CN112980151B - Organic silicon modified polyester resin with tensile toughness and preparation method thereof - Google Patents
Organic silicon modified polyester resin with tensile toughness and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention relates to an organic silicon modified polyester resin with tensile toughness and a preparation method thereof, wherein the organic silicon modified polyester resin with tensile toughness comprises the following components: a high-temperature-resistant and high-toughness curing agent and organic silicon modified polyester resin; the weight ratio of the high-temperature-resistant high-toughness curing agent to the organic silicon modified polyester resin is 2-3; the high-temperature-resistant and high-toughness curing agent is prepared by mixing and reacting polyol and isocyanate, wherein the molar ratio of-NCO to-OH is 1.2-1.6. The invention can solve the problems of poor heat resistance of the tough polyester for the current industrial coating and poor toughness of the organic silicon modified polyester resin.
Description
Technical Field
The invention relates to an organic silicon modified polyester resin, in particular to an organic silicon modified polyester resin with tensile toughness and a preparation method thereof.
Background
Currently, industrial high-toughness polyesters are widely applied in coatings, wherein coil steel coatings and iron printing coatings are most widely applied, but the industrial high-toughness polyesters generally have poor high-temperature resistance and are limited in high-temperature environments or special applications. Therefore, in many patents, high heat resistance of polyester is achieved by incorporating silicone having high heat resistance, but the defect that toughness is deteriorated is difficult to complement, and a temperature of more than 280 ℃ is required for curing. It is far from being desirable for some coatings to require high toughness and post-forming.
Disclosure of Invention
The invention aims to solve the technical problem of providing an organic silicon modified polyester resin with tensile toughness and a preparation method thereof, and solves the problems of poor heat resistance of tough polyester for the current industrial coating and poor toughness of the organic silicon modified polyester resin.
In order to solve the technical problems, the invention adopts a technical scheme that: the organic silicon modified polyester resin with tensile toughness comprises the following components: a high-temperature-resistant and high-toughness curing agent and organic silicon modified polyester resin; the weight ratio of the high-temperature-resistant high-toughness curing agent to the organic silicon modified polyester resin is (2-3);
the high-temperature-resistant and high-toughness curing agent is prepared by mixing and reacting polyol and isocyanate, wherein the molar ratio of-NCO to-OH is 1.2-1.6.
Further, one or more of trimethylolethane, trimethylolpropane, neopentyl glycol and polycarbonate diol are adopted as the polyol.
Further, one or more of isophthalic acid, terephthalic acid, succinic acid and adipic acid are adopted as the polybasic acid.
Further, the isocyanate adopts one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and hydrogenated xylylene diisocyanate (HMDI).
Furthermore, the organic silicon modified polyester resin is prepared by adopting the reaction of polyester resin and an organic silicon intermediate, and the weight ratio of the polyester resin to the organic silicon intermediate is (100).
The invention also provides a preparation method of the organic silicon modified polyester resin with tensile toughness, which comprises the following steps:
(1) Removing water from polyalcohol, adding a solvent, dropwise adding isocyanate at 75-80 ℃ to ensure that-NCO is within-OH molar ratio of 1.2-1.6, and preserving heat for 2 hours after dropwise adding to obtain a mixture A with solid content of 55-60%; dripping 18-20 parts by weight of sealant and 20-25 parts by weight of solvent into 100 parts by weight of the mixture A, keeping the temperature at 75-80 ℃ for 1.5 hours intermittently, adding 0.005-0.01 part by weight of catalyst, and reacting for 2 hours until the viscosity of the system is unchanged to obtain a high-temperature-resistant and high-toughness curing agent;
(2) And (2) adding the high-temperature-resistant and high-toughness curing agent obtained in the step (1) and the organic silicon modified polyester resin with the solid content of 60-65% into a reaction kettle according to the weight ratio of 2-3.
Further, the polyalcohol adopts one or more of trimethylolethane, trimethylolpropane, neopentyl glycol and polycarbonate diol; the isocyanate ester adopts one or more of Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI) hydrogenated xylylene diisocyanate (HMDI).
Further, the blocking agent is one or a mixture of more of butanone oxime, 3, 5-dimethylimidazole and diethyl malonate.
Further, the catalyst adopts one or a mixture of more of zinc octoate, stannous octoate and bismuth isooctanoate.
Further, the solvent of the high-temperature-resistant and high-toughness curing agent adopts a 150# solvent and/or a DBE solvent.
Further, the organic silicon modified polyester resin is prepared by adopting the following steps:
(1) Adding 25-30 parts by weight of polyhydric alcohol and 25-35 parts by weight of polybasic acid into a reaction container, heating to 120 ℃, stirring, continuously heating to 230 ℃, cooling when the acid value is less than 6, and adding a solvent for dilution when the temperature is reduced to 120 ℃;
(2) Taking 20-25 parts by weight of polyester resin obtained in the step (1), adding 1-5 parts by weight of organic silicon intermediate and 1-2 parts by weight of solvent into a reaction container protected by nitrogen, stirring for 1-1.5 hours at 80 ℃, adding 0.1-0.2 part by weight of catalyst, heating to 135-140 ℃, and preserving heat for 4-4.5 hours; and finally, cooling to 120 ℃, adding 2-3 parts by weight of solvent, and uniformly mixing to obtain the organic silicon modified polyester resin.
The advantages of the invention are as follows:
(1) The invention can solve the problems of poor heat resistance of the tough polyester and poor toughness of the organic silicon modified polyester resin for the current industrial coating, and the obtained organic silicon modified polyester resin can meet the curing condition of <240 ℃, and has excellent high temperature resistance and toughness;
(2) According to the invention, the high-toughness and excellent heat-resistant closed curing agent is synthesized, the high-toughness organic silicon modified polyester resin is prepared at the same time, and finally the polyester resin with high tensile property and high temperature resistance is obtained by optimizing the proportion of the curing agent and the organic silicon modified polyester;
(3) The finished resin synthesized by the method can be directly used, the single-component thermal self-crosslinking can be realized without adding a curing agent, the tough coating with high toughness and pencil hardness of 2-3H can be prepared by adding the resin and necessary fillers in the using process, and the method can be used for post-forming and special process requirements.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be embodied in other specific forms than those described herein, and it will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the present invention.
Example 1: a preparation method of an organic silicon modified polyester resin with tensile toughness comprises the following steps:
(1) Preparing a high-temperature-resistant and high-toughness curing agent:
taking 14.1 kg of trimethylolethane, 14.1 kg of trimethylolpropane, 10.4 kg of neopentyl glycol and 92 kg of polycarbonate diol, adding the materials into a reaction kettle, heating to 100 ℃, vacuumizing to remove water in the materials, adding 107.75 kg of a 150# solvent and 107.75 kg of a DBE solvent, setting the temperature to be 75-80 ℃, then dropwise adding a mixture of 30 kg of HMDI (4, 4' -dicyclohexylmethane diisocyanate) and 147.2 kg of IPDI (isophorone diisocyanate), wherein the molar ratio of NCO is-OH is 1.26, dropwise adding the mixture for about 1 hour, keeping the temperature for two hours, dropwise adding 60.4 kg of a blocking agent butanone oxime, finally adding 150# solvent and 32 kg of the DBE solvent, keeping the temperature for 1.5 hours at 75 ℃, adding 0.02 kg of a catalyst zinc octoate for reacting for about 2 hours until the viscosity of the system is not changed, and preparing a high-temperature-resistant and high-toughness curing agent for later use;
(2) Preparing high-toughness organic silicon modified polyester resin:
a. taking 7.67 kg of trimethylolpropane, 20.31 kg of neopentyl glycol, 24.7 kg of isophthalic acid and 5.2 kg of adipic acid into a reaction kettle, heating to 120 ℃, starting stirring, continuously heating to 230 ℃ at a heating rate of 10 ℃/h, starting cooling when the acid value to be measured is less than 6, adding a PMA solvent when the temperature is reduced to 120 ℃, and diluting to obtain a solid with a solid content of 65% for later use;
b. taking 20 kg of the polyester resin, adding 3 kg of DC-217 organic silicon intermediate and 1.61 kg of PMA solvent into a reaction kettle with nitrogen protection, stirring for about 1 hour at 80 ℃, adding 0.1 kg of n-butyl titanate, heating to 135 ℃, keeping the temperature for 4.5 hours, cooling to 120 ℃ after sampling is transparent, adding 2.06 kg of n-butyl alcohol, and uniformly mixing to obtain high-toughness organic silicon modified polyester with the solid content of 60%;
(3) And (3) adding the high-temperature-resistant and high-toughness curing agent synthesized in the step (1) and the high-toughness organic silicon modified polyester resin synthesized in the step (2) into a reaction kettle according to the weight ratio of 2.
Example 2: a preparation method of an organic silicon modified polyester resin with tensile toughness comprises the following steps:
(1) Preparing a high-temperature-resistant and high-toughness curing agent:
taking 14.1 kg of trimethylolethane, 14.1 kg of trimethylolpropane, 10.4 kg of neopentyl glycol and 92 kg of polycarbonate diol, adding the materials into a reaction kettle, heating to 100 ℃, vacuumizing to remove water in the materials, adding 107.75 kg of 150# solvent and 107.75 kg of DBE solvent at a set temperature of 80 ℃, then dropwise adding 30 kg of HMDI and 147.2 kg of IPDI mixture, wherein the molar ratio of NCO to OH is 1.26, dropwise adding the sealant agent butanone oxime 60.4 kg, finally adding 32 kg of 150# solvent and 32 kg of DBE solvent, continuously keeping the temperature at 75-80 ℃ for 1.5 hours, adding 0.02 kg of zinc octoate serving as a catalyst, reacting for about 2 hours until the viscosity of the system is not changed, and preparing a high-temperature-resistant and high-toughness curing agent for later use;
(2) Preparation of high-toughness organic silicon modified polyester resin:
a. taking 8.5 kg of trimethylolethane, 21.1 kg of neopentyl glycol, 25.5 kg of isophthalic acid and 6.0 kg of adipic acid into a reaction kettle, heating to 120 ℃, starting stirring, continuously heating to 230 ℃ at a heating rate of 10 ℃/h, starting cooling when the acid ester to be detected is less than 6, adding a PMA solvent when the temperature is reduced to 120 ℃, and diluting to obtain 65% of solid content for later use;
b. taking 20 kg of the polyester resin, adding 3 kg of DC-217 organic silicon intermediate and 1.61 kg of PMA solvent into a reaction kettle with nitrogen protection, stirring for about 1.5 hours at 80 ℃, adding 0.1 kg of n-butyl titanate, heating to 140 ℃, keeping the temperature for 4 hours, cooling to 120 ℃ after sampling and transparency, adding 2.06 kg of n-butyl alcohol, and uniformly mixing to obtain high-toughness organic silicon modified polyester with 60% of solid content;
(3) And (3) adding the high-temperature-resistant and high-toughness curing agent synthesized in the step (1) and the high-toughness organic silicon modified polyester resin synthesized in the step (2) into a reaction kettle according to the weight ratio of 2.
Example 3: a preparation method of an organic silicon modified polyester resin with tensile toughness comprises the following steps:
(1) Preparing a high-temperature-resistant and high-toughness curing agent:
taking 14.1 kg of trimethylolethane, 14.1 kg of trimethylolpropane, 10.4 kg of neopentyl glycol and 92 kg of polycarbonate diol, adding the materials into a reaction kettle, heating to 100 ℃, vacuumizing to remove water in the raw materials, adding 107.75 kg of 150# solvent and 107.75 kg of DBE, setting the temperature to 80 ℃, then dropwise adding 30 kg of HMDI and 147.2 kg of IPDI mixture, keeping the molar ratio of NCO to-OH to be 1.26, dropwise adding 60.4 kg of sealant butanone oxime, finally adding 32 kg of 150# solvent and 32 kg of DBE solvent, continuously keeping the temperature at 80 ℃ for 1.5 hours, adding zinc octoate serving as a catalyst, reacting for about 2 hours until the viscosity of the system is not changed, and preparing a high-temperature-resistant and high-toughness curing agent for later use;
(2) Preparing high-toughness organic silicon modified polyester resin:
a. taking 4.56 kg of trimethylolpropane, 19.6 kg of neopentyl glycol, 4.55 kg of trimethylolethane, 22.5 kg of isophthalic acid and 4.8 kg of adipic acid into a reaction kettle, heating to 120 ℃, starting stirring, continuously heating to 230 ℃ at a heating rate of 10 ℃/h, starting cooling when the temperature of an acid ester to be detected is less than 6, adding a PMA solvent when the temperature is reduced to 120 ℃, and diluting to obtain 65% of solid content for later use;
b. taking 20 kg of the polyester resin, adding 1.5 kg of Wake 232 organic silicon intermediate, 1.5 kg of Dow Corning 3074 organic silicon intermediate and 1.61 kg of PMA solvent into a reaction kettle with nitrogen protection, stirring for about 1-1.5 hours at 80 ℃, adding 0.1 kg of n-butyl titanate, heating to 140 ℃, keeping the temperature for 4.5 hours, cooling to 120 ℃ after sampling is transparent, adding 2.06 kg of n-butyl alcohol, and uniformly mixing to obtain the high-toughness organic silicon modified polyester with the solid content of 60%.
(3) Adding the synthesized high-temperature-resistant and high-toughness curing agent and the high-toughness organic silicon modified polyester resin into a reaction kettle according to the weight ratio of 2.
Example 4: a preparation method of an organic silicon modified polyester resin with tensile toughness comprises the following steps:
(1) Preparing a high-temperature-resistant and high-toughness curing agent:
adding 156.2 kg of polycarbonate diol into a reaction kettle, heating to 100 ℃, vacuumizing to remove water in raw materials, adding 120 kg of a 150# solvent and 120 kg of a DBE solvent, setting the temperature to be 75-80 ℃, then dropwise adding a mixture of 30 kg of HMDI (4, 4' -dicyclohexylmethane diisocyanate) and 147.2 kg of IPDI (isophorone diisocyanate), wherein the molar ratio of NCO to-OH is 1.6, dropwise adding for about 1.5 hours, and keeping the temperature for two hours to obtain a mixture A; then 114.8 kg of sealant 3.5-dimethyl imidazole is dripped into the mixture A, finally 57.4 kg of 150# solvent and 57.4 kg of DBE solvent are added, the temperature is kept at 75-80 ℃ for 1.5 hours, and then 0.06 kg of catalyst stannous octoate is added for reaction for about 2 hours until the viscosity of the system is not changed, so as to prepare the high-temperature-resistant and high-toughness curing agent for later use;
(2) Preparation of high-toughness organic silicon modified polyester resin: the same as example 1;
(3) And (3) adding the high-temperature-resistant and high-toughness curing agent synthesized in the step (1) and the high-toughness organic silicon modified polyester resin synthesized in the step (2) into a reaction kettle according to the weight ratio of 3.
Example 5: a preparation method of an organic silicon modified polyester resin with tensile toughness comprises the following steps:
(1) Preparing a high-temperature-resistant and high-toughness curing agent:
adding 10.4 kg of neopentyl glycol and 133.8 kg of polycarbonate diol into a reaction kettle, heating to 100 ℃, vacuumizing to remove moisture in the raw materials, adding 116.4 kg of a 150# solvent and 116.4 kg of a DBE solvent, setting the temperature to be 75-80 ℃, then dropwise adding a mixture of 30 kg of HMDI (4, 4' -dicyclohexylmethane diisocyanate) and 147.2 kg of IPDI (isophorone diisocyanate), wherein the molar ratio of NCO to-OH is 1.5, finishing dropwise adding for about 1-1.5 hours, and keeping the temperature for two hours to obtain a mixture A; dropwise adding 105.3 kg of sealant diethyl malonate into the mixture A, finally adding 55.4 kg of 150# solvent and 55.4 kg of DBE solvent, continuously keeping the temperature at 75-80 ℃ for 1.5 hours, adding 0.03 kg of catalyst zinc octoate, reacting for about 2 hours until the viscosity of the system is unchanged, and preparing the high-temperature-resistant and high-toughness curing agent for later use;
(2) Preparing high-toughness organic silicon modified polyester resin: the same as example 1;
(3) And (3) adding the high-temperature-resistant and high-toughness curing agent synthesized in the step (1) and the high-toughness organic silicon modified polyester resin synthesized in the step (2) into a reaction kettle according to the weight ratio of 2.5, stirring and dispersing for 1 hour at the temperature of 60-70 ℃, and filtering with 200-mesh filter cloth to obtain the organic silicon modified polyester resin with tensile toughness.
Example 6: a preparation method of an organic silicon modified polyester resin with tensile toughness comprises the following steps:
(1) Preparing a high-temperature-resistant and high-toughness curing agent:
adding 60 kg of trimethylolethane and 19.7 kg of trimethylolpropane into a reaction kettle, heating to 100 ℃, vacuumizing to remove water in the raw materials, adding 84 kg of 150# solvent and 84 kg of DBE, setting the temperature to be 75-80 ℃, then dropwise adding 152.1 kg of hexamethylene diisocyanate to ensure that the-NCO is in a-OH molar ratio of 1.4, finishing dropwise adding for about 1.5 hours, keeping the temperature for two hours, dropwise adding 81.5 kg of butanone oxime serving as a sealing agent, finally adding 40 kg of 150# solvent and 40 kg of DBE solvent, keeping the temperature for 1.5 hours at 75-80 ℃, adding 0.02 kg of bismuth isooctanoate serving as a catalyst to react for about 2 hours, and preparing a high-temperature-resistant and high-toughness curing agent for later use until the viscosity of the system is unchanged;
(2) Preparation of high-toughness organic silicon modified polyester resin: the same as example 1;
(3) Adding the synthesized high-temperature-resistant and high-toughness curing agent and the high-toughness organic silicon modified polyester resin into a reaction kettle according to the weight ratio of 2.
Comparative example 1:
commercially available coil steel polyester polyol, polyester polyol 055 and C202 from Foshan spring millet packaging material Co., ltd, and cyanamide curing agent CYMEL 303. 1-4 g of CYMEL303 is added into 10 g of polyester polyol, and the curing condition is 240 ℃, the micro-yellow discoloration appears in 10min, and the brown yellowing appears seriously in 10min at 280 ℃.
The performance parameters of the above examples are shown in the following table:
the tensile toughness of examples 1-6 above was measured according to ASTM D4145. The performance indexes show that the organosilicon modified polyester resin prepared by the method can be cured at a low temperature of less than or equal to 240 ℃, has excellent tensile toughness and high temperature resistance, the toughness can meet the condition that when an aluminum sheet is 1-1.5 mm, the aluminum sheet can optimally reach 0T, and does not yellow in an environment of 280 ℃ for more than 10min, and other properties are not influenced. The organosilicon modified polyester resin prepared by the general method can be cured at the temperature of more than 280 ℃, and the toughness can only meet the requirement that the aluminum sheet can reach 1-2T when the thickness is 1-1.5 mm, and the aluminum sheet turns brown after being placed in an environment of 280 ℃ for more than 10 min.
The organosilicon modified polyester resin product can be cured at a low temperature of less than 240 ℃, has excellent tensile toughness and high temperature resistance, can reach 0T optimally when the aluminum sheet is 1-1.5 mm, is not yellowed for more than 10min at 280 ℃, and is not influenced by other properties. The coating prepared by adding the fillers with different properties can be directly used without adding a curing agent, and the single-component thermal self-crosslinking can be realized, so that the tough coating with high toughness and pencil hardness of 2-3H can be prepared by adding resin and necessary fillers in the using process, can be used for post-forming and special process requirements, and solves the problems of high-temperature curing and insufficient toughness at present.
The silicone modified polyester resin with tensile toughness and the preparation method thereof provided by the present application are described in detail above, and the principle and the embodiment of the present application are explained in the present application by applying specific examples, and the description of the above examples is only used to help understanding the method and the core idea of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (5)
1. An organic silicon modified polyester resin with tensile toughness is characterized by comprising the following components: high-temperature-resistant and high-toughness curing agent and organic silicon modified polyester resin; the weight ratio of the high-temperature-resistant high-toughness curing agent to the organic silicon modified polyester resin is 2-3;
the preparation process of the high-temperature-resistant and high-toughness curing agent comprises the following steps:
removing water from polyalcohol, adding a solvent, dropwise adding isocyanate at 75-80 ℃ to ensure that-NCO is in a-OH molar ratio of 1.2-1.6, and keeping the temperature for 2 hours after dropwise adding to obtain a mixture A with the solid content of 55-60%; dripping 18-20 parts by weight of sealant and 20-25 parts by weight of solvent into 100 parts by weight of the mixture A, keeping the temperature at 75-80 ℃ for 1.5 hours intermittently, adding 0.005-0.01 part by weight of catalyst, and reacting for 2 hours until the viscosity of the system is unchanged to obtain a high-temperature-resistant and high-toughness curing agent;
the polyalcohol adopts one or more of trimethylolethane, trimethylolpropane, neopentyl glycol and polycarbonate diol; the isocyanate is one or more of Hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI) hydrogenated xylylene diisocyanate (HMDI);
the organic silicon modified polyester resin is prepared by the following steps:
(1) Adding 25-30 parts by weight of polyhydric alcohol and 25-35 parts by weight of polybasic acid into a reaction container, heating to 120 ℃, stirring, continuously heating to 230 ℃, cooling when the acid value is less than 6, and adding a solvent for dilution when the temperature is reduced to 120 ℃;
(2) Taking 20-25 parts by weight of polyester resin obtained in the step (1), adding 1-5 parts by weight of organic silicon intermediate and 1-2 parts by weight of solvent into a reaction container protected by nitrogen, stirring for 1-1.5 hours at 80 ℃, adding 0.1-0.2 part by weight of catalyst, heating to 135-140 ℃, and preserving heat for 4-4.5 hours; and finally, cooling to 120 ℃, adding 2-3 parts by weight of solvent, and uniformly mixing to obtain the organic silicon modified polyester resin.
2. A preparation method of an organic silicon modified polyester resin with tensile toughness is characterized by comprising the following steps:
(1) Removing water from polyalcohol, adding a solvent, dropwise adding isocyanate at 75-80 ℃ to ensure that-NCO is within-OH molar ratio of 1.2-1.6, and preserving heat for 2 hours after dropwise adding to obtain a mixture A with solid content of 55-60%; dripping 18-20 parts by weight of sealant and 20-25 parts by weight of solvent into 100 parts by weight of the mixture A, continuously preserving the heat at 75-80 ℃ for 1.5 hours, adding 0.005-0.01 part by weight of catalyst, and reacting for 2 hours until the viscosity of the system is unchanged to obtain a high-temperature-resistant and high-toughness curing agent; the polyalcohol adopts one or more of trimethylolethane, trimethylolpropane, neopentyl glycol and polycarbonate diol; the isocyanate adopts one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and hydrogenated xylylene diisocyanate (HMDI);
(2) Adding the high-temperature-resistant and high-toughness curing agent obtained in the step (1) and the organic silicon modified polyester resin with the solid content of 60-65% into a reaction kettle according to the weight ratio of 2-3;
the organic silicon modified polyester resin is prepared by the following steps:
(1) Adding 25-30 parts by weight of polyhydric alcohol and 25-35 parts by weight of polybasic acid into a reaction container, heating to 120 ℃, stirring, continuously heating to 230 ℃, cooling when the acid value is less than 6, and adding a solvent for dilution when the temperature is reduced to 120 ℃;
(2) Taking 20-25 parts by weight of polyester resin obtained in the step (1), adding 1-5 parts by weight of organic silicon intermediate and 1-2 parts by weight of solvent into a reaction container protected by nitrogen, stirring for 1-1.5 hours at 80 ℃, adding 0.1-0.2 part by weight of catalyst, heating to 135-140 ℃, and preserving heat for 4-4.5 hours; and finally, cooling to 120 ℃, adding 2-3 parts by weight of solvent, and uniformly mixing to obtain the organic silicon modified polyester resin.
3. The method for producing the silicone-modified polyester resin with tensile toughness according to claim 2, characterized in that: the blocking agent is one or a mixture of more of butanone oxime, 3, 5-dimethylimidazole and diethyl malonate.
4. The method for producing the silicone-modified polyester resin with tensile toughness according to claim 2, characterized in that: the catalyst adopts one or a mixture of more of zinc octoate, stannous octoate and bismuth isooctanoate.
5. The method for producing the silicone-modified polyester resin with tensile toughness according to claim 2, characterized in that: the solvent of the high-temperature-resistant and high-toughness curing agent adopts a 150# solvent and/or a DBE solvent.
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