CN111100279A - Fluorine-containing copolyester for powder coating and preparation method thereof - Google Patents
Fluorine-containing copolyester for powder coating and preparation method thereof Download PDFInfo
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- CN111100279A CN111100279A CN201811265269.7A CN201811265269A CN111100279A CN 111100279 A CN111100279 A CN 111100279A CN 201811265269 A CN201811265269 A CN 201811265269A CN 111100279 A CN111100279 A CN 111100279A
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- fluorine
- powder coating
- monomer
- acid
- containing copolyester
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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
-
- 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
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses a fluorine-containing copolyester for powder coating, which is prepared by taking a dihydric alcohol monomer, a dicarboxylic acid monomer and a fluorine modified monomer as raw materials and sequentially carrying out esterification reaction and polycondensation reaction; the fluorine modified monomer is one or a mixture of potassium fluotitanate and fluotitanic acid. The invention also discloses a preparation method of the fluorine-containing copolyester for the powder coating, which comprises the steps of adding a dihydric alcohol monomer, a dicarboxylic acid monomer and a fluorine modified monomer into a polymerization reaction kettle, and carrying out esterification reaction at 200-250 ℃ and 0-0.3 MPa; and after the esterification reaction is finished, heating to 270-280 ℃, and reducing the pressure to be less than 100Pa to obtain the fluorine-containing copolyester for the powder coating. The copolyester is prepared into powder coating, the powder coating is sprayed on a stainless steel plate, the weather resistance of the coating is tested according to GBT14522-2008, and after manual acceleration for nearly 1000 hours, the gloss retention of the coating is still kept at 60%, so that the coating has excellent weather resistance.
Description
Technical Field
The invention belongs to the field of powder coating, and relates to fluorine-containing copolyester for powder coating and a preparation method thereof.
Background
The powder coating is researched and put into use from the middle of the 40 th year in the 20 th century, and along with the improvement and development of the preparation process and the coating technology of the powder coating, the powder coating is gradually paid attention from various countries, and the average growth speed of the powder coating in the year is up to more than 8%. Particularly, since the 21 st century, the environmental protection of human beings is more and more important, and the limit on the discharge amount of VOC in the atmosphere is increasingly strict, so that the powder coating plays a very important role in the coating world.
At present, with the expansion of the powder coating market, especially in the field of outdoor powder coatings, users will choose weather-resistant powder coatings to avoid frequent secondary coating. Therefore, development of a polyester resin for weather-resistant powder coating materials is becoming a trend.
Most of the catalysts used in the synthesis of polyester resin for powder coating at present are tin catalysts, and one or two of monobutyl tin oxide, dibutyl tin oxide, dihydroxy butyl tin chloride and stannous oxalate are usually selected. Tin is known as heavy metal, and with the green development of the powder coating industry, the industry has a higher and higher call for developing polyester resin for powder coatings without containing organic tin.
The polyester for weather-resistant powder coating adopted in the current coating industry is prepared from conventional materials such as neopentyl glycol, diethylene glycol, 2-methyl 1.3-propanediol, isophthalic acid, adipic acid and the like, and the conventional formula determines that the prepared copolyester has poor weather resistance. For example, Chinese patent application 201110360033.3 entitled carboxyl-terminated polyester resin for super weather-resistant powder coating and its preparation method.
The weather resistance of the polyester resin can be prolonged by adding fluorine element into the polyester resin, but partial defects still exist. For example, CN106750222A, "a carboxyl-terminated fluorine-containing resin for super-weather-resistant powder coating and its preparation method" is prepared by reacting fluorine-containing alcohol, sodium hydroxide, and propylene oxide to obtain a fluorine-containing epoxy compound, polycondensing and end-capping polyol, polyacid, and branching agent to obtain a polyester resin intermediate, and adding the fluorine-containing epoxy compound into the polyester intermediate to prepare the carboxyl-terminated fluorine-containing polyester resin for super-weather-resistant powder coating. However, the fluorine-containing alcohol is expensive, and the polyester preparation process is complex and not beneficial to industrialization. Chinese patent ZL201510009803.8 discloses "polyester resin for super weather-resistant powder coating, powder coating using the same, and method for preparing the same" wherein the weather resistance is improved by adding tetrafluoroisophthalic acid, hexafluoroglutaric acid, etc. as fluorine-containing monomers at the stage of polyester resin synthesis. The patent also has the problems that the usage amount of the fluorine-containing monomer is large, the price is very high, and industrialization cannot be realized.
Disclosure of Invention
The invention aims to realize green and environment-friendly production of copolyester for powder coating and improve the weather resistance of the copolyester, and provides fluorine-containing copolyester for powder coating and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a fluorine-containing copolyester for powder coating is prepared from dihydric alcohol monomer, dicarboxylic acid monomer and fluorine modified monomer through esterification and polycondensation reactions.
The preparation method of the fluorine-containing copolyester for the powder coating comprises the following steps:
esterification reaction: adding a dihydric alcohol monomer, a dicarboxylic acid monomer and a fluorine modified monomer into a polymerization reaction kettle according to the molar ratio of 1.1-1.8: 1 of alcohol acid, carrying out esterification reaction at 200-250 ℃ and 0-0.3MPa, and finishing the esterification reaction when the esterification water yield reaches a theoretical value;
and (3) polycondensation reaction:
and after the esterification reaction is finished, raising the temperature in the reaction kettle to 270-280 ℃, starting a vacuum system, reducing the pressure to be below 100Pa, reacting under the condition, and preparing the fluorine-containing copolyester with the viscosity meeting the requirement for the powder coating according to the change of the stirring power of the polymerization kettle.
The dicarboxylic acid monomer is one or more of terephthalic acid, isophthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid, sebacic acid and succinic acid; preferably one or more of terephthalic acid, isophthalic acid and/or adipic acid, 1, 4-cyclohexanedicarboxylic acid, sebacic acid and succinic acid.
The dihydric alcohol monomer is one or more of ethylene glycol, diethylene glycol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol and 2-methyl-1, 3-propanediol; preferably one or more of ethylene glycol, diethylene glycol and/or 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol, 2-methyl-1, 3-propanediol.
The fluorine modified monomer is one or a mixture of potassium fluotitanate and fluotitanic acid, and fluorine is introduced into the fluorine modified monomer, so that the weather resistance of the polyester is improved; and titanium element is introduced to play a role of a catalyst. The addition amount of the fluorine modified monomer is 100-2000ppm of the dicarboxylic acid monomer.
The fluorine-containing copolyester for the powder coating has the intrinsic viscosity of 0.2-0.4dL/g, the molecular weight of 5000-8000, the glass transition temperature of 50-65 ℃ and the acid value of 20-40 mgKOH/g.
The application of the fluorine-containing copolyester in preparing powder coating base material. The copolyester is adopted to prepare a powder coating, the powder coating is sprayed on a stainless steel plate, a weather resistance test is carried out on a coating, the test standard is GBT14522-2008, and the light retention rate of the coating is still maintained at 60% after manual acceleration for nearly 1000 h.
Compared with the prior art, the invention has the beneficial effects that:
one or two of potassium fluotitanate and fluotitanic acid are used as a catalyst and a fluorine modified monomer, the two fluorine modified monomers have moderate price (about 4 ten thousand/ton), and the prepared fluorine-containing copolyester for the powder coating does not contain heavy metal tin, and is a copolyester for green environment-friendly powder coating; the product is prepared into powder coating base material with good weather resistance.
Detailed Description
Example 1
Adding dicarboxylic acid monomers, diol monomers and fluotitanic acid into a 2.5-liter polymerization reaction kettle according to a formula shown in a table 1; wherein the dicarboxylic acid monomer consists of terephthalic acid, isophthalic acid and adipic acid, and the diol monomer consists of ethylene glycol, neopentyl glycol, 1, 4-cyclohexanedimethanol and diethylene glycol.
After the monomers are added into the system, nitrogen is replaced, the temperature is raised, the esterification reaction is carried out at 200-250 ℃ and 0-0.3MPa, and the esterification end point is reached when the esterification water yield reaches the theoretical value. And (3) releasing the system pressure to normal pressure, starting a vacuum system, reducing the pressure to below 100Pa, simultaneously raising the temperature in the reaction kettle to 280 ℃ for reaction under the condition, and preparing the fluorine-containing copolyester with the viscosity meeting the requirement for the powder coating according to the change of the stirring power of the polymerization kettle.
Example 2
The same raw material ratio as that of example 1 was adopted, the amount of fluotitanic acid was adjusted to 0.8g, and the fluorine-containing copolyester for powder coating was prepared according to the process conditions of example 1.
Example 3
Adding dicarboxylic acid monomers, diol monomers and potassium fluotitanate into a 2.5-liter polymerization reaction kettle according to a formula shown in a table 1; wherein the dicarboxylic acid monomer comprises terephthalic acid, isophthalic acid, sebacic acid and 1, 4-cyclohexanedicarboxylic acid, and the diol monomer comprises ethylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol and diethylene glycol.
The required fluorine-containing copolyester for powder coating is prepared according to the process conditions of example 1.
Example 4
Adding dicarboxylic acid monomers and diol monomers, potassium fluotitanate and fluotitanic acid into a 20-liter polymerization reaction kettle according to a formula shown in a table 1; wherein, the dicarboxylic acid monomer consists of terephthalic acid and isophthalic acid, and the diol monomer consists of ethylene glycol, 2-methyl-1, 3-propanediol and diethylene glycol according to a molar ratio.
The required fluorine-containing copolyester for powder coating is prepared according to the process conditions of example 1.
Example 5
Adding dicarboxylic acid monomers and diol monomers, potassium fluotitanate and fluotitanic acid into a 20-liter polymerization reaction kettle according to a formula shown in a table 1; wherein, the dicarboxylic acid monomer consists of terephthalic acid and isophthalic acid, and the diol monomer consists of ethylene glycol, 2-methyl-1, 3-propanediol and diethylene glycol.
The required fluorine-containing copolyester for powder coating is prepared according to the process conditions of example 1.
Table 1: fluorine-containing copolyester formula for powder coating and performance
The fluorine-containing copolyester for the powder coating synthesized in the embodiments 1 to 5 of the invention is respectively and uniformly mixed with a curing agent (TGIC), a flatting agent BYK-3902P, titanium dioxide, an auxiliary agent (an adhesion promoter AP-3800) and a filler (calcium carbonate) according to the proportion in the table 2, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving in a screw extruder to prepare the powder coating. The powder coating was sprayed onto stainless steel panels and the coatings were tested for weatherability using the weatherability test standard GBT14522-2008 with the test performance results shown in table 2. Therefore, after artificial acceleration for nearly 1000 hours, the light retention rate of the coating is still kept above 60%, and the coating has excellent weather resistance.
Table 2: powder coating composition and coating properties
Claims (9)
1. The fluorine-containing copolyester for the powder coating is characterized by being prepared by taking a dihydric alcohol monomer, a dicarboxylic acid monomer and a fluorine modified monomer as raw materials and sequentially carrying out esterification reaction and polycondensation reaction.
2. The fluorine-containing copolyester for powder coating according to claim 1, wherein the fluorine-modified monomer is one or a mixture of potassium fluotitanate and fluotitanic acid.
3. The fluorine-containing copolyester for powder coating according to claim 1 or 2, wherein the amount of the fluorine-modified monomer added is 100-2000ppm of the dicarboxylic acid monomer.
4. The fluorine-containing copolyester for powder coating according to claim 1, wherein the fluorine-containing copolyester for powder coating has an intrinsic viscosity of 0.2-0.4dL/g, a molecular weight of 5000-8000, a glass transition temperature of 50-65 ℃ and an acid value of 20-40 mgKOH/g.
5. The method for preparing fluorine-containing copolyester for powder coating according to claim 1, characterized by comprising the steps of:
esterification reaction: adding a dihydric alcohol monomer, a dicarboxylic acid monomer and a fluorine modified monomer into a polymerization reaction kettle according to the molar ratio of 1.1-1.8: 1 of alcohol acid, carrying out esterification reaction at 200-250 ℃ and 0-0.3MPa, and finishing the esterification reaction when the esterification water yield reaches a theoretical value;
and (3) polycondensation reaction: and reacting at 270-280 ℃ and under the pressure of 100Pa after the esterification reaction to obtain the fluorine-containing copolyester for the powder coating.
6. The method for preparing fluorine-containing copolyester for powder coating according to claim 5, wherein the dicarboxylic acid monomer is one or more of terephthalic acid, isophthalic acid, adipic acid, 1, 4-cyclohexanedicarboxylic acid, sebacic acid, and succinic acid; the diol monomer is one or more of ethylene glycol, diethylene glycol, 1, 6-hexanediol, neopentyl glycol, 1, 4-cyclohexanedimethanol and 2-methyl-1, 3-propanediol.
7. The method for preparing fluorine-containing copolyester for powder coating according to claim 5, wherein the fluorine-modified monomer is one or a mixture of potassium fluotitanate and fluotitanic acid.
8. The method for preparing fluorine-containing copolyester for powder coating according to claim 5, wherein the amount of the fluorine-modified monomer added is 100-2000ppm of dicarboxylic acid monomer.
9. Use of a fluorine-containing copolyester for powder coating according to claim 1 for preparing a powder coating base.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811265269.7A CN111100279A (en) | 2018-10-29 | 2018-10-29 | Fluorine-containing copolyester for powder coating and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811265269.7A CN111100279A (en) | 2018-10-29 | 2018-10-29 | Fluorine-containing copolyester for powder coating and preparation method thereof |
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| CN111100279A true CN111100279A (en) | 2020-05-05 |
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| CN201811265269.7A Pending CN111100279A (en) | 2018-10-29 | 2018-10-29 | Fluorine-containing copolyester for powder coating and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326832A (en) * | 1989-03-23 | 1994-07-05 | Dsm N.V. | Powder paint and a polyester resin for powder paint |
| CN103289067A (en) * | 2013-06-26 | 2013-09-11 | 天津虹炎科技有限公司 | Flame-retardant polyester resin |
| CN104530408A (en) * | 2015-01-08 | 2015-04-22 | 黄山市向荣新材料有限公司 | Polyester resin for ultra-weather-proof powder coating, powder coating with resin and preparing method for powder coating |
| CN106146815A (en) * | 2016-07-29 | 2016-11-23 | 中国石化仪征化纤有限责任公司 | A kind of fluorine-containing copolyesters and preparation method thereof |
| CN106750222A (en) * | 2016-11-30 | 2017-05-31 | 安徽神剑新材料股份有限公司 | A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof |
-
2018
- 2018-10-29 CN CN201811265269.7A patent/CN111100279A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5326832A (en) * | 1989-03-23 | 1994-07-05 | Dsm N.V. | Powder paint and a polyester resin for powder paint |
| CN103289067A (en) * | 2013-06-26 | 2013-09-11 | 天津虹炎科技有限公司 | Flame-retardant polyester resin |
| CN104530408A (en) * | 2015-01-08 | 2015-04-22 | 黄山市向荣新材料有限公司 | Polyester resin for ultra-weather-proof powder coating, powder coating with resin and preparing method for powder coating |
| CN106146815A (en) * | 2016-07-29 | 2016-11-23 | 中国石化仪征化纤有限责任公司 | A kind of fluorine-containing copolyesters and preparation method thereof |
| CN106750222A (en) * | 2016-11-30 | 2017-05-31 | 安徽神剑新材料股份有限公司 | A kind of extra-weather-proof fluorine-containing polyester resin of end carboxyl used for powder coating and preparation method thereof |
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Application publication date: 20200505 |