CN111234134B - High-performance glycidyl versatate modified polysiloxane resin and preparation method thereof - Google Patents
High-performance glycidyl versatate modified polysiloxane resin and preparation method thereof Download PDFInfo
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- CN111234134B CN111234134B CN202010131236.4A CN202010131236A CN111234134B CN 111234134 B CN111234134 B CN 111234134B CN 202010131236 A CN202010131236 A CN 202010131236A CN 111234134 B CN111234134 B CN 111234134B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Abstract
The invention discloses a high-performance glycidyl versatate modified polysiloxane resin and a preparation method thereof. The resin is prepared by taking ethyl silicate, vinyl triethoxysilane, a catalyst, tertiary carbonic acid glycidyl ester, acrylic esters, monomers, an initiator and a solvent as raw materials, and synthesizing the high-performance tertiary carbonic acid glycidyl ester modified polysiloxane resin. By introducing the tertiary carbonic acid glycidyl ester, the performances of water resistance, acid resistance, alkali resistance and the like are improved. Compared with the common acrylic acid modified polysiloxane resin, the high-performance tertiary carboxylic acid glycidyl ester modified polysiloxane resin has narrower molecular weight distribution, lower viscosity and a proper amount of reactive groups, has better miscibility with other resins, and a paint film formed after crosslinking has better water resistance, acid resistance and alkali resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to high-performance glycidyl versatate modified polysiloxane resin and a preparation method thereof.
Background
The siloxane takes Si-O-Si as a main chain, and the bond energy (450 kJ/mol) of Si-O bonds is larger than the bond energy (345 kJ/mo 1) of C-C bonds and the bond energy (351 kJ/mol) of C-O bonds of common organic high polymers. Therefore, the silicone resin has excellent heat resistance and ultraviolet light aging resistance. Because the silicone resin and the acrylic resin have good miscibility, the polysiloxane containing active groups and the acrylic resin containing active groups are usually subjected to condensation modification so as to reduce the cost of the resin and combine the weather resistance and the adhesion performance of the polysiloxane containing active groups and the acrylic resin containing active groups.
Although the weather resistance of the common siloxane or acrylic modified siloxane resin coating on the market is excellent, the water resistance of a paint film is general, and particularly the acid resistance is weak. The paint film is easy to rust and damage when being subjected to acid corrosion. At present, due to the fact that labor cost is high, frequent coating construction, maintenance and the like easily cause environmental pollution, and safety and environmental protection problems are easily caused. The tertiary carbonic acid glycidyl ester has an active epoxy group, acrylic resin can be introduced through acrylic acid, and then the tertiary carbonic acid glycidyl ester and siloxane prepolymer are subjected to chemical modification, so that the performances such as acid resistance and alkali resistance are improved. Meanwhile, the tertiary carbonic acid glycidyl ester has larger steric hindrance effect, protects ester bonds and has excellent water resistance. Therefore, a high-performance glycidyl versatate modified polysiloxane resin coating with long service life and excellent weather resistance, water resistance and acid corrosion resistance is favored.
Disclosure of Invention
The invention aims to provide a preparation method of a high-performance glycidyl versatate modified polysiloxane resin aiming at the problems in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a high-performance glycidyl versatate modified polysiloxane resin is composed of the following components in parts by weight:
in some specific embodiments: the weight portions of the ethyl silicate, the vinyl triethoxysilane, the catalyst, the tertiary carbonic acid glycidyl ester, the acrylate, the monomer, the initiator and the solvent are 8-12 parts, 15-20 parts, 2-4.5 parts, 8.5-12 parts, 35-52 parts, 0.7-1.4 parts and 20-25 parts in sequence.
In some specific embodiments: the catalyst is selected from one or more of water, hydrochloric acid and acetic acid; preferably, the catalyst is a mixture of water and hydrochloric acid, and the weight parts of the catalyst are 2-4.3 parts and 0.1-0.2 part in sequence. The mass concentration of the hydrochloric acid is 37%.
In some specific embodiments: the acrylic esters and the monomers are selected from one or more of acrylic acid, butyl acrylate, methyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate and styrene.
In some specific embodiments: the acrylate and the monomer comprise 8-13 parts of styrene, 3-9 parts of hydroxyethyl acrylate, 7-13 parts of methyl methacrylate, 14-18 parts of butyl acrylate and 0.5-1 part of acrylic acid.
In some specific embodiments: the initiator is selected from one or more of di-tert-amyl peroxide, azobisisobutyronitrile and benzoyl peroxide.
In some specific embodiments: the solvent is selected from one or more of dimethylbenzene, methylbenzene and butyl acetate.
The high-performance glycidyl versatate modified polysiloxane resin comprises the following steps:
the first step is as follows: uniformly mixing ethyl silicate and vinyl triethoxysilane, heating to 45-55 deg.C, slowly adding catalyst under the temperature condition, and finishing the addition for 1.5-2 h; heating to 50-60 ℃, reacting for 2-3h, and then carrying out reduced pressure distillation to obtain a polysiloxane prepolymer;
the second step: introducing nitrogen, uniformly mixing the prepared polysiloxane prepolymer and the tertiary carbonic acid glycidyl ester, heating to 145-160 ℃, and slowly adding the mixed solution of the acrylate, the monomer and the initiator under the temperature condition; and after the addition is finished, continuing to perform copolymerization reaction for 4-6h, cooling to 80-100 ℃ after the reaction is finished, adding a solvent, and diluting to obtain the high-performance glycidyl versatate modified polysiloxane resin.
The method comprises the following steps: the viscosity range of the high-performance glycidyl versatate modified polysiloxane resin is 15-30 seconds (format, 25 ℃), and the non-volatile component is 75-80 percent.
The invention has the beneficial effects that:
the invention discloses a preparation method of high-performance glycidyl versatate modified polysiloxane resin. The resin takes ethyl silicate, vinyl triethoxysilane, a catalyst, glycidyl versatate, acrylates and monomers, an initiator, a solvent and the like as raw materials, wherein the acrylates and the monomers are selected from one or more of acrylic acid, butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and styrene, and the high-performance glycidyl versatate modified polysiloxane resin is synthesized by a chemical synthesis modification method with the glycidyl versatate and a siloxane prepolymer according to a specific raw material ratio. The water resistance, acid resistance, alkali resistance and other performances of the product are improved by introducing the tertiary carbonic acid glycidyl ester. Compared with the common acrylic acid modified polysiloxane resin, the high-performance tertiary carbonic acid glycidyl ester modified polysiloxane resin has narrower molecular weight distribution, lower viscosity and a proper amount of reactive groups, has better miscibility with other resins, and a paint film formed after crosslinking has excellent water resistance (more than or equal to 400 h), acid resistance (more than or equal to 368 h) and alkali resistance (more than or equal to 360 h); the conventional acrylic modified polysiloxane resin has water resistance (more than or equal to 268 h), acid resistance (more than or equal to 240 h) and alkali resistance (more than or equal to 242 h).
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
the components and the mass percent of the components adopted by the high-performance glycidyl versatate modified polysiloxane resin are shown in the table I.
The preparation method of the high-performance glycidyl versatate modified polysiloxane resin in the invention from the example 1 to the example 4 is as follows:
the first step is as follows: uniformly mixing the ethyl silicate and the vinyl triethoxysilane, heating to 45-50 ℃, slowly adding the catalyst at a constant speed under the temperature condition, and finishing the addition for 1.5-2 hours; then the temperature is raised to 55 ℃, the reaction is carried out for 2.5h at 55 ℃, then the polysiloxane prepolymer is prepared by reduced pressure distillation, and then the temperature is lowered to room temperature.
The second step: and introducing nitrogen, uniformly mixing the prepared polysiloxane prepolymer and the tertiary carbonic acid glycidyl ester of the component, heating to 150 ℃, adding the acrylate of the component and the mixed solution of the monomer and the initiator under the temperature condition, and dripping the mixed solution of the monomer and the initiator for 3 hours. And after the addition is finished, continuing to perform copolymerization reaction for 5 hours, cooling to 90 ℃ after the reaction is finished, and adding a solvent for dilution to obtain the high-performance tertiary carboxylic acid glycidyl ester modified polysiloxane resin.
Watch 1
The specific parameters of the prepared high-performance glycidyl versatate modified polysiloxane resin are shown in the second table.
Watch two
| Serial number | Item | Example 1 | Example 2 | Example 3 | Example 4 |
| 1 | Limpidity and transparency | Clear and transparent | Clear and transparent | Clear and transparent | Clear and transparent |
| 2 | Color (Fe-Co method), number | 3 | 4 | 3 | 3 |
| 3 | Viscosity (grid/25 ℃ C.), s | 25 | 26 | 28 | 37 |
| 4 | Acid value of mgKOH/g | 4.7 | 4.1 | 4.5 | 6.5 |
| 5 | Fineness, mum | 15 | 15 | 15 | 15 |
| 6 | Non-volatile fraction of% | 75.2 | 78.1 | 79.8 | 77.2 |
The high-performance glycidyl versatate modified polysiloxane resin 60 percent prepared in the embodiment 1 to the embodiment 4 is mixed and ground with rutile titanium dioxide 25 percent, zinc oxide 7.8 percent, xylene solvent 3.3 percent, butyl acetate solvent 3.3 percent and dispersant 0.5 percent until the fineness is less than 20 mu m, and then added with defoamer 0.1 percent to be mixed evenly to prepare the high-performance glycidyl versatate modified polysiloxane resin. According to the standard requirements of HG/T4755-2014 polysiloxane coating, the mechanical property, the chemical resistance, the industrial climate aging resistance and other properties are tested by plate making, and the test properties are shown in Table III.
Performance index of paint made from high-performance tertiary carboxylic acid glycidyl ester modified polysiloxane resin
Claims (5)
1. A high-performance glycidyl versatate modified polysiloxane resin is characterized in that: the resin comprises the following components in parts by weight:
2-16 parts of ethyl silicate;
4.5-22.5 parts of vinyl triethoxysilane;
0.3-5 parts of a catalyst;
5-15 parts of tertiary carbonic acid glycidyl ester;
30-60 parts of acrylate and a monomer;
0.1-5.5 parts of initiator;
15-30 parts of a solvent;
wherein, the compositions of the acrylic esters and the monomers are 8-13 parts of styrene, 3-9 parts of hydroxyethyl acrylate, 7-13 parts of methyl methacrylate, 14-18 parts of butyl acrylate and 0.5-1 part of acrylic acid; the solvent is selected from one or more of dimethylbenzene, methylbenzene and butyl acetate;
the preparation method of the resin comprises the following steps:
the first step is as follows: uniformly mixing ethyl silicate and vinyl triethoxysilane, heating to 45-55 ℃, slowly adding a catalyst under the temperature condition, and finishing the addition for 1.5-2 hours; heating to 50-60 ℃, reacting for 2-3h, and then carrying out reduced pressure distillation to obtain a polysiloxane prepolymer;
the second step is that: introducing nitrogen, uniformly mixing the prepared polysiloxane prepolymer and the tertiary carbonic acid glycidyl ester, heating to 145-160 ℃, and slowly adding the mixed solution of the acrylate, the monomer and the initiator under the temperature condition; and after the addition is finished, continuing to perform copolymerization reaction for 4-6h, cooling to 80-100 ℃ after the reaction is finished, and adding a solvent for dilution to obtain the high-performance tertiary carbonic acid glycidyl ester modified polysiloxane resin.
2. The high performance glycidyl versatate-modified polysiloxane resin according to claim 1, characterized in that: the weight portions of the ethyl silicate, the vinyl triethoxysilane, the catalyst, the tertiary carbonic acid glycidyl ester, the acrylate and the monomer, the initiator and the solvent are 8-12 parts, 15-20 parts, 2-4.5 parts, 8.5-12 parts, 35-52 parts, 0.7-1.4 parts and 20-25 parts in sequence.
3. The high performance glycidyl versatate-modified polysiloxane resin according to claim 1 or 2, characterized in that: the catalyst is selected from one or more of water, hydrochloric acid and acetic acid.
4. The high performance glycidyl versatate-modified polysiloxane resin according to claim 3, which is characterized in that: the catalyst is a mixture of water and hydrochloric acid, and the weight parts of the catalyst are 1-8 parts and 0.1-1 part in sequence.
5. The high performance glycidyl versatate-modified polysiloxane resin according to claim 1 or 2, which is characterized in that: the initiator is selected from one or more of di-tert-amyl peroxide, azobisisobutyronitrile and benzoyl peroxide.
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| CN202010131236.4A CN111234134B (en) | 2020-02-28 | 2020-02-28 | High-performance glycidyl versatate modified polysiloxane resin and preparation method thereof |
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| CN202010131236.4A CN111234134B (en) | 2020-02-28 | 2020-02-28 | High-performance glycidyl versatate modified polysiloxane resin and preparation method thereof |
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| CN111234134B true CN111234134B (en) | 2023-01-17 |
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| CN100588664C (en) * | 2006-08-11 | 2010-02-10 | 上海市涂料研究所 | Water acrylic resin and preparing method thereof |
| CN101935425B (en) * | 2010-09-16 | 2012-08-29 | 江门市制漆厂有限公司 | Modified polyurethane (PU) acrylic resin and preparation method thereof |
| CN105237676A (en) * | 2015-10-22 | 2016-01-13 | 佛山市高明同德化工有限公司 | Water-soluble organosilicon-modified acrylic resin and preparation method thereof |
| CN107033296A (en) * | 2017-05-08 | 2017-08-11 | 南京长江涂料有限公司 | Extra-weather-proof polysiloxane-modified acrylic resin and finish paint preparation method |
| CN108084367A (en) * | 2017-12-29 | 2018-05-29 | 安徽科邦树脂科技有限公司 | A kind of antibiotic property acrylic resin |
| CN108707207B (en) * | 2018-06-22 | 2020-10-09 | 河北科技大学 | Solvent-free hydroxyl acrylic resin and preparation method and application thereof |
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