CN111647149A - Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof - Google Patents
Polyester resin with excellent wear resistance and chemical resistance for powder and preparation method thereof Download PDFInfo
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- CN111647149A CN111647149A CN202010643690.8A CN202010643690A CN111647149A CN 111647149 A CN111647149 A CN 111647149A CN 202010643690 A CN202010643690 A CN 202010643690A CN 111647149 A CN111647149 A CN 111647149A
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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
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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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
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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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
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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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- 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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- 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
- C09D5/03—Powdery paints
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Abstract
The invention belongs to the technical field of polyester resin preparation, and particularly relates to a powder polyester resin with excellent wear resistance and chemical resistance, and a preparation method thereof. The polyester resin provided by the invention is mainly obtained by polymerizing 3, 3-bis (chloromethyl) oxetane, neopentyl glycol diglycidyl ether, terephthalic acid, neopentyl glycol, tris (2-hydroxyethyl) isocyanurate, 1, 4-naphthalenedicarboxylic acid and 5-nitroisophthalic acid. The polyester resin obtained by the invention is used in powder coating of N, N, N ', N' -tetra (2-hydroxyethyl) adipamide (HAA) curing system, so that a coating film with excellent wear resistance and chemical resistance can be obtained, and the resistance to acetic acid with 5 percent, sulfuric acid with 5 percent, NaOH with 5 percent, methanol, ethyl acetate, acetone, xylene and acrylic acid with 5 grades can be achieved; no change after 2 hours of water boiling; the wear resistance reaches more than 3.8L/mum.
Description
Technical Field
The invention belongs to the technical field of polyester resin preparation, and particularly relates to a powder polyester resin with excellent wear resistance and chemical resistance, and a preparation method thereof.
Background
The powder coating has good protective performance and decorative performance, so the powder coating is widely applied to the conventional coating industry at present, such as the coating of guardrails of expressways, outdoor units of air conditioners, indoor metal tables and chairs and the like. In order to enhance the decorative effect, most of the table tops of newly-built chemical laboratories are made of metal, such as tinplate, aluminum alloy and the like, although the common polyester powder coating is used for coating, the polyester resin used in the common polyester powder coating is mostly polymerized by common terephthalic acid, adipic acid, diethylene glycol, ethylene glycol and the like, and finally the formed coating film has insufficient hardness and poor wear resistance and chemical resistance, and is easy to wear after long-term use. Due to the special environment of a chemical laboratory, different conventional medicines are scattered carelessly in the using process, and the medicines can damage the coating film of the common powder coating, so that the coating film on the metal table top is discolored, bubbled and even cracked.
CN110183617A discloses a transparent powder 50: 50 polyester resin, a preparation method and application thereof, and the product disclosed in the patent document has greatly improved performances in the aspects of wear resistance and light transmittance, and can be used for preparing transparent powder coating with excellent wear resistance. But not simultaneously resistant to chemicals.
CN109679467A discloses a polyester resin for indoor powder coating and a preparation method thereof, the method provides the polyester resin for indoor powder coating, which is characterized in that: the composite material is prepared from the following raw materials in percentage by mass: 3-4% of neopentyl glycol, 10-14% of ethylene glycol, 12-15% of diethylene glycol, 0.4-0.8% of trimethylolpropane, 60-65% of terephthalic acid, 0.2-0.5% of isophthalic acid, 0.3-0.5% of trimellitic anhydride, 0.08-0.1% of monobutyl tin oxide and 0.3-0.5% of 18/16 tertiary amine. The polyester resin prepared by the method has the following characteristics: 1. when the melting flow is flat, the melting viscosity is low, so that the powder coating has enough leveling time, the leveling property of a coating film is good, and the luster is high; 2. the adhesive force to the coated object is good, and no primary coating is needed; 3. the preparation range of the coating is wide, and the coating with different performance requirements and curing speed can be prepared; 4. the physical mechanical property and chemical resistance of the coating film are good. The chemical resistance is good, but the wear resistance is still to be further improved.
Therefore, there is a need to invent a polyester resin for powder having both abrasion resistance and chemical resistance against the above-mentioned state of the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides a polyester resin for powder, which has a micromolecule chlorinated polyether chain segment with excellent wear resistance and chemical resistance and excellent wear resistance and chemical resistance;
the invention also provides a preparation method of the polyester resin.
The polyester resin provided by the invention is mainly obtained by polymerizing 3, 3-bis (chloromethyl) oxetane, neopentyl glycol diglycidyl ether, terephthalic acid, neopentyl glycol, tris (2-hydroxyethyl) isocyanurate, 1, 4-naphthalenedicarboxylic acid and 5-nitroisophthalic acid.
The polyester resin comprises the following main raw materials in parts by mole:
20-35% of 3, 3-bis (chloromethyl) oxetane; 10-18 parts of neopentyl glycol diglycidyl ether; 15-25 parts of N, N-dimethylacetamide; 14-28 parts of terephthalic acid; 15-32 parts of neopentyl glycol; 6-13 parts of 1, 4-naphthalenedicarboxylic acid; 4-8 parts of tris (2-hydroxyethyl) isocyanurate; 5-10% of 5-nitroisophthalic acid;
preferably, 20-34 parts of 3, 3-bis (chloromethyl) oxetane; 10-17 parts of neopentyl glycol diglycidyl ether; 15-24 parts of N, N-dimethylacetamide; 14-27 parts of terephthalic acid; 15-31 parts of neopentyl glycol; 6-12 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid;
preferably, 20-33 parts of 3, 3-bis (chloromethyl) oxetane; 10-16 parts of neopentyl glycol diglycidyl ether; 15-23 parts of N, N-dimethylacetamide; 14-26 parts of terephthalic acid; 15-30 parts of neopentyl glycol; 6-11 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid;
preferably, 20-32 parts of 3, 3-bis (chloromethyl) oxetane; 10-17 parts of neopentyl glycol diglycidyl ether; 15-22 parts of N, N-dimethylacetamide; 14-25 parts of terephthalic acid; 15-29 parts of neopentyl glycol; 6-10 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid;
preferably, 20-31 parts of 3, 3-bis (chloromethyl) oxetane; 10-16 parts of neopentyl glycol diglycidyl ether; 15-21 parts of N, N-dimethylacetamide; 14-26 parts of terephthalic acid; 15-28 parts of neopentyl glycol; 6-12 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid;
preferably, 20-30 parts of 3, 3-bis (chloromethyl) oxetane; 10-16 parts of neopentyl glycol diglycidyl ether; 15-21 parts of N, N-dimethylacetamide; 14-25 parts of terephthalic acid; 15-28 parts of neopentyl glycol; 6-11 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-8 parts of 5-nitroisophthalic acid;
preferably, 20-29 parts of 3, 3-bis (chloromethyl) oxetane; 10-15 parts of neopentyl glycol diglycidyl ether; 15-24 parts of N, N-dimethylacetamide; 14-24 parts of terephthalic acid; 15-27 parts of neopentyl glycol; 6-10 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid;
preferably, 20-28 parts of 3, 3-bis (chloromethyl) oxetane; 11-16 parts of neopentyl glycol diglycidyl ether; 15-23 parts of N, N-dimethylacetamide; 14-25 parts of terephthalic acid; 15-26 parts of neopentyl glycol; 6-10 parts of 1, 4-naphthalenedicarboxylic acid; 4-6 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid;
preferably, 22-29 parts of 3, 3-bis (chloromethyl) oxetane; 10-17 parts of neopentyl glycol diglycidyl ether; 15-24 parts of N, N-dimethylacetamide; 14-27 parts of terephthalic acid; 15-31 parts of neopentyl glycol; 6-12 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-8 parts of 5-nitroisophthalic acid;
preferably, 3, 3-bis (chloromethyl) oxetane 27; neopentyl glycol diglycidyl ether 14; n, N-dimethylacetamide 20; 20 parts of terephthalic acid; neopentyl glycol 23; 1, 4-naphthalenedicarboxylic acid 9; tris (2-hydroxyethyl) isocyanurate 6; 5-nitroisophthalic acid 7;
preferably, 3, 3-bis (chloromethyl) oxetane 28; neopentyl glycol diglycidyl ether 15; n, N-dimethylacetamide 21; 21 parts of terephthalic acid; neopentyl glycol 21; 1, 4-naphthalenedicarboxylic acid 8; tris (2-hydroxyethyl) isocyanurate 6; 5-Nitro isophthalic acid 7.
The polyester resin also uses a catalyst in the preparation process;
the catalyst comprises a catalyst for polymerizing small-molecule chlorinated polyether and an esterification reaction catalyst;
the catalyst for polymerizing the small molecular chlorinated polyether is triisobutyl aluminum, and the using amount of the catalyst is 0.05-0.15 percent of the mass of 3, 3-bis (chloromethyl) oxetane;
the esterification catalyst is monobutyl tin oxide, and the using amount of the esterification catalyst is 0.1-0.3% of the total molar amount of the raw materials.
The polyester resin also uses an antioxidant in the preparation process; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the using amount of the antioxidant is 0.2-0.5% of the total molar amount of the main raw materials.
The preparation method of the polyester resin for powder with excellent wear resistance and chemical resistance comprises the following steps:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating and carrying out heat preservation reaction, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to carry out micromolecule chlorinated polyether polymerization reaction, and continuously carrying out heat preservation reaction after dropwise adding;
(2) adding neopentyl glycol diglycidyl ether into the material in the step (1) to participate in copolymerization reaction, heating, and carrying out heat preservation reaction;
(3) adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst namely monobutyl tin oxide into the materials in the step (2) to perform esterification polymerization reaction, after the materials are uniformly mixed, gradually heating up under the protection of nitrogen, removing micromolecular water and solvent N, N-dimethylacetamide while heating up for reaction, and performing heat preservation reaction until no obvious distillate is evaporated out;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the material in the step (3) for chain extension reaction, gradually heating and carrying out heat preservation reaction; reacting under vacuum;
(5) and (3) cooling, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating again to perform esterification reaction, cooling after the reaction is stopped, discharging at high temperature, cooling the polyester resin by using a steel belt with condensed water, and crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
The preparation method of the polyester resin for powder with excellent wear resistance and chemical resistance is characterized in that (1), the temperature is raised to 70-90 ℃ and the temperature is kept;
preferably, in the step (1), 3-bis (chloromethyl) oxetane is dripped to carry out micromolecule chlorinated polyether polymerization reaction, and the dripping is controlled to be finished within 3-4 h;
preferably, in the step (1), 3-bis (chloromethyl) oxetane is dripped, and then the reaction is kept for 2.5-3.5 h.
Preferably, in the step (2), the heating rate is 8-12 ℃/h;
preferably, in the step (2), the temperature is gradually increased from 70-90 ℃ to 130-150 ℃ during temperature rising;
preferably, in the step (2), the reaction is carried out for 2-4 h under the condition of heat preservation.
Preferably, in (3), when the epoxy equivalent of the mixture is more than 1000g/mol, neopentyl glycol, terephthalic acid, 1, 4-naphthalene dicarboxylic acid and esterification catalyst of monobutyl tin oxide are added for esterification polymerization
Preferably, in the step (3), the temperature is gradually increased to 200-220 ℃ under the protection of nitrogen;
preferably, in the step (3), the heating rate is controlled to be 6-8 ℃/h;
preferably, in the step (3), the reaction is kept at the temperature until no obvious distillate is distilled out, and the acid value of the reactant is less than 60 mgKOH/g;
preferably, in the step (4), the temperature is gradually increased to 230-240 ℃ for heat preservation reaction for 1-2 h, and the temperature increase rate is controlled to be 8-12 ℃/h;
preferably, in the step (4), the reaction is carried out for 2-4 h under the condition of keeping the vacuum degree of 50-70 mmHg;
preferably, in the step (4), the vacuum is stopped when the acid value is reduced to below 18 mgKOH/g;
preferably, in the step (5), when the temperature is reduced to 200-220 ℃, 5-nitroisophthalic acid is added for carboxyl end capping reaction;
preferably, in the step (5), the temperature is raised to 230-240 ℃ again to carry out esterification reaction for 3-5 h;
preferably, in the step (5), the esterification reaction is stopped until the acid value of the reactant is 37-45 mgKOH/g;
preferably, in the step (5), the temperature is reduced to 190-210 ℃.
The preparation method of the polyester resin for powder with excellent wear resistance and chemical resistance comprises the following steps:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating to 70-90 ℃, keeping the temperature, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to perform micromolecule chlorinated polyether polymerization reaction, controlling the dropwise addition within 3-4 h, and continuously keeping the temperature for 2.5-3.5 h;
(2) adding neopentyl glycol diglycidyl ether into the material obtained in the step (1) to participate in copolymerization reaction, gradually heating from 70-90 ℃ to 130-150 ℃ at a heating rate of 8-12 ℃/h, and carrying out heat preservation reaction for 2-4 h;
(3) when the epoxy equivalent of the mixture is more than 1000g/mol, adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst monobutyl tin oxide for esterification polymerization reaction, after the materials are uniformly mixed, gradually heating to 200-220 ℃ under the protection of nitrogen, removing small molecular water and a solvent N, N-dimethylacetamide while heating for reaction, controlling the heating rate to be 6-8 ℃/h, and carrying out heat preservation reaction until no obvious distillate is evaporated out, wherein the acid value of a reactant is less than 60 mgKOH/g;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the mixture obtained in the step (3) for chain extension reaction, gradually heating to 230-240 ℃, and carrying out heat preservation reaction for 1-2 h, wherein the heating rate is controlled to be 8-12 ℃/h; then, reacting for 2-4 h under the vacuum degree of 50-70 mmHg, promoting the formation of macromolecular polyester resin, and stopping vacuum drawing when the acid value is reduced to below 18 mgKOH/g;
(5) and (3) when the temperature is reduced to 200-220 ℃, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating to 230-240 ℃ again to perform esterification reaction for 3-5 h, stopping the reaction when the acid value of the reactant is 37-45 mgKOH/g, cooling to 190-210 ℃, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
The polyester resin prepared by the method has an acid value of 37-45 mgKOH/g, a softening point: 115 to 123 ℃.
The invention has the beneficial effects that:
the invention provides a special polyester resin which is matched with a curing system of N, N, N ', N' -tetra (2-hydroxyethyl) adipamide (HAA) and has excellent wear resistance and chemical resistance, the obtained polyester resin molecule has a micromolecule chlorinated polyether chain segment with excellent wear resistance and chemical resistance, simultaneously, raw materials with high hardness and outstanding chemical resistance such as 1, 4-naphthalenedicarboxylic acid, tri (2-ethoxyl) isocyanurate, 5-nitroisophthalic acid and the like are matched, meanwhile, the neopentyl glycol diglycidyl ether participates in the reaction, so that the adhesive force with a metal substrate and the chemical resistance can be effectively improved, and finally the neopentyl glycol diglycidyl ether can be used in the powder coating of an N, N, N ', N' -tetra (2-hydroxyethyl) adipamide (HAA) curing system to obtain a coating film with excellent wear resistance and chemical resistance.
Detailed Description
The present invention will now be further described with reference to specific embodiments in order to enable those skilled in the art to better understand the present invention.
Example 1
The preparation method of the polyester resin for powder with excellent wear resistance and chemical resistance comprises the following steps:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating to 80 ℃, keeping the temperature, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to perform micromolecular chlorinated polyether polymerization reaction within 3.5 hours, and then continuously keeping the temperature for reaction for 3 hours;
(2) adding neopentyl glycol diglycidyl ether into the material obtained in the step (1) to participate in copolymerization reaction, gradually heating from 80 ℃ to 140 ℃ at a heating rate of 10 ℃/h, and carrying out heat preservation reaction for 3 h;
(3) when the epoxy equivalent of the mixture is more than 1000g/mol, adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst monobutyl tin oxide for esterification polymerization reaction, after the materials are uniformly mixed, gradually heating to 210 ℃ under the protection of nitrogen, removing micromolecular water and a solvent N, N-dimethylacetamide while heating for reaction, controlling the heating rate to be 7 ℃/h, and carrying out heat preservation reaction until no obvious distillate is evaporated out, wherein the acid value of a reactant is less than 60 mgKOH/g;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the mixture obtained in the step (3) for chain extension reaction, gradually heating to 235 ℃, and keeping the temperature for reaction for 1.5h, wherein the heating rate is controlled to be 10 ℃/h; then keeping the vacuum degree of 60mmHg for reaction for 3 hours to promote the formation of macromolecular polyester resin, and stopping vacuum drawing when the acid value is reduced to below 18 mgKOH/g;
(5) and when the temperature is reduced to 210 ℃, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating to 235 ℃ again to perform esterification reaction for 4 hours, stopping the reaction when the acid value of the reactant is 37-45 mgKOH/g, cooling to 200 ℃, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
Example 2
The preparation method of the polyester resin for powder with excellent wear resistance and chemical resistance comprises the following steps:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating to 70 ℃, keeping the temperature, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to perform micromolecular chlorinated polyether polymerization reaction within 3 hours, and then continuously keeping the temperature for reaction for 2.5 hours;
(2) adding neopentyl glycol diglycidyl ether into the material obtained in the step (1) to participate in copolymerization reaction, gradually heating from 70 ℃ to 130 ℃ at a heating rate of 8 ℃/h, and carrying out heat preservation reaction for 2 h;
(3) when the epoxy equivalent of the mixture is more than 1000g/mol, adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst monobutyl tin oxide for esterification polymerization reaction, after the materials are uniformly mixed, gradually heating to 200 ℃ under the protection of nitrogen, removing micromolecular water and a solvent N, N-dimethylacetamide while heating for reaction, controlling the heating rate to be 6 ℃/h, and carrying out heat preservation reaction until no obvious distillate is evaporated out, wherein the acid value of a reactant is less than 60 mgKOH/g;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the mixture obtained in the step (3) for chain extension reaction, gradually heating to 230 ℃, and keeping the temperature for reaction for 1 hour, wherein the heating rate is controlled to be 8 ℃/h; then keeping the vacuum degree of 50mmHg for reaction for 2 hours to promote the formation of macromolecular polyester resin, and stopping vacuum drawing when the acid value is reduced to below 18 mgKOH/g;
(5) and (2) when the temperature is reduced to 200 ℃, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating to 230 ℃ again to perform esterification reaction for 3 hours, stopping the reaction when the acid value of the reactant is 37-45 mgKOH/g, cooling to 190 ℃, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
Example 3
The preparation method of the polyester resin for powder with excellent wear resistance and chemical resistance comprises the following steps:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating to 90 ℃, keeping the temperature, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to perform micromolecular chlorinated polyether polymerization reaction within 4 hours, and then continuously keeping the temperature for reaction for 3.5 hours;
(2) adding neopentyl glycol diglycidyl ether into the material obtained in the step (1) to participate in copolymerization reaction, gradually heating from 90 ℃ to 150 ℃ at a heating rate of 12 ℃/h, and carrying out heat preservation reaction for 4 h;
(3) when the epoxy equivalent of the mixture is more than 1000g/mol, adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst monobutyl tin oxide for esterification polymerization reaction, after the materials are uniformly mixed, gradually heating to 220 ℃ under the protection of nitrogen, removing micromolecular water and a solvent N, N-dimethylacetamide while heating for reaction, controlling the heating rate to be 8 ℃/h, and carrying out heat preservation reaction until no obvious distillate is evaporated out, wherein the acid value of a reactant is less than 60 mgKOH/g;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the mixture obtained in the step (3) for chain extension reaction, gradually heating to 240 ℃, and keeping the temperature for reaction for 2 hours, wherein the heating rate is controlled to be 12 ℃/h; then keeping the vacuum degree of 70mmHg for reaction for 4 hours to promote the formation of macromolecular polyester resin, and stopping vacuum drawing when the acid value is reduced to below 18 mgKOH/g;
(5) and when the temperature is reduced to 220 ℃, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating to 240 ℃ again to perform esterification reaction for 5 hours, stopping the reaction when the acid value of the reactant is 37-45 mgKOH/g, cooling to 210 ℃, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
Examples 4 to 6 are the same as the method in example 1 of the present invention, except that the amount of the raw materials is slightly different, as shown in table 1 below:
TABLE 1 molar parts ratios of the respective raw materials in examples 1 to 6
| Examples1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| 3, 3-bis (chloromethyl) oxetane | 28 | 20 | 35 | 24 | 32 | 30 |
| Neopentyl glycol diglycidyl ether | 14 | 10 | 18 | 12 | 16 | 15 |
| N, N-dimethyl acetamide | 20 | 15 | 25 | 18 | 26 | 24 |
| Terephthalic acid (TPA) | 21 | 14 | 28 | 18 | 26 | 25 |
| Neopentyl glycol | 23 | 15 | 32 | 17 | 30 | 28 |
| 1, 4-naphthalenedicarboxylic acid | 10 | 6 | 13 | 7 | 11 | 12 |
| Tris (2-hydroxyethyl) isocyanurate | 6 | 4 | 8 | 5 | 7 | 6 |
| 5-Nitro-isophthalic acid | 8 | 5 | 10 | 6 | 7 | 9 |
The acid value and softening point of the polyester resin obtained in each example are shown in table 2 below:
TABLE 2 acid number and softening point of the products of examples 1-6
Comparative example 1
Polyester resin for commercial ordinary HAA curing system, acid value: 31mgKOH/g, softening point 108 ℃, model CE3098, and is purchased from Zhejiang pine New materials Co.
Example 7
The products in the examples were applied to the powder coating formulation as follows for the performance examination, in particular as follows:
the N, N, N ', N' -tetrakis (2-hydroxyethyl) adipamide (HAA) system powder coating formulation, in parts by weight, is generally as follows:
preparing a coating layer: mixing the materials uniformly according to the requirements of the formula of the N, N, N ', N' -tetra (2-hydroxyethyl) adipamide (HAA) system powder coating, extruding by a double-screw extruder, tabletting, crushing the tablets, and sieving to prepare the powder coating. The powder coating is sprayed on the galvanized iron substrate after surface treatment by an electrostatic spray gun, the film thickness is about 80 mu m, and then the powder coating is baked and cured at 180 ℃/10min to obtain the coating.
The detection of the coating index is based on GB/T21776 2008 'Standard guide for powder coating and coating detection';
the wear resistance test is carried out according to GB/T23988-;
the chemical corrosion resistance is carried out according to the method of step A of standard 4.40.5.1 of GB/T17657-2013, the chemical corrosion condition is at room temperature for 24h, the surface change is observed, the chemical is selected from conventional chemical in a chemical laboratory, the grade is 1 grade to 5 grade, and the higher the grade is, the stronger the chemical resistance is. Wherein, the 5 percent acetic acid, the 5 percent sulfuric acid and the 5 percent NaOH are mass concentration.
TABLE 3 basic properties of the products of the examples and comparative examples after application
| Sample (I) | Apparent appearance of coating film | Impact (50cm) | Gloss (60 degree angle) | Boiling resistant water boiling (2h) | Abrasion resistance (L/. mu.m) |
| Example 1 | Leveling | Positive and negative impact through | 92.5 | Without change | 3.86 |
| Example 2 | Leveling | Positive and negative impact through | 92.2 | Without change | 3.81 |
| Example 3 | Leveling | Positive and negative impact through | 91.9 | Without change | 3.97 |
| Example 4 | Leveling | Positive and negative impact through | 92.6 | Without change | 3.84 |
| Example 5 | Leveling | Positive and negative impact through | 92.7 | Without change | 3.93 |
| Example 6 | Leveling | Positive and negative impact through | 92.3 | Without change | 3.88 |
| Comparative example 1 | Leveling | Positive and negative impact through | 92.1 | Slight loss of light | 1.89 |
TABLE 4 chemical resistance of the products of the examples and comparative examples after application
| Sample (I) | 5% acetic acid | 5% sulfuric acid | 5％NaOH | Methanol | Ethyl acetate | Acetone (II) | Xylene | Acrylic acid |
| Example 1 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 |
| Example 2 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 |
| Example 3 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 |
| Example 4 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 |
| Example 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 |
| Example 6 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 | Grade 5 |
| Comparative example 1 | Grade 3 | Stage 2 | Stage 2 | Grade 3 | Grade 3 | Stage 2 | Stage 2 | Grade 3 |
As can be seen from tables 3 and 4, after the product of the invention is applied to powder coating, the coating film is smooth; in the impact property (50cm) examination, positive and negative impacts pass; the gloss (60 degree angle) reaches more than 91.9; no change is found in the observation of boiling resistance (2 h); the wear resistance is higher than 3.8L/mum in the investigation; after the product is applied, the resistance to 5% acetic acid, 5% sulfuric acid, 5% NaOH, methanol, ethyl acetate, acetone, xylene and acrylic acid can reach 5 grades;
the product in comparative example 1 was smooth in film appearance after application, with slight loss of gloss occurring during poaching (2h) test; in the examination of the abrasion resistance, only 1.89L/. mu.m. The product of comparative example 1 was resistant to 5% acetic acid, 5% sulfuric acid, 5% NaOH, methanol, ethyl acetate, acetone, xylene, and acrylic acid after application to 3, 2, 3, 2, and 3 grades, respectively. It is seen that the chemical resistance is far from the present invention.
The invention provides a special polyester resin which is matched with a curing system of N, N, N ', N' -tetra (2-hydroxyethyl) adipamide (HAA) and has excellent wear resistance and chemical resistance, and the obtained polyester resin molecule has a micromolecule chlorinated polyether chain segment with excellent wear resistance and chemical resistance; in addition, the invention also combines the raw materials with high hardness and outstanding chemical resistance, such as 1, 4-naphthalenedicarboxylic acid, tris (2-hydroxyethyl) isocyanurate, 5-nitroisophthalic acid and the like; and the neopentyl glycol diglycidyl ether participates in the reaction, can effectively improve the adhesive force with a metal substrate and the chemical resistance, and is finally used in the powder coating of an N, N, N ', N' -tetra (2-hydroxyethyl) adipamide (HAA) curing system to obtain a coating film with excellent wear resistance and chemical resistance.
Claims (10)
1. The polyester resin for powder with excellent wear resistance and chemical resistance is characterized by being mainly obtained by polymerizing 3, 3-bis (chloromethyl) oxetane, neopentyl glycol diglycidyl ether, terephthalic acid, neopentyl glycol, tris (2-hydroxyethyl) isocyanurate, 1, 4-naphthalenedicarboxylic acid and 5-nitroisophthalic acid.
2. The polyester resin for powders with excellent abrasion resistance and chemical resistance as claimed in claim 1, wherein the molar parts of the main raw materials of the polyester resin are as follows:
20-35% of 3, 3-bis (chloromethyl) oxetane; 10-18 parts of neopentyl glycol diglycidyl ether; 15-25 parts of N, N-dimethylacetamide; 14-28 parts of terephthalic acid; 15-32 parts of neopentyl glycol; 6-13 parts of 1, 4-naphthalenedicarboxylic acid; 4-8 parts of tris (2-hydroxyethyl) isocyanurate; 5-10% of 5-nitroisophthalic acid;
preferably, 20-34 parts of 3, 3-bis (chloromethyl) oxetane; 10-17 parts of neopentyl glycol diglycidyl ether; 15-24 parts of N, N-dimethylacetamide; 14-27 parts of terephthalic acid; 15-31 parts of neopentyl glycol; 6-12 parts of 1, 4-naphthalenedicarboxylic acid; 4-7 parts of tris (2-hydroxyethyl) isocyanurate; 5-9 parts of 5-nitroisophthalic acid.
3. The polyester resin for powders having excellent abrasion resistance and chemical resistance as claimed in claim 1, wherein a catalyst is further used in the preparation process of the polyester resin;
the catalyst comprises a catalyst for polymerizing small-molecule chlorinated polyether and an esterification reaction catalyst;
the catalyst for polymerizing the small molecular chlorinated polyether is triisobutyl aluminum, and the using amount of the catalyst is 0.05-0.15 percent of the mass of 3, 3-bis (chloromethyl) oxetane;
the esterification catalyst is monobutyl tin oxide, and the using amount of the esterification catalyst is 0.1-0.3% of the total molar amount of the raw materials.
4. The polyester resin for powders having excellent abrasion resistance and chemical resistance as claimed in claim 1, wherein an antioxidant is further used in the preparation process of the polyester resin; the antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and the using amount of the antioxidant is 0.2-0.5% of the total molar amount of the main raw materials.
5. The process for preparing polyester resin for powder excellent in abrasion resistance and chemical resistance according to claim 1, comprising the steps of:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating and carrying out heat preservation reaction, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to carry out micromolecule chlorinated polyether polymerization reaction, and continuously carrying out heat preservation reaction after dropwise adding;
(2) adding neopentyl glycol diglycidyl ether into the material in the step (1) to participate in copolymerization reaction, heating, and carrying out heat preservation reaction;
(3) adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst namely monobutyl tin oxide into the materials in the step (2) to perform esterification polymerization reaction, after the materials are uniformly mixed, gradually heating up under the protection of nitrogen, removing micromolecular water and solvent N, N-dimethylacetamide while heating up for reaction, and performing heat preservation reaction until no obvious distillate is evaporated out;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the material in the step (3) for chain extension reaction, gradually heating and carrying out heat preservation reaction; reacting under vacuum;
(5) and (3) cooling, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating again to perform esterification reaction, cooling after the reaction is stopped, discharging at high temperature, cooling the polyester resin by using a steel belt with condensed water, and crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
6. The method for preparing polyester resin for powder with excellent abrasion resistance and chemical resistance according to claim 5, wherein in the step (1), the temperature is raised to 70-90 ℃ and kept;
preferably, in the step (1), 3-bis (chloromethyl) oxetane is dripped to carry out micromolecule chlorinated polyether polymerization reaction, and the dripping is controlled to be finished within 3-4 h;
preferably, in the step (1), 3-bis (chloromethyl) oxetane is dripped, and then the reaction is kept for 2.5-3.5 h.
7. The method for preparing polyester resin for powder with excellent abrasion resistance and chemical resistance according to claim 5, wherein in the step (2), the temperature rise rate is 8-12 ℃/h;
preferably, in the step (2), the temperature is gradually increased from 70-90 ℃ to 130-150 ℃ during temperature rising;
preferably, in the step (2), the reaction is carried out for 2-4 h under the condition of heat preservation.
8. The method for preparing polyester resin for powder excellent in abrasion resistance and chemical resistance according to claim 5, wherein in (3), when the epoxy equivalent of the mixture is more than 1000g/mol, neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and the esterification catalyst monobutyltin oxide are added to conduct the esterification polymerization
Preferably, in the step (3), the temperature is gradually increased to 200-220 ℃ under the protection of nitrogen;
preferably, in the step (3), the heating rate is controlled to be 6-8 ℃/h;
preferably, in the step (3), the reaction is kept at the temperature until no obvious distillate is distilled out, and the acid value of the reactant is less than 60 mgKOH/g;
preferably, in the step (4), the temperature is gradually increased to 230-240 ℃ for heat preservation reaction for 1-2 h, and the temperature increase rate is controlled to be 8-12 ℃/h;
preferably, in the step (4), the reaction is carried out for 2-4 h under the condition of keeping the vacuum degree of 50-70 mmHg;
preferably, in the step (4), the vacuum is stopped when the acid value is reduced to below 18 mgKOH/g;
preferably, in the step (5), when the temperature is reduced to 200-220 ℃, 5-nitroisophthalic acid is added for carboxyl end capping reaction;
preferably, in the step (5), the temperature is raised to 230-240 ℃ again to carry out esterification reaction for 3-5 h;
preferably, in the step (5), the esterification reaction is stopped until the acid value of the reactant is 37-45 mgKOH/g;
preferably, in the step (5), the temperature is reduced to 190-210 ℃.
9. The process for preparing polyester resin for powder excellent in abrasion resistance and chemical resistance according to claim 1, comprising the steps of:
(1) adding N, N-dimethylacetamide and triisobutylaluminum as a catalyst into a reaction kettle, starting stirring and uniformly mixing, heating to 70-90 ℃, keeping the temperature, introducing nitrogen into the reaction kettle, gradually dropwise adding 3, 3-bis (chloromethyl) oxetane to perform micromolecule chlorinated polyether polymerization reaction, controlling the dropwise addition within 3-4 h, and continuously keeping the temperature for 2.5-3.5 h;
(2) adding neopentyl glycol diglycidyl ether into the material obtained in the step (1) to participate in copolymerization reaction, gradually heating from 70-90 ℃ to 130-150 ℃ at a heating rate of 8-12 ℃/h, and carrying out heat preservation reaction for 2-4 h;
(3) when the epoxy equivalent of the mixture is more than 1000g/mol, adding neopentyl glycol, terephthalic acid, 1, 4-naphthalenedicarboxylic acid and an esterification reaction catalyst monobutyl tin oxide for esterification polymerization reaction, after the materials are uniformly mixed, gradually heating to 200-220 ℃ under the protection of nitrogen, removing small molecular water and a solvent N, N-dimethylacetamide while heating for reaction, controlling the heating rate to be 6-8 ℃/h, and carrying out heat preservation reaction until no obvious distillate is evaporated out, wherein the acid value of a reactant is less than 60 mgKOH/g;
(4) adding an antioxidant and tris (2-hydroxyethyl) isocyanurate into the mixture obtained in the step (3) for chain extension reaction, gradually heating to 230-240 ℃, and carrying out heat preservation reaction for 1-2 h, wherein the heating rate is controlled to be 8-12 ℃/h; then, reacting for 2-4 h under the vacuum degree of 50-70 mmHg, promoting the formation of macromolecular polyester resin, and stopping vacuum drawing when the acid value is reduced to below 18 mgKOH/g;
(5) and (3) when the temperature is reduced to 200-220 ℃, adding 5-nitroisophthalic acid to perform carboxyl end-capping reaction, heating to 230-240 ℃ again to perform esterification reaction for 3-5 h, stopping the reaction when the acid value of the reactant is 37-45 mgKOH/g, cooling to 190-210 ℃, discharging at high temperature while the reactant is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for powder with excellent wear resistance and chemical resistance.
10. The polyester resin for powder with excellent wear resistance and chemical resistance as claimed in claim 1, wherein the acid value of the polyester resin is 37 to 45mgKOH/g, and the softening point: 115 to 123 ℃.
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| CN113817149B (en) * | 2021-09-30 | 2022-12-02 | 黄山市向荣新材料有限公司 | Polyester resin with excellent water resistance for powder coating and preparation method thereof |
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