CN110746590A - Polyether amine modified waterborne alkyd resin and preparation method thereof - Google Patents
Polyether amine modified waterborne alkyd resin and preparation method thereof Download PDFInfo
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- CN110746590A CN110746590A CN201911137219.5A CN201911137219A CN110746590A CN 110746590 A CN110746590 A CN 110746590A CN 201911137219 A CN201911137219 A CN 201911137219A CN 110746590 A CN110746590 A CN 110746590A
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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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 relates to polyether amine modified waterborne alkyd resin and a preparation method thereof, wherein the polyether amine modified waterborne alkyd resin comprises the following components in parts by weight: 20.0-40.0 parts of vegetable oil, 4.0-12.0 parts of polyether amine, 20.0-50.0 parts of organic acid anhydride, 25.0-70.0 parts of polyol, 10.0-25.0 parts of dimethylbenzene, 2.5-6.0 parts of n-octanoic acid, 3.5-7.0 parts of dimethylolpropionic acid, 0.5-1.0 part of sodium bicarbonate, 4.0-12.0 parts of neutralizing agent, 0.1-0.5 part of dibutyltin dilaurate and 100.0-200.0 parts of deionized water; the polyether amine modified waterborne alkyd resin prepared by the invention has stable performance because the structures of the polyether amine containing three functionalities and the waterborne alkyd resin are connected through chemical bonds; the coating has the characteristics of good water resistance, corrosion resistance, impact resistance, outdoor weather resistance, high hardness, good fullness and the like, and can be used for internal and external wall coatings, water-based industrial coatings, water-based wood coatings and the like.
Description
Technical Field
The invention relates to a modified waterborne alkyd resin, in particular to a polyether amine modified waterborne alkyd resin and a preparation method thereof, belonging to the technical field of waterborne resin synthesis.
Background
The alkyd resin is an important resin for paint, and has the advantages of abundant monomer sources, low price, multiple varieties, large formula change, convenience for chemical modification and good performance; the alkyd paint has the characteristics of good construction performance, high film fullness, good flexibility and the like, and is widely applied to decoration and protection of steel structures. The characteristics of easy construction and cross-linking with oxygen make it self-dry and universal and widely used. Therefore, alkyd resins have been an important position in the paint industry since the development of alkyd resins, but alkyd paints have the obvious disadvantages of slow drying of the coating film, low hardness, poor water resistance, poor corrosion resistance, insufficient impact resistance, poor outdoor weatherability and the like.
Modification of alkyd resins has long received considerable attention and has led to certain efforts to improve their properties. Chinese patent CN109306037A discloses a water-based acrylic acid modified alkyd resin and a preparation method thereof, and the alkyd resin is prepared from 22-24% of dry or semi-dry vegetable oleic acid, 14-15% of side chain-carrying triol, 13-14% of phthalic anhydride, 0.05-0.15% of color reducing agent, 1-3% of reflux xylene, 0.7-1% of maleic anhydride, 2.5-2.7% of trimellitic anhydride, 4-5% of methyl methacrylate, 6-8% of styrene, 1-2% of butyl acrylate, 0.5-1% of initiator and 28-29% of propylene glycol methyl ether.
Chinese patent CN107778489A discloses an organosilicon modified waterborne alkyd resin and a preparation method thereof, wherein the components of the organosilicon modified waterborne alkyd resin comprise, by mass, 10-13 parts of an organosilicon prepolymer, 32-36 parts of fatty oil, 20-25 parts of trimethylolpropane, 1.5-2.0 parts of dibutyltin dilaurate, 20-23 parts of isophthalic acid, 6-7 parts of diethylene glycol, 3-4 parts of benzoic acid, 0.5-0.8 part of maleic anhydride, 14-16 parts of trimellitic anhydride, 12-15 parts of propylene glycol monomethyl ether, 10-13 parts of isopropanol, 17-18 parts of N, N-dimethylethanolamine and 100-110 parts of water.
The above-mentioned technical invention has improved properties, but has poor hardness, impact resistance and outdoor weatherability.
Disclosure of Invention
In order to solve the technical problems, the invention adds the polyether amine with good comprehensive performance, and in order to increase the hardness and outdoor weather resistance of a paint film, the polyether amine with three functionalities is connected with the water-based alkyd resin structure through a chemical bond, so that the performance is stable.
The polyether amine is a polymer with a main chain of a polyether structure and an active functional group at the tail end of the polymer as an amino group. While the amine groups offer the possibility of reacting polyetheramines with a wide variety of compounds. The special molecular structure of the polyether amine endows the polyether amine with excellent comprehensive performance, and the polyether amine has a series of performances of good toughness, impact resistance, corrosion inhibition, oxidation resistance and the like, and is widely applied to a plurality of fields.
The invention aims to provide a polyether amine modified waterborne alkyd resin.
The invention also provides a preparation method of the polyether amine modified waterborne alkyd resin.
The invention adopts the following technical scheme: the invention relates to polyether amine modified waterborne alkyd resin which comprises the following components in parts by weight: 20.0-40.0 parts of vegetable oil, 4.0-12.0 parts of polyether amine, 20.0-50.0 parts of organic acid anhydride, 25.0-70.0 parts of polyhydric alcohol, 10.0-25.0 parts of dimethylbenzene, 2.5-6.0 parts of n-octanoic acid, 3.5-7.0 parts of dimethylolpropionic acid, 0.5-1.0 part of sodium bicarbonate, 4.0-12.0 parts of neutralizing agent, 0.1-0.5 part of dibutyltin dilaurate and 100.0-200.0 parts of deionized water.
The polyether amine is trifunctional polyether amine, and the average molecular weight of the trifunctional polyether amine is 800-2000.
The vegetable oil is one or more of refined linseed oil, soybean oil, castor oil, palm oil and rapeseed oil.
The organic acid anhydride is one or a combination of more of hexahydrophthalic anhydride, acetic anhydride and maleic anhydride.
The polyhydric alcohol is one or a combination of more of butanediol, neopentyl glycol, diethylene glycol, trimethylolpropane, glycerol and pentaerythritol.
The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
The invention provides a preparation method of polyether amine modified waterborne alkyd resin, which comprises the following steps:
a) adding vegetable oil, polyol, organic acid anhydride, dimethylolpropionic acid and dimethylbenzene in sequence according to the weight part of the formula in a multifunctional reaction kettle, and introducing N under low-speed stirring2To remove O in the reaction kettle2；
b) Heating to 110-120 ℃, keeping the temperature for 1.5h, removing free water, quickly heating to 150-160 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, heating to 180 ℃, keeping the temperature for reaction for 1.0-1.5 h, then heating to 210-220 ℃ at the speed of 20 ℃/h, keeping the temperature for reaction for 1.0-1.5 h, and separating water generated by the reaction out by a water separator;
c) cooling to 160 ℃, adding sodium bicarbonate, dibutyltin dilaurate and polyether amine, heating to 210-220 ℃ at the speed of 30 ℃/h, carrying out heat preservation reaction for 1.5-2.0 h, adding n-octanoic acid, carrying out heat preservation reaction, measuring the acid value every 15-30 min, stopping the reaction when the acid value is 45-50 mgKOH/g, evaporating xylene serving as a solvent, recovering the evaporated xylene for the next reaction, cooling to below 50 ℃, adding a neutralizer, dispersing at a high speed, adding deionized water according to the formula amount, continuously stirring and dispersing uniformly, and filtering to obtain the polyether amine modified waterborne alkyd resin.
The invention provides polyether amine modified waterborne alkyd resin with excellent comprehensive performance and a preparation method thereof. The polyether amine modified waterborne alkyd resin prepared by the invention has the characteristics of good water resistance, corrosion resistance, impact resistance, outdoor weather resistance, high hardness, good flexibility, good fullness and the like, and can be used for internal and external wall coatings, waterborne industrial coatings, waterborne wood coatings and the like.
Detailed Description
The preparation of the polyetheramine-modified waterborne alkyd is further described in connection with the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
The polyether amine modified waterborne alkyd resin comprises the following components in parts by weight: 30.0 parts of soybean oil, 8.0 parts of polyetheramine, 30.0 parts of hexahydrophthalic anhydride, 15.0 parts of neopentyl glycol, 35.0 parts of trimethylolpropane, 18.0 parts of dimethylbenzene, 4.0 parts of n-octanoic acid, 5.0 parts of dimethylolpropionic acid, 0.7 part of sodium bicarbonate, 9.0 parts of triethylamine, 0.2 part of dibutyltin dilaurate and 150.0 parts of deionized water.
The preparation method of the polyether amine modified waterborne alkyd resin in the embodiment comprises the following steps:
a) sequentially adding soybean oil, neopentyl glycol, trimethylolpropane, hexahydrophthalic anhydride, dimethylolpropionic acid and dimethylbenzene into a multifunctional reaction kettle according to the weight part of the formula, and introducing N under low-speed stirring2To remove O in the reaction kettle2；
b) Heating to 120 ℃, keeping the temperature for 1.5h, removing free water, quickly heating to 150-160 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, heating to 180 ℃, keeping the temperature for reaction for 1.5h, then heating to 210-220 ℃ at the speed of 20 ℃/h, keeping the temperature for reaction for 1.0h, and separating water generated by the reaction by using a water separator;
c) cooling to 160 ℃, adding sodium bicarbonate, dibutyltin dilaurate and polyether amine, heating to 210-220 ℃ at the speed of 30 ℃/h, carrying out heat preservation reaction for 2.0h, adding n-octanoic acid, carrying out heat preservation reaction, measuring the acid value every 15-30 min, stopping the reaction when the acid value range is 48mgKOH/g, evaporating to remove a solvent xylene, recovering the evaporated xylene, using the recovered xylene for the next reaction, cooling to 45 ℃, adding triethylamine, dispersing at a high speed, adding deionized water with the formula amount, continuously stirring and dispersing uniformly, and filtering to obtain the polyether amine modified waterborne alkyd resin with the solid content of 45.2%.
Example 2
The polyether amine modified waterborne alkyd resin comprises the following components in parts by weight: 20.0 parts of palm oil, 6.0 parts of polyether amine, 20.0 parts of maleic anhydride, 20.0 parts of hexahydrophthalic anhydride, 25.0 parts of diethylene glycol, 23.0 parts of pentaerythritol, 15.0 parts of xylene, 3.5 parts of n-octanoic acid, 5.2 parts of dimethylolpropionic acid, 0.6 part of sodium bicarbonate, 6.5 parts of ammonia water, 0.2 part of dibutyltin dilaurate and 140.0 parts of deionized water.
The preparation method of the polyether amine modified waterborne alkyd resin in the embodiment comprises the following steps:
a) sequentially adding palm oil, diethylene glycol, pentaerythritol, maleic anhydride, hexahydrophthalic anhydride, dimethylolpropionic acid and xylene according to the weight part of the formula in a multifunctional reaction kettle, and introducing N under low-speed stirring2To remove O in the reaction kettle2；
b) Heating to 120 ℃, keeping the temperature for 1.5h, removing free water, quickly heating to 150-160 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, heating to 180 ℃, keeping the temperature for reaction for 1.0h, then heating to 210-220 ℃ at the speed of 20 ℃/h, keeping the temperature for reaction for 1.5h, and separating water generated by the reaction by using a water separator;
c) cooling to 160 ℃, adding sodium bicarbonate, dibutyltin dilaurate and polyether amine, heating to 210-220 ℃ at the speed of 30 ℃/h, carrying out heat preservation reaction for 2.0h, adding n-octanoic acid, carrying out heat preservation reaction, measuring the acid value every 15-30 min, stopping the reaction when the acid value range is 47mgKOH/g, evaporating to remove solvent xylene, recovering the evaporated xylene, using the recovered xylene for the next reaction, cooling to 45 ℃, adding ammonia water, dispersing at a high speed, adding deionized water with the formula amount, continuously stirring and dispersing uniformly, and filtering to obtain the polyether amine modified waterborne alkyd resin with the solid content of 46.2%.
Example 3
The polyether amine modified waterborne alkyd resin comprises the following components in parts by weight: 25.0 parts of castor oil, 8.0 parts of polyetheramine, 25.0 parts of hexahydrophthalic anhydride, 12.0 parts of acetic anhydride, 45.0 parts of trimethylolpropane, 15.0 parts of dimethylbenzene, 5.0 parts of n-octanoic acid, 5.5 parts of dimethylolpropionic acid, 0.6 part of sodium bicarbonate, 9.0 parts of triethylamine, 0.2 part of dibutyltin dilaurate and 140.0 parts of deionized water.
The preparation method of the polyether amine modified waterborne alkyd resin in the embodiment comprises the following steps:
a) in a multifunctional reaction kettleIn the formula, according to the weight portion of the formula, castor oil, trimethylolpropane, hexahydrophthalic anhydride, acetic anhydride, dimethylolpropionic acid and dimethylbenzene are added in turn, and N is introduced under the condition of low-speed stirring2To remove O in the reaction kettle2；
b) Heating to 110 ℃, keeping the temperature for 1.5h, removing free water, quickly heating to 150-160 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, heating to 180 ℃, keeping the temperature for reaction for 1.5h, then heating to 210-220 ℃ at the speed of 20 ℃/h, keeping the temperature for reaction for 1.0h, and separating water generated by the reaction by using a water separator;
c) cooling to 160 ℃, adding sodium bicarbonate, dibutyltin dilaurate and polyether amine, heating to 210-220 ℃ at the speed of 30 ℃/h, carrying out heat preservation reaction for 2.0h, adding n-octanoic acid, carrying out heat preservation reaction, measuring the acid value every 15-30 min, stopping the reaction when the acid value range is 480mgKOH/g, evaporating to remove a solvent xylene, recovering the evaporated xylene, using the recovered xylene for the next reaction, cooling to 45 ℃, adding triethylamine, dispersing at a high speed, adding deionized water with the formula amount, continuously stirring and dispersing uniformly, and filtering to obtain the polyether amine modified waterborne alkyd resin with the solid content of 46.5%.
The inventive examples were compared with conventional waterborne alkyds (comparative) according to the relevant standards and the performance criteria tested are shown in table 1.
Wherein, the drying speed is as follows: detection is carried out according to the specification of GB 1728;
adhesion force: detecting according to the regulation of GB/T1720-1988;
hardness: detecting according to the regulation of GB/T6739-2006;
water resistance: detecting according to the regulation of GB/T1733-93;
salt spray resistance: detecting according to the regulation of GB/T1771-1991;
impact resistance: detection was carried out according to the protocol (GB/T1732-1993);
flexibility: detection was carried out according to the protocol (GB/T1731-1993);
artificial aging resistance: detecting according to the regulation of (GB/T14522);
filiform corrosion: detection was carried out according to the regulation of (GB/T13452.4-92).
Table 1: performance specification of coating
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| Water resistance | 520h | 480h | 520h | 120h |
| Adhesion force | Level 0 | Level 0 | Level 0 | Stage 2 |
| Watch stem | 2.5h | 3h | 2.5h | 6h |
| Dried bean curd | 18h | 18h | 18h | 24h |
| Hardness of | 2H | 2H | 2H | B |
| Resistance to salt fog | 1000h | 800h | 1000h | 120h |
| Fullness (visual inspection) | Good effect | Good effect | Good effect | In general |
| Filiform corrosion | Light and slight | Light and slight | Light and slight | Severe severity of disease |
| Resistance to artificial aging | 1000h | 960h | 1000h | 120h |
| Impact resistance | Normal paint film | Normal paint film | Normal paint film | Cracking of paint film |
| Flexibility/mm | 1 | 1 | 1 | 2 |
It can be seen from table 1 that the adhesion, filiform corrosion, drying speed, impact resistance, water resistance, hardness, artificial aging resistance, etc. of the examples of the present invention far exceed those of conventional waterborne alkyd resins.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (6)
1. A polyether amine modified waterborne alkyd resin is characterized in that: the composition comprises the following components in parts by weight: 20.0-40.0 parts of vegetable oil, 4.0-12.0 parts of polyether amine, 20.0-50.0 parts of organic acid anhydride, 25.0-70.0 parts of polyol, 10.0-25.0 parts of dimethylbenzene, 2.5-6.0 parts of n-octanoic acid, 3.5-7.0 parts of dimethylolpropionic acid, 0.5-1.0 part of sodium bicarbonate, 4.0-12.0 parts of neutralizing agent, 0.1-0.5 part of dibutyltin dilaurate and 100.0-200.0 parts of deionized water, wherein the polyether amine is trifunctional polyether amine and has the average molecular weight of 800-2000.
2. The polyetheramine-modified waterborne alkyd resin of claim 1, wherein: the vegetable oil is one or more of refined linseed oil, soybean oil, castor oil, palm oil and rapeseed oil.
3. The polyetheramine-modified waterborne alkyd resin of claim 1, wherein: the organic acid anhydride is one or a combination of more of hexahydrophthalic anhydride, acetic anhydride and maleic anhydride.
4. The polyetheramine-modified waterborne alkyd resin of claim 1, wherein: the polyhydric alcohol is one or a combination of more of butanediol, neopentyl glycol, diethylene glycol, trimethylolpropane, glycerol and pentaerythritol.
5. The polyetheramine-modified waterborne alkyd resin of claim 1, wherein: the neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
6. The method of claim 1, wherein the method comprises the steps of: the preparation method comprises the following preparation processes:
a) adding vegetable oil, polyol, organic acid anhydride, dimethylolpropionic acid and dimethylbenzene in sequence according to the weight part of the formula in a multifunctional reaction kettle, and introducing N under low-speed stirring2To remove O in the reaction kettle2；
b) Heating to 110-120 ℃, keeping the temperature for 1.5h, removing free water, quickly heating to 150-160 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, heating to 180 ℃, keeping the temperature for reaction for 1.0-1.5 h, then heating to 210-220 ℃ at the speed of 20 ℃/h, keeping the temperature for reaction for 1.0-1.5 h, and separating water generated by the reaction out by a water separator;
c) cooling to 160 ℃, adding sodium bicarbonate, dibutyltin dilaurate and polyether amine, heating to 210-220 ℃ at the speed of 30 ℃/h, carrying out heat preservation reaction for 1.5-2.0 h, adding n-octanoic acid, carrying out heat preservation reaction, measuring the acid value every 15-30 min, stopping the reaction when the acid value is 45-50 mgKOH/g, evaporating xylene serving as a solvent, recovering the evaporated xylene for the next reaction, cooling to below 50 ℃, adding a neutralizer, dispersing at a high speed, adding deionized water according to the formula amount, continuously stirring and dispersing uniformly, and filtering to obtain the polyether amine modified waterborne alkyd resin.
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| CN112646154A (en) * | 2020-12-18 | 2021-04-13 | 合众（佛山）化工有限公司 | Triplecene derivative modified waterborne alkyd resin and preparation method thereof |
| CN113999346A (en) * | 2021-11-25 | 2022-02-01 | 合众（佛山）化工有限公司 | SIS elastomer modified waterborne alkyd resin and preparation method thereof |
| CN114044889A (en) * | 2021-12-27 | 2022-02-15 | 合众（佛山）化工有限公司 | High-wear-resistance scratch-resistant modified alkyd resin and preparation method thereof |
| CN114044887A (en) * | 2021-12-09 | 2022-02-15 | 合众（佛山）化工有限公司 | Hyperbranched hydroxypropyl distarch phosphate modified waterborne alkyd resin and preparation method thereof |
| CN114196302A (en) * | 2021-12-09 | 2022-03-18 | 合众（佛山）化工有限公司 | Hyperbranched modified alkyd resin water-based anticorrosive paint |
| CN114230741A (en) * | 2021-12-15 | 2022-03-25 | 合众（佛山）化工有限公司 | Allyl polyoxyethylene ether phosphate modified waterborne alkyd resin and preparation method thereof |
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| CN112646154A (en) * | 2020-12-18 | 2021-04-13 | 合众（佛山）化工有限公司 | Triplecene derivative modified waterborne alkyd resin and preparation method thereof |
| CN113999346A (en) * | 2021-11-25 | 2022-02-01 | 合众（佛山）化工有限公司 | SIS elastomer modified waterborne alkyd resin and preparation method thereof |
| CN114044887A (en) * | 2021-12-09 | 2022-02-15 | 合众（佛山）化工有限公司 | Hyperbranched hydroxypropyl distarch phosphate modified waterborne alkyd resin and preparation method thereof |
| CN114196302A (en) * | 2021-12-09 | 2022-03-18 | 合众（佛山）化工有限公司 | Hyperbranched modified alkyd resin water-based anticorrosive paint |
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| CN114044889A (en) * | 2021-12-27 | 2022-02-15 | 合众（佛山）化工有限公司 | High-wear-resistance scratch-resistant modified alkyd resin and preparation method thereof |
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