CN112079998B - Polyester resin with excellent mechanical properties and weather resistance for powder coating and preparation method thereof - Google Patents
Polyester resin with excellent mechanical properties and weather resistance for powder coating and preparation method thereof Download PDFInfo
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- CN112079998B CN112079998B CN202010960269.XA CN202010960269A CN112079998B CN 112079998 B CN112079998 B CN 112079998B CN 202010960269 A CN202010960269 A CN 202010960269A CN 112079998 B CN112079998 B CN 112079998B
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
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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
- 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
Abstract
The invention discloses a polyester resin for powder coating with excellent mechanical property and weatherability and a preparation method thereof, wherein the formula comprises the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid, and 1.5-5% of end-capping agent 1,4-cyclohexanedicarboxylic acid; the formula of the invention is beneficial to improving the mechanical property and weather resistance of the coating template; the production method of the invention adds the isophthalic acid separately for two times, so that the structure is more regular, the reactants are easier to be transparent, and the production method is further beneficial to improving the weather resistance.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to polyester resin for powder coating with excellent mechanical property and weather resistance and a preparation method thereof.
Background
At present, the demand for weather-resistant polyester resin in the market is continuously increased, and the common polyester resin is excellent weather resistance and super weather resistance, and powder manufacturers do not want to adopt high-price super weather-resistant polyester resin alone but can choose excellent weather resistance and super weather resistance to be matched for use due to cost consideration, but the polyester of the two resins also brings certain defects to the surface of a coating film and the mechanical property and the like when the two resins are mixed, so that the polyester resin with weather resistance between the two resins is not in the market at present, and therefore the polyester resin needs to be designed to solve the problems.
GB5237.4-2017 aluminum alloy based building section 4 part: the performance grades of the 4.1.4 film layers in the powder spraying sectional material are classified into I grade, II grade and III grade according to the test result of accelerated weather resistance. And QUALICOAT quality standard quality control Specification for building aluminum section surface paint spraying and powder coating 15 th edition 2.12.1 accelerated aging test, except 3 rd class of powder, a classification is carried out according to the light retention rate after the accelerated aging test (1000 h xenon lamp aging test): the powder has a light-retaining rate of 50% or more of type 1 powder, a light-retaining rate of 75% or more of type 1.5 powder, and a light-retaining rate of 90% or more of type 2 powder.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a polyester resin having both excellent mechanical properties and excellent weather resistance.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a polyester resin for powder coating with excellent mechanical properties and weather resistance and a preparation method thereof, wherein the mechanical properties and weather resistance of a coating template are improved and the market demand is met by using trimethylolpropane, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxypivalyl hydroxypivalate, isophthalic acid and 1,4-cyclohexanedicarboxylic acid in a matching way.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the polyester resin for the powder coating with excellent mechanical properties and weather resistance comprises the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid and 1.5-5% of end-capping agent 1,4-cyclohexanedicarboxylic acid.
The polyester resin for powder coating with excellent mechanical properties and weather resistance further comprises the following components in percentage by mass: 0.09% of esterification catalyst, 0.2% of antioxidant and 0.08% of accelerator.
The polyester resin for powder coating, which has excellent mechanical properties and excellent weather resistance, comprises an esterification catalyst comprising: monobutyl tin oxide, dibutyl tin oxide, tributyl tin oxide, stannous oxalate.
The polyester resin for powder coating, which has excellent mechanical properties and excellent weather resistance, comprises the following antioxidants: antioxidant 1010, antioxidant 168 and antioxidant 1076.
The polyester resin for powder coating with excellent mechanical properties and weather resistance comprises the following components in percentage by weight: triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide and triphenylmethyl phosphonium bromide.
The polyester resin for the powder coating with excellent mechanical properties and excellent weather resistance comprises the following components in percentage by mass: neopentyl glycol 30.6%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 3%, hydroxypivalic acid neopentyl glycol monoester 5.4%, terephthalic acid 25%, isophthalic acid 24%, end-capping agent isophthalic acid 4%, end-capping agent adipic acid 1.5%, end-capping agent 1,4-cyclohexanedicarboxylic acid 4.5%, monobutyltin oxide 0.09%, antioxidant 1010.1%, antioxidant 168.1%, and triphenylethylphosphonium bromide 0.08%.
A preparation method of polyester resin for powder coating with excellent mechanical properties and weather resistance comprises the following steps:
step one, preparing raw materials according to a formula;
the formula comprises the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid, 1.5-5% of end-capping agent 1,4-cyclohexanedicarboxylic acid, 0.09% of esterification catalyst, 0.2% of antioxidant and 0.08% of promoter;
step two, heating the reaction kettle, adding neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester, adding terephthalic acid, isophthalic acid and an esterification catalyst, gradually heating under the protection of nitrogen, and then cooling;
and step three, sequentially adding end capping agent isophthalic acid, end capping agent adipic acid and end capping agent 1,4-cyclohexanedicarboxylic acid, heating, performing vacuum operation, cooling, adding antioxidant and accelerator, reacting, and discharging to obtain the polyester resin.
The preparation method of the polyester resin for the powder coating with excellent mechanical properties and weather resistance comprises the following steps:
step one, preparing raw materials according to a formula;
the formula comprises the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid, 1.5-5% of end-capping agent 1,4-cyclohexanedicarboxylic acid, 0.09% of esterification catalyst, 0.2% of antioxidant and 0.08% of accelerator;
step two, heating the reaction kettle to 70-100 ℃, adding neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester, adding terephthalic acid, isophthalic acid and an esterification catalyst, gradually heating to 240-250 ℃ under the protection of nitrogen, maintaining until the acid value is measured to be 12-20mgKOH/g, and then cooling to 210-230 ℃;
and step three, adding end capping agent isophthalic acid, end capping agent adipic acid and end capping agent 1,4-cyclohexanedicarboxylic acid in sequence, heating to 235-240 ℃ for maintaining until the acid value of the reactant is 44-50mgKOH/g, performing vacuum operation, maintaining the pressure at-0.090-0.100 MPa until the acid value of the reactant is 32-37mgKOH/g, cooling to 200-210 ℃, adding an antioxidant and an accelerator, maintaining for 30-40min, and discharging to obtain the polyester resin.
The invention has the advantages that:
according to the formula, trimethylolpropane, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxypivalyl hydroxypivalate, isophthalic acid and 1,4-cyclohexanedicarboxylic acid are matched for use, so that the mechanical property and the weather resistance of a coating template are improved;
according to the formula, 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester are compounded, so that the impact resistance of the polyester resin can be improved;
the 1,4-cyclohexanedicarboxylic acid matched formula in the formula can obviously improve the weather resistance of the polyester resin;
the production method of the invention adds the isophthalic acid separately for two times, so that the structure is more regular, the reactant is easier to be transparent, and the production method is beneficial to improving the weather resistance.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The polyester resin for the powder coating with excellent mechanical properties and weather resistance comprises the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid, 1.5-5% of end-capping agent 1,4-cyclohexanedicarboxylic acid, 0.09% of esterification catalyst, 0.2% of antioxidant and 0.08% of accelerator.
As an example, the esterification catalyst comprises: monobutyl tin oxide, dibutyl tin oxide, tributyl tin oxide, stannous oxalate. The antioxidant includes: antioxidant 1010, antioxidant 168 and antioxidant 1076. The accelerator comprises: triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, and triphenylmethyl phosphonium bromide.
Because CHDM (1,4-cyclohexanedimethanol) has a symmetrical structure, the arrangement of polymer chains is beneficial to forming hydrogen bonds among the polymer chains, so that the movement of the polymer is limited, and the mechanical property of the coating is improved. At the same time, the "chair, cage" motion of the para-substituted cyclohexane ring can provide flexibility to the coating. The combination of these two properties allows a certain balance between the hardness and flexibility required for the coating. Secondly, the high symmetry of CHDM (1,4-cyclohexanedimethanol) also improves the crystallinity of the polyester resin and the glass transition temperature compared to when aliphatic diols are used, thus improving the thermal stability and weather resistance of the powder coating. Further, since the primary hydroxyl group of CHDM is not sterically hindered, it is easily accessible to the raw acid molecule when the polyester resin is produced, and then easily accessible to the crosslinking agent when the polyester resin is crosslinked and cured, so that a polymer can be produced in a short time, and the use of CHDM can partially or completely replace the use of ethylene glycol. HPN (hydroxypivalyl hydroxypivalate) has a structure in which quaternary carbon atoms are contained on both sides of an ester group, so that the ester is not easy to hydrolyze and oxidize, and has good flexibility due to the structure of a carbodiimide group, and therefore, a saturated polyester prepared by using HPN has excellent stability and mechanical properties. In addition, the 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester compound is found in experiments, has a synergistic effect, and can improve the impact resistance of the polyester resin.
CHDA (1,4 cyclohexanedicarboxylic acid) has high solubility, the esterification reaction is fast, the reaction time can be shortened, and the corrosion resistance, the thermal stability and the hydrolysis resistance are excellent, so that the weather resistance of the coating can be improved by matching with the formula disclosed by the invention, and even orange peel of the powder coating can be reduced.
The technical effects of the formula and the preparation method are verified by experiments;
example 1: the formula comprises the following components in percentage by mass: neopentyl glycol 35%, trimethylolpropane 1.3%,1,4-cyclohexanedimethanol 1%, hydroxypivalic acid neopentyl glycol monoester 4%, terephthalic acid 33%, isophthalic acid 18%, capping agent: isophthalic acid 2%, adipic acid 4%,1,4-cyclohexane dicarboxylic acid 1.5%, esterification catalyst selected from monobutyl tin oxide 0.09%, antioxidant selected from 1010,0.1%,168,0.1%, and promoter selected from triphenyl ethyl phosphonium bromide 0.08%.
Example 2: the formula comprises the following components in percentage by mass: neopentyl glycol 30%, trimethylolpropane 1.3%,1,4-cyclohexanedimethanol 1%, hydroxypivalic acid neopentyl glycol monoester 8%, terephthalic acid 20%, isophthalic acid 32%, capping agent: isophthalic acid 2%, adipic acid 2%,1,4-cyclohexane dicarboxylic acid 1.5%, esterification catalyst selected from monobutyl tin oxide 0.09%, antioxidant selected from 1010,0.1%,168,0.1%, and promoter selected from triphenyl ethyl phosphonium bromide 0.08%.
Example 3: the formula comprises the following components in percentage by mass: neopentyl glycol 32%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 3%, hydroxypivalic acid neopentyl glycol monoester 5.4%, terephthalic acid 25%, isophthalic acid 18%, capping agent: 8 percent of isophthalic acid, 2.4 percent of adipic acid, 5 percent of 1,4-cyclohexanedicarboxylic acid, 0.09 percent of monobutyltin oxide serving as an esterification catalyst, 1010,0.1 percent of antioxidant, 168,0.1 percent of accelerator and 0.08 percent of triphenyl ethyl phosphonium bromide serving as an accelerator.
Example 4: the formula comprises the following components in percentage by mass: neopentyl glycol 30%, trimethylolpropane 1%,1,4-cyclohexanedimethanol 4%, hydroxypivalic acid neopentyl glycol monoester 4%, terephthalic acid 25%, isophthalic acid 23%, capping agent: isophthalic acid 2%, adipic acid 0%,1,4-cyclohexanedicarboxylic acid 5%, esterification catalyst selected from monobutyltin oxide 0.09%, antioxidant selected from 1010,0.1%,168,0.1%, and promoter selected from triphenylethylphosphorus bromide 0.08%.
Best mode 5: the formula comprises the following components in percentage by mass: neopentyl glycol 30.6%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 3%, hydroxypivalic acid neopentyl glycol monoester 5.4%, terephthalic acid 25%, isophthalic acid 24%, capping agent: isophthalic acid 4%, adipic acid 1.5%,1,4-cyclohexane dicarboxylic acid 4.5%, esterification catalyst is monobutyl tin oxide 0.09%, antioxidant is 1010,0.1%,168,0.1%, and accelerant is triphenyl ethyl phosphorus bromide 0.08%.
Comparative example 1: the formula comprises the following components in percentage by mass: neopentyl glycol 33%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 0%, hydroxypivalic acid neopentyl glycol monoester 5.5%, terephthalic acid 25.3%, isophthalic acid 24.3%, capping agent: isophthalic acid 4%, adipic acid 2%,1,4-cyclohexane dicarboxylic acid 4.5%, esterification catalyst selected from monobutyl tin oxide 0.09%, antioxidant selected from 1010,0.1%,168,0.1%, and promoter selected from triphenyl ethyl phosphonium bromide 0.08%. In contrast to the preferred embodiment, 1,4 cyclohexanedimethanol is missing.
Comparative example 2: the formula comprises the following components in percentage by mass: neopentyl glycol 34.2%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 3%, hydroxypivalic acid neopentyl glycol monoester 0%, terephthalic acid 25.8%, isophthalic acid 24.7%, capping agent: isophthalic acid 4%, adipic acid 2%,1,4-cyclohexane dicarboxylic acid 4.6%, esterification catalyst selected from monobutyl tin oxide 0.09%, antioxidant selected from 1010,0.1%,168,0.1%, and promoter selected from triphenyl ethyl phosphonium bromide 0.08%. In contrast to the most preferred embodiment, hydroxypivalic acid neopentyl glycol monoester was absent.
Comparative example 3: the formula comprises the following components in percentage by mass: neopentyl glycol 30.6%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 3%, hydroxypivalic acid neopentyl glycol monoester 5.4%, terephthalic acid 26%, isophthalic acid 25.6%, capping agent: 6 percent of isophthalic acid, 2 percent of adipic acid, 0 percent of 1,4-cyclohexanedicarboxylic acid, 0.09 percent of monobutyltin oxide serving as an esterification catalyst, 1010,0.1 percent of antioxidant, 168,0.1 percent of antioxidant and 0.08 percent of triphenyl ethylphosphorus bromide serving as an accelerator. In contrast to the preferred embodiment, 1,4-cyclohexanedicarboxylic acid is missing.
The above formulations were prepared as follows for samples 1, 2, 3, 4, 5, comparative samples 1, 2, 3.
Step one, preparing raw materials according to a formula;
and step two, raising the temperature of the reaction kettle to 70-100 ℃, adding neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester, adding terephthalic acid, isophthalic acid and an esterification catalyst, gradually raising the temperature to 240-250 ℃ under the protection of nitrogen, maintaining the temperature until the acid value is measured to be 12-20mgKOH/g, and then cooling to 210-230 ℃.
And step three, adding one or more of end capping agents of isophthalic acid, adipic acid and 1,4-cyclohexanedicarboxylic acid in sequence, heating to 235-240 ℃ for maintaining until the acid value of the reactant is 44-50mgKOH/g, performing vacuum operation (the pressure is maintained at-0.090-0.100 MPa) until the acid value of the reactant is 32-37mgKOH/g, cooling to 200-210 ℃, adding an antioxidant and an accelerator, and maintaining for 30-40min to obtain the finished product.
The formulation used in example 5, i.e. the optimum formulation, was: neopentyl glycol 30.6g, trimethylolpropane 1.2g,1, 4-cyclohexanedimethanol 3g, hydroxypivalic acid neopentyl glycol monoester 5.4g, terephthalic acid 25g, isophthalic acid 28g, adipic acid 1.5g,1, 4-cyclohexanedicarboxylic acid 4.5g. Comparative sample 4 was prepared as follows:
step one, preparing raw materials according to a formula;
and step two, raising the temperature of the reaction kettle to 70-100 ℃, adding neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester, adding terephthalic acid, isophthalic acid and an esterification catalyst, gradually raising the temperature to 240-250 ℃ under the protection of nitrogen, maintaining the temperature until the acid value is measured to be 12-22mgKOH/g, and then cooling to 210-230 ℃.
And step three, sequentially adding one or more of a blocking agent adipic acid and 1,4-cyclohexanedicarboxylic acid, heating to 235-240 ℃ for maintaining until the acid value of the reactant is 44-50mgKOH/g, performing vacuum operation (the pressure is maintained at-0.090-0.100 MPa) until the acid value of the reactant is 32-37mgKOH/g, cooling to 200-210 ℃, adding an antioxidant and an accelerator, and maintaining for 30-40min to obtain the material.
Compared with the preparation method of the invention, the preparation method has the following differences: the isophthalic acid is not added in two portions but is added in one portion in step two.
Samples 1, 2, 3, 4, 5 and comparative samples 1, 2, 3, 4 were cured with TGIC and the resulting coating films were tested by (ISO 15184, 1996) pencil hardness, adhesion (GB/T9286-1998), impact resistance GB/T1732-1993, bending resistance GB/T6742-1986, salt spray resistance GBT 1771-1991, weather resistance GB/T1865-1997.
Powder coating Performance test (baking conditions: 200 ℃ C., 15 minutes) with Excellent mechanical Properties and Excellent weatherability
And (4) analyzing results:
from samples 1-5, it can be seen that sample 5 is the most preferred sample within this range of formulations, with excellent mechanical properties and excellent weathering performance.
As can be seen from the comparison of samples 1-5 with comparative sample 1, the addition of 1,4-cyclohexanedimethanol can bring certain improvements to mechanical properties and impact.
It is clear from the comparison of samples 1 to 5 with comparative sample 2 that the addition of hydroxypivalyl hydroxypivalate results in a powder coating having greater flexibility and impact properties.
Compared with the comparative samples 1 and 2 and the sample 5, the 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester compound has cooperativity, and the ability of improving the impact resistance of the polyester resin by the compound can not be achieved by single use;
as can be seen from the comparison of samples 1-5 with comparative sample 3, 1,4-cyclohexanedicarboxylic acid, when used with the formulation of the present invention, provides a coating film with good weatherability and superior surface effect.
It is understood from the comparison between samples 1 to 5 and comparative sample 3 that the addition of isophthalic acid separately allows the polyester resin to permeate more easily and the weather resistance to be improved.
According to the invention, trimethylolpropane, 1,4-cyclohexanedimethanol, hydroxypivalic acid hydroxypivalyl hydroxypivalate, isophthalic acid and 1,4-cyclohexanedicarboxylic acid are matched for use in the formula, and the isophthalic acid is added in batches in the preparation method in the process, so that the prepared polyester resin and TGIC are cured, and the obtained coating has excellent mechanical properties and weather resistance and meets the market demand.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalents or equivalent changes fall within the protection scope of the present invention.
Claims (5)
1. The polyester resin for the powder coating with excellent mechanical properties and weather resistance is characterized by comprising the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid, 1.5-5% of end-capping agent 1, 4-cyclohexanedicarboxylic acid, 0.09% of esterification catalyst, 0.2% of antioxidant and 0.08% of accelerator;
the preparation method of the polyester resin for the powder coating comprises the following steps:
step one, preparing raw materials according to a formula;
the formula comprises the following components in percentage by mass: 30-35% of neopentyl glycol, 1-1.6% of trimethylolpropane, 1-4% of 1,4-cyclohexanedimethanol, 4-8% of hydroxypivalic acid neopentyl glycol monoester, 20-33% of terephthalic acid, 18-32% of isophthalic acid, 2-8% of end-capping agent isophthalic acid, 0-4% of end-capping agent adipic acid, 1.5-5% of end-capping agent 1,4-cyclohexanedicarboxylic acid, 0.09% of esterification catalyst, 0.2% of antioxidant and 0.08% of promoter;
step two, heating the reaction kettle to 70-100 ℃, adding neopentyl glycol, trimethylolpropane, 1,4-cyclohexanedimethanol and hydroxypivalic acid neopentyl glycol monoester, adding terephthalic acid, isophthalic acid and an esterification catalyst, gradually heating to 240-250 ℃ under the protection of nitrogen, maintaining until the acid value is measured to be 12-20mgKOH/g, and then cooling to 210-230 ℃;
and step three, adding end capping agent isophthalic acid, end capping agent adipic acid and end capping agent 1,4-cyclohexanedicarboxylic acid in sequence, heating to 235-240 ℃ for maintaining until the acid value of the reactant is 44-50mgKOH/g, performing vacuum operation, maintaining the pressure at-0.090-0.100 MPa until the acid value of the reactant is 32-37mgKOH/g, cooling to 200-210 ℃, adding an antioxidant and an accelerator, maintaining for 30-40min, and discharging to obtain the polyester resin.
2. The polyester resin for powder coating excellent in mechanical properties and weather resistance as claimed in claim 1, wherein the esterification catalyst comprises: monobutyl tin oxide, dibutyl tin oxide, tributyl tin oxide, stannous oxalate.
3. The polyester resin for powder coating excellent in mechanical properties and weather resistance as claimed in claim 1, wherein the antioxidant comprises: antioxidant 1010, antioxidant 168 and antioxidant 1076.
4. The polyester resin for powder coating material excellent in mechanical properties and weather resistance as claimed in claim 1, wherein the accelerator comprises: triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide and triphenylmethyl phosphonium bromide.
5. The polyester resin for powder coating of claim 1, which has excellent mechanical properties and excellent weather resistance, wherein the formulation comprises, in mass percent: neopentyl glycol 30.6%, trimethylolpropane 1.2%,1,4-cyclohexanedimethanol 3%, hydroxypivalic acid neopentyl glycol monoester 5.4%, terephthalic acid 25%, isophthalic acid 24%, end-capping agent isophthalic acid 4%, end-capping agent adipic acid 1.5%, end-capping agent 1,4-cyclohexanedicarboxylic acid 4.5%, monobutyltin oxide 0.09%, antioxidant 1010.1%, antioxidant 168.1%, and triphenylethylphosphonium bromide 0.08%.
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