (0.01mol)184-IPTMS, 4.49g (0.002mol) PDMS-1-2000-IPTMS, 4.93g (0.03mol) propyltrimethoxysilane and 6g of acetone were mixed, stirred well and warmed to 45 ℃. A mixture of 0.043g of oxalic acid and 2.05g (0.114mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 55 ℃ for 9 hours. Thereafter, 1.95g (0.012mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 75 ℃ to conduct the reaction for 3 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a3,
wherein X is
R 1 is-CH 3 and-CH 2 CH 3 ，R 2 Is composed of
，R 3 is-CH 2 CH 3 )。
(4) Curing of photosensitive silicone resins
100 parts by mass of epoxy acrylate resin, 2 parts by mass of photosensitive organic silicon resin (A3) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then coated on a wood board, and then irradiated by ultraviolet light, and cured to form a film.
Example 4
(1) Preparation of siloxane photoinitiator HMBP-IPTES
10.61g (0.05mol) of HMBP (4-hydroxymethyldiphenylketone) and 0.16g of dibutyltin dilaurate were dissolved in 5g of methylethylketone, and 12.32g (0.06mol) of IPTS was added dropwise. The temperature is raised to 60 ℃, the stirring reaction is continued for 7 hours, and after the normal hexane is washed, the reduced pressure distillation is carried out to obtain the siloxane photoinitiator HMBP-IPTES.
(2) Preparation of siloxane PDMS
The procedure of example 1 was used to prepare the siloxylated PDMS-1-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.18g (0.01mol) of HMBP-IPTMS, 3.62g (0.003mol) of PDMS-1-1000-IPTMS, 4.77g (0.035mol) of methyltrimethoxysilane and 4g of acetone were mixed, stirred well and warmed to 45 ℃. A mixture of 0.051g of glacial acetic acid and 2.52g (0.144mol) of deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 6 hours. Then, 2.11g (0.013mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 2 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a4,
wherein X is
R 1 is-CH 3 ，R 2 Is composed of
，R 3 is-CH 3 )。
(4) Curing of photosensitive silicone resins
100 parts by mass of urethane acrylate resin, 1 part by mass of photosensitive silicone resin (A4) and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then a film is coated on a wood board, and then ultraviolet irradiation is performed to cure the mixture to form a film.
Example 5
(1) Preparation of siloxane photoinitiator ABP-IPTES
9.91g (0.05mol) of ABP (4-aminodiphenylketone) and 0.03g of dibutyltin dilaurate were dissolved in 5g of methyl ethyl ketone, and 10.27g (0.05mol) of IPTS was added dropwise. The temperature is raised to 40 ℃, the stirring reaction is continued for 5 hours, and after the normal hexane is washed, the siloxane photoinitiated ABP-IPTES is obtained by reduced pressure distillation.
(2) Preparation of siloxane PDMS
The procedure of example 2 was used to prepare the siloxylated PDMS-2-1000-IPTES.
(3) Preparation of photosensitive organic silicon resin
4.04g (0.01mol) ABP-IPTES, 4.48g (0.003mol) PDMS-1-1000-IPTMS, 3.85g (0.02mol) ethyltriethoxysilane and 5g isopropanol were mixed, stirred well and warmed to 50 ℃. A mixture of 0.051g concentrated HCl and 1.78g (0.099mol) deionized water was then added dropwise to the flask over 1 h. The temperature of the reaction mixture was then raised to 60 ℃ for 5 hours. Thereafter, 1.63g (0.01mol) of hexamethyldisiloxane was added to the flask, and the temperature was raised to 70 ℃ to conduct the reaction for 2.5 hours while maintaining the temperature. After the reaction was completed, the lower layer solution was allowed to stand for separation, and then the solvent and the low-boiling residue in the organic phase were removed at 50 ℃/130mmHg to obtain a photosensitive silicone resin (a5,
wherein X is
R 1 is-CH 3 and-CH 3 ，R 2 Is composed of
，R 3 is-CH 2 CH 3 )。
(4) Curing of photosensitive silicone resins
100 parts by mass of polyester acrylate resin, 1 part by mass of photosensitive silicone resin (A5) and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone are mixed, and then a film is coated on a steel plate, and then ultraviolet irradiation is performed to cure the mixture to form a film.
Comparative example 1
(1) Curing of urethane acrylate resins
Mixing 100 parts by mass of urethane acrylate resin and 3 parts by mass of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone, coating a film on a PMMA plate, irradiating by ultraviolet light, and curing to form a film.
Comparative example 2
(1) Curing of epoxy acrylate resins
Mixing 100 parts by mass of epoxy acrylate resin and 4 parts by mass of photoinitiator alpha, alpha-diethoxyacetophenone, coating a film on a PVC plate, and then irradiating by ultraviolet light to cure and form a film.
Comparative example 3
(1) Curing of polyester acrylate resins
100 parts by mass of polyester acrylate resin and 3 parts by mass of photoinitiator 1-hydroxy-cyclohexyl benzophenone are mixed, and then a film is coated on a PC plate, and then ultraviolet irradiation is carried out to cure the mixture to form a film.
With reference to the test methods and test standards of table 1, the following technical performance tests were performed on the paint films of the above examples 1 to 5 and comparative examples 1 to 3, and the results of the performance tests are as follows: the test results are shown in table 3:
as can be seen from the performance test results of examples 1-5 and comparative examples 1-3 in Table 3, the hardness of the photosensitive organic silicon resin prepared in examples 1-5 of the invention can reach 4H when being used as a photocuring antifouling coating; the initial water drop angle of the coating reaches more than 110 degrees, the initial hexadecane contact angle reaches more than 37 degrees, the coating has good fingerprint and contamination resistance effects, and after 3000 times and 5000 times of friction cycle tests, the coating still has high water and hexadecane contact angles, so that the long-acting antifouling effect can be kept; the comparative examples 1 to 3 have poor wear resistance, no antifouling and fingerprint resistance and low double bond conversion rate under the condition of not adding photosensitive organic silicon resin.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the photosensitive organic silicon resin is characterized by comprising the following steps:
(1) preparation of siloxane photoinitiators
Dissolving a photoinitiator and a catalyst I in a solvent I, then dropwise adding isocyanate siloxane, raising the temperature to 40-60 ℃, continuously stirring for reacting for 5-8 hours, washing with n-hexane, and carrying out reduced pressure distillation to obtain a siloxane photoinitiator;
(2) preparation of siloxane PDMS
Mixing hydroxyl-terminated PDMS, isocyanate siloxane, a catalyst I and a solvent II, heating to 50-70 ℃, stirring for reaction for 5-10 hours, washing with acetonitrile, and carrying out reduced pressure distillation to obtain siloxane PDMS;
(3) preparation of photosensitive organic silicon resin
Mixing the siloxane photoinitiator, the siloxane PDMS, alkyl siloxane and a solvent III, heating to 40-60 ℃, dropwise adding a mixture of a catalyst II and deionized water, completing dropwise adding within 0.5-1 hour, heating to 50-60 ℃, stirring for 5-10 hours, adding hexamethyldisiloxane, heating to 60-80 ℃, stirring for 1-3 hours, standing for layering, taking down a layer, and carrying out reduced pressure distillation to obtain photosensitive organic silicon resin;
wherein the catalyst I is at least one of dibutyltin dilaurate, stannous octoate and butyltin diacetate; the solvent I is at least one of chloroform, tetrahydrofuran and methyl ethyl ketone; the solvent II is at least one of methyl ethyl ketone, ethyl acetate, acetone, toluene, xylene and tetrahydrofuran; the catalyst II is at least one of glacial acetic acid, formic acid, hydrochloric acid, oxalic acid and sulfuric acid; the solvent III is at least one of methanol, ethanol, isopropanol, ethyl formate, ethyl acetate, toluene, xylene and tetrahydrofuran;
the siloxane photoinitiator described in step (1) has the following structure:
wherein X is derived from a small molecule photoinitiator with hydroxyl or amino, namely benzoin, benzil, alkyl benzophenones, benzophenones and thioxanthone compounds with hydroxyl or amino; r 1 is-CH 3 or-CH 2 CH 3 ；
The siliconized PDMS in step (2) has the following structure:
wherein R is 1 is-CH 3 or-CH 2 CH 3 ，R 2 Is composed of
Is a natural number of 8-64; when R is 2 In the latter case, both end positions are connected
The alkyl siloxane in step (3) has the following structure:
R 3 -Si(OR 1 ) 3
wherein R is 1 is-CH 3 or-CH 2 CH 3 ，R 3 is-CH 3 、-CH 2 CH 3 or-CH 2 CH 2 CH 3 ；
The isocyanate siloxane in the steps (1) and (2) is at least one of 3-isocyanate propyl trimethoxy silane and 3-isocyanate propyl triethoxy silane.
2. A process for preparing a photosensitive silicone resin according to claim 1, wherein the molar ratio of the photoinitiator to the isocyanate siloxane in step (1) is 1 (1 to 1.5); the dosage of the catalyst I is 0.1-3% of the total mass of the photoinitiator and the isocyanate siloxane.
3. The process for producing a photosensitive silicone resin according to claim 1,
the weight average molecular weight of the hydroxyl-terminated PDMS in the step (2) is 1000-5000 g/mol;
the molar ratio of the hydroxyl-terminated PDMS to the isocyanate siloxane in the step (2) is 1 (1-5); the dosage of the catalyst I is 0.1-3% of the total mass of the hydroxyl-terminated PDMS and the isocyanate siloxane.
4. The method according to claim 1, wherein the molar amount of deionized water used in step (3) is 3 to 9 times the total molar amount of the siloxane photoinitiator, siloxane PDMS and alkyl siloxane;
the amount of the catalyst II used in the step (3) is 0.1-5% of the mass of the deionized water;
the mole ratio of the siloxane photoinitiator, the siloxane PDMS, the alkyl siloxane and the hexamethyldisiloxane in the step (3) is 1 (0.01-1): 1-5): 0.5-2.
5. A photosensitive silicone resin characterized by being produced by the production method according to any one of claims 1 to 4.
6. The application of photosensitive organic silicon resin is characterized in that the photosensitive organic silicon resin, the multifunctional acrylate resin and the photoinitiator according to claim 5 are mixed, and then a film is coated on a substrate, and then ultraviolet irradiation is carried out to cure the mixture into a film;
wherein the photoinitiator is selected from one or more of 2,4, 6-trimethyl benzoyl diethyl phosphonate, 2-phenyl-2, 2-dimethylamino-1- (4-morpholinyl phenyl) -1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, alpha-diethoxy acetophenone, 1-hydroxy-cyclohexyl benzophenone and 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide;
the dosage of the photoinitiator is 1 to 5 percent of the total mass of the multifunctional acrylate resin and the photosensitive organic silicon resin;
the multifunctional acrylate resin is selected from one or more of polyurethane acrylate resin, epoxy acrylate resin and polyester acrylate resin;
the base material is selected from one or more of a PC plate, a PMMA plate, a wood plate, a steel plate and a glass plate.
7. The use according to claim 6, wherein the photosensitive silicone resin is used in an amount of 1% to 15% by mass of the multifunctional acrylate resin.
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| US6174977B1 (en) * | 1998-10-26 | 2001-01-16 | Toyo Ink Mfg. Co., Ltd. | Cold curable resin composition and base material coated with the same |
| CN104479098A (en) * | 2014-12-19 | 2015-04-01 | 江南大学 | Preparation method of polyfunctional UV (Ultraviolet)-cured organic silicon resin |
| CN108329831A (en) * | 2018-02-02 | 2018-07-27 | 浙江科思达新材料有限公司 | A kind of antifouling low-surface-energy polysiloxane composition and application |
| CN113773501A (en) * | 2021-09-08 | 2021-12-10 | 广东致格纳米科技有限公司 | Preparation method of curable silicon-based hybrid resin |
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| US6174977B1 (en) * | 1998-10-26 | 2001-01-16 | Toyo Ink Mfg. Co., Ltd. | Cold curable resin composition and base material coated with the same |
| CN104479098A (en) * | 2014-12-19 | 2015-04-01 | 江南大学 | Preparation method of polyfunctional UV (Ultraviolet)-cured organic silicon resin |
| CN108329831A (en) * | 2018-02-02 | 2018-07-27 | 浙江科思达新材料有限公司 | A kind of antifouling low-surface-energy polysiloxane composition and application |
| CN113773501A (en) * | 2021-09-08 | 2021-12-10 | 广东致格纳米科技有限公司 | Preparation method of curable silicon-based hybrid resin |
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