CN111234185A - High-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating and synthesis method thereof - Google Patents
High-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating and a synthesis method thereof. The invention adopts esterification polycondensation two-step method and vacuum process to synthesize high-crystallinity bifunctional polyester, uses symmetric terephthalic acid, adipic acid and 1, 6-hexanediol as main bodies, controls the melting point, viscosity and crystallinity of a system through other monomers of dihydric alcohol and dibasic acid with even number of carbon atoms, adjusts the dosage of each monomer, controls the ratio of the total carboxyl and the total hydroxyl mole number of the system, and synthesizes the high-crystallinity bifunctional polyester resin, wherein the prepared polyester resin has an acid value of 30-36mgKOH/g, a hydroxyl value of 18-23mgKOH/g, a viscosity of 3000-6000mPa.s/160 ℃, and a melting point of 90-120 ℃. The invention has the advantages of simple synthesis process, short time consumption and economic production cost, and the prepared polyester is used for curing TGIC-B1530 double-system powder at 170 ℃, has excellent delustering performance, fine board surface and excellent leveling and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a high-crystallinity bifunctional polyester resin for a low-temperature curing extinction powder coating and a synthesis method thereof.
Background
With the upgrading of environmental protection requirements, the application field of the powder coating is continuously expanded, and the polyester resin which is the main raw material for determining the performance of the powder coating is greatly developed. However, high gloss and bright powder coatings are harmful to the eyes due to their relatively heavy reflection after film formation, and therefore matte powder coatings are gaining increasing attention in the market due to their natural, elegant, and paint film defect concealing advantages. The principle of the matting powder is that the uniformity and continuity of a coating film are destroyed by a chemical or physical method, so that light irradiates the surface of the coating film to generate diffuse reflection and scattering, thereby obtaining a matting coating. Generally, physical matting is mainly achieved by adding inorganic fillers, stearate, wax powder, synthetic resins and the like to increase the roughness of the surface of a coating film; the chemical extinction is mainly to add IPN extinction agent, extinction curing agent, resin or curing agent with larger difference of mixing reaction speed, dry mixing of powder with different curing speed and the like, so that the surface of the coating film generates microscopic roughness to achieve extinction. Whether chemical extinction or physical extinction, the defects of high extinction gloss, poor mechanical performance, poor fineness, poor plate surface leveling and the like exist more or less, and the perfect balance cannot be achieved. Chinese patent CN108084415A discloses carboxyl-hydroxyl terminated polyester with acid value of 35-45mgKOH/g, hydroxyl value of 10-25mgKOH/g, melt viscosity of 1000-. Chinese patent CN109293905A discloses a bifunctional polyester resin with good extinction performance and a preparation method and application thereof, the bifunctional polyester has an acid value of 15-35mgKOH/g, a hydroxyl value of 20-60mgKOH/g, a viscosity of 4000-5500mpa.s/200 ℃, extinction gloss of 6.6-8.9%/60 degrees, five additives for leveling, and a mechanical property of positive and negative 50kg.cm, and because the melt viscosity at 200 ℃ is higher, the resin structures are all amorphous structures, the problems of incapability of low-temperature curing, poor flow leveling of low-temperature curing and high extinction gloss occur. Chinese patent CN102627755A discloses a method for synthesizing semi-crystalline polyester resin with low viscosity and high toughness for powder coating, wherein the semi-crystalline polyester is synthesized by two steps of hexanediol, terephthalic acid and a capping agent, the semi-crystalline polyester resin has low viscosity and low melting point, HAA is adopted for curing to prepare powder, and the obtained coating has good leveling property and does not mention the problem of extinction. Chinese patent CN103483565A discloses a semi-crystalline polyester resin for TGIC cured high leveling powder coating and a synthesis method thereof, the invention adopts long carbon chain symmetric alcohol and acid esterification polycondensation to obtain the semi-crystalline resin, the melting point of the resin is 100-130 ℃, the viscosity is 400-3000mPa.s, the prepared powder coating has good leveling and mechanical properties, the polyester does not contain a bifunctional structure, and the polyester does not have the condition of low-temperature curing extinction problem. Chinese patent CN107513339A discloses a semi-crystalline polyester resin for polyisocyanate-cured high-leveling powder coating and a preparation method thereof, the invention adopts the esterification of a mixture of 1,4 butanediol, ethylene glycol and neopentyl glycol and succinic anhydride to obtain a hydroxyl-terminated semi-crystalline polyester resin, and then the resin and amorphous resin are mixed to prepare powder to obtain a high-leveling coating, the polyester does not contain a bifunctional structure and does not have the condition of low-temperature curing extinction problem. It can be seen from the above patents that the synthesized polyester resin is basically a single bifunctional or semi-crystalline resin, the application of which is limited to high gloss and high leveling or conventional baking temperature delustering, and which is not related to the field of low temperature curing delustering powder, especially to a low temperature curing delustering polyester resin with low delustering gloss, good leveling property and good mechanical property.
From the application perspective, the high-crystallinity bifunctional polyester is synthesized by adopting an esterification polycondensation two-step method and a vacuum process, symmetrical terephthalic acid, adipic acid and symmetrical 1, 6-hexanediol are taken as main bodies, the melting point and viscosity of a system are controlled by other monomers of dihydric alcohol with even number of carbon atoms and dibasic acid, the using amount of each monomer is adjusted, the ratio of the total carboxyl and the total hydroxyl mole number of the system is controlled, and the high-crystallinity bifunctional polyester resin is synthesized. The file retrieval result shows that the high-crystallinity bifunctional polyester resin synthesized by the invention and the low-temperature curing extinction powder field thereof have few reports.
Disclosure of Invention
1. The invention aims to provide a high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating, which has the characteristics of excellent extinction performance, fine board surface, leveling property and excellent mechanical property in the field of low-temperature curing extinction powder due to high crystallinity, bifunctional structure, multiple flexible synthetic monomers and proper curing accelerator.
2. The invention also aims to provide a preparation method of the high-crystallinity bifunctional polyester resin for the low-temperature curing extinction powder coating.
3. The high-crystallinity bifunctional polyester resin for the low-temperature curing extinction powder coating and the synthesis method thereof are characterized in that the high-crystallinity bifunctional polyester resin for the powder coating comprises the following raw materials in parts by mass:
40-55 wt% of terephthalic acid, 30-50 wt% of 1, 6-hexanediol, 5-25 wt% of adipic acid, 0.05-0.2 wt% of esterification catalyst, 0-7 wt% of terephthalic acid, 0-9 wt% of ethylene glycol, 0-6 wt% of butanediol, 0-10 wt% of sebacic acid, 0-20 wt% of lauric acid, 0.05-0.12 wt% of esterification antioxidant and 0.02-0.2 wt% of curing accelerator.
4. The high crystallinity difunctional polyester resin for low temperature curing matting powder coating according to claim 1 characterized in that the ratio of the total moles of carboxyl groups of all carboxylic acids to the total moles of hydroxyl groups of all alcohols is 1.0270-1.0360.
5. The high-crystallinity bifunctional polyester resin for low-temperature-curable extinction powder coatings as claimed in claim 1, wherein the theoretical average functionality calculated from the formula monomers is 2, and the number average molecular weight is 2000-3000.
6. The high-crystallinity bifunctional polyester resin for low-temperature-curable matting powder coating material as claimed in claim 1, wherein the polyester resin is simultaneously end-capped with a large number of carboxyl groups and hydroxyl groups, and has an acid value of 30-36mgKOH/g, a hydroxyl value of 18-23mgKOH/g, a viscosity of 3000-6000mpa.s/160 ℃.
7. The high-crystallinity bifunctional polyester resin for low-temperature-curing extinction powder coatings according to claim 1, characterized in that the polyester resin structure consists of amorphous parts and crystalline parts, the crystallinity is 60-90%, and the DSC melting point is 90-120 ℃.
8. The high crystallinity difunctional polyester resin for low temperature curing matting powder coating according to claim 1 characterized in that the esterification catalyst is one of n-propyl zirconate or isopropyl zirconate.
9. The high-crystallinity bifunctional polyester resin for low-temperature-curing extinction powder coatings according to claim 1, characterized in that the esterification antioxidant is 70% phosphorous acid aqueous solution.
10. The high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating of claim 1, wherein the curing accelerator is one or a combination of more than two of 18-crown-6, 15-crown-5, N-bromosuccinimide, quaternary ammonium salt, quaternary phosphonium salt and tertiary amine.
Specifically, the quaternary ammonium salt comprises tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltriethylammonium chloride and tetrabutylammonium diacetate; the quaternary phosphonium salts include triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, and triphenylpropylphosphonium bromide, and the tertiary amines include octadecyl dimethyl tertiary amine, and dodecyl dimethyl tertiary amine.
11. A process for preparing a high crystallinity difunctional polyester resin for low temperature curing matting powder coatings as described in any one of claims 1 to 8, characterized in that said process comprises the steps of:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: the temperature of the top of the tower is controlled to be less than or equal to 102 ℃ in the esterification, wherein the temperature is increased from 60 ℃ to 80 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.5-1 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and the esterification antioxidant is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 30min-60min, and sampling to test indexes, namely an acid value of 41-44mgKOH/g and a hydroxyl value of 28-32 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 10 to 20min, the sampling test shows that the acid value is 30 to 36mgKOH/g, the hydroxyl value is 18 to 23mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the solidified accelerant, and slowly cooling and crystallizing the material to be a milky solid for later use.
12. The high crystallinity difunctional polyester resin for low temperature curing matting powder coating according to claim 1 characterized in that it is mainly used for curing under 170 ℃ 15min of TGIC-B1530 system.
Compared with the prior art, the invention has the following advantages:
1. the synthetic polyester resin raw material of the invention takes terephthalic acid, adipic acid and 1, 6-hexanediol as main bodies, and other symmetrical monomers are mainly used for adjusting crystallinity, melting point and viscosity.
2. The raw materials used for synthesizing the polyester resin are symmetrical monomers, and have more long carbon chain dihydric alcohol or dibasic acid, so that the synthesized resin has excellent flexibility and the mechanical property of the extinction coating is excellent; in addition, different long carbon chain monomers lead the microcosmic shrinkage of the extinction coating to be inconsistent during curing, and are more beneficial to reducing the extinction gloss.
3. The polyester resin synthesized by the invention has a terminal hydroxyl-carboxyl bifunctional structure, is used for a TGIC-B1530 dual-curing system, and can further reduce the extinction gloss due to the inconsistent curing rates of carboxyl and TGIC epoxy groups and hydroxyl and B1530-NCO groups; in addition, due to the closed characteristic of B1530, the melting viscosity of the powder system in the curing process can be greatly reduced, and the leveling property of the low-temperature curing extinction powder coating is improved.
4. The polyester resin synthesized by the invention has high crystallinity and low melting point (90-120 ℃), so that the viscosity of the polyester resin at 160 ℃ is only 3000-6000mPa.s, and the leveling of a powder system can be obviously improved; in addition, the crystalline part and the amorphous part are inconsistent to the curing shrinkage rate of the system, so that the extinction efficiency of the coating can be improved.
5. According to the invention, through selection of the curing accelerator and the synthetic monomer, the synthetic resin can be used for curing extinction powder at a low temperature (170 ℃), is energy-saving and emission-reducing, and meets the requirements of national policies.
6. When the resin synthesized by the invention is cured at 170 ℃/15min, the extinction gloss is below 15 percent, the leveling is above 6-grade, the impact performance reaches positive and negative 50kg.cm, the board surface is fine and smooth, and the resin is very suitable for the field of low-temperature curing extinction powder.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.
Example 1
1. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating comprises the following raw materials in parts by mass: 47.9g of 1, 6-hexanediol, 45.5g of terephthalic acid, 21.1g of adipic acid, 0.86g of n-propyl zirconate, 0.55g of phosphorous acid, 60.25g of 18-crown ether and 0.46g of methyl triethyl ammonium chloride.
2. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating is prepared by the following steps:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: in the esterification, the temperature at the top of the tower is controlled to be less than or equal to 102 ℃, wherein the temperature is increased from 70 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.8 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and phosphorous acid is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 45min, and sampling to test indexes, namely an acid value of 42.23mgKOH/g and a hydroxyl value of 30.42 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 11min, the sampling test shows that the acid value is 33.62mgKOH/g and the hydroxyl value is 20.13mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the reinforcing accelerant, and slowly cooling and crystallizing the material to be a milky white solid for later use, wherein the resin A is numbered.
Example 2
1. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating comprises the following raw materials in parts by mass: 37.1g of 1, 6-hexanediol, 5.1g of terephthalyl alcohol, 5.1g of 1, 4-butanediol, 51.1g of terephthalic acid, 16.2g of adipic acid, 0.86g of n-propyl zirconate, 0.75g of phosphorous acid, 50.35g of 15-crown ether and 0.26g of tetrabutylammonium chloride.
2. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating is prepared by the following steps:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: in the esterification, the temperature at the top of the tower is controlled to be less than or equal to 102 ℃, wherein the temperature is increased from 70 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.8 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and phosphorous acid is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 42min, and sampling to test indexes, wherein the acid value is 41.13mgKOH/g and the hydroxyl value is 31.24 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 12min, the sampling test shows that the acid value is 31.77mgKOH/g and the hydroxyl value is 21.35mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the reinforcing accelerant, and slowly cooling and crystallizing the material to be a milky white solid for later use, wherein the number of the resin B is serial.
Example 3
1. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating comprises the following raw materials in parts by mass: 39.1g of 1, 6-hexanediol, 5.4g of ethylene glycol, 48.1g of terephthalic acid, 17.1g of adipic acid, 5.4g of lauric acid, 0.66g of isopropyl zirconate, 0.68g of phosphorous acid, 60.34g of 18-crown ether and 0.38g of benzyltrimethylammonium chloride.
2. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating is prepared by the following steps:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: in the esterification, the temperature at the top of the tower is controlled to be less than or equal to 102 ℃, wherein the temperature is increased from 70 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.8 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and phosphorous acid is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 48min, and sampling to test indexes, namely an acid value of 43.21mgKOH/g and a hydroxyl value of 29.45 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 14min, the sampling test shows that the acid value is 33.12mgKOH/g and the hydroxyl value is 19.18mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the reinforcing accelerant, and slowly cooling and crystallizing the material to be a milky white solid for later use, wherein the resin C is numbered.
Example 4
1. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating comprises the following raw materials in parts by mass: 44.9g of 1, 6-hexanediol, 4.1g of butanediol, 42.7g of terephthalic acid, 11.1g of adipic acid, 12.4g of succinic acid, 0.71g of n-propyl zirconate, 0.75g of phosphorous acid, 50.45g of 15-crown ether and 0.28g of triphenyl ethyl phosphorus bromide.
2. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating is prepared by the following steps:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: in the esterification, the temperature at the top of the tower is controlled to be less than or equal to 102 ℃, wherein the temperature is increased from 70 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.8 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and phosphorous acid is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 39min, and sampling to test indexes, namely an acid value of 43.54mgKOH/g and a hydroxyl value of 31.08 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 13min, the sampling test shows that the acid value is 33.98mgKOH/g and the hydroxyl value is 20.35mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the reinforcing accelerant, and slowly cooling and crystallizing the material to be a milky white solid for later use, wherein the resin D is numbered.
Example 5
1. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating comprises the following raw materials in parts by mass: 42.3g of 1, 6-hexanediol, 2.9g of ethylene glycol, 52.6g of terephthalic acid, 10.5g of adipic acid, 0.81g of isopropyl zirconate, 0.85g of phosphorous acid, 60.17g of 18-crown ether and 0.66g of octadecyl dimethyl tertiary amine.
2. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating is prepared by the following steps:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: in the esterification, the temperature at the top of the tower is controlled to be less than or equal to 102 ℃, wherein the temperature is increased from 70 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.8 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and phosphorous acid is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 48min, and sampling to test indexes, namely an acid value of 41.09mgKOH/g and a hydroxyl value of 31.57 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 14min, the sampling test shows that the acid value is 32.33mgKOH/g and the hydroxyl value is 21.56mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the reinforcing accelerant, and slowly cooling and crystallizing the material to be a milky white solid for later use, wherein the resin E is numbered.
Example 6
1. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating comprises the following raw materials in parts by mass: 34.6g of 1, 6-hexanediol, 3.3g of ethylene glycol, 5.2g of 1, 4-butanediol, 41.8g of terephthalic acid, 15.18g of adipic acid, 14.3g of lauric acid, 0.71g of isopropyl zirconate, 0.72g of phosphorous acid, 15-crown-50.37 g, and 0.46g of cetyltrimethylammonium bromide.
2. A high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating is prepared by the following steps:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: in the esterification, the temperature at the top of the tower is controlled to be less than or equal to 102 ℃, wherein the temperature is increased from 70 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.8 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and phosphorous acid is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 41min, and sampling to test indexes, namely an acid value of 42.85mgKOH/g and a hydroxyl value of 29.54/mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 15min, the sampling test shows that the acid value is 33.78mgKOH/g and the hydroxyl value is 21.85mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the reinforcing accelerant, and slowly cooling and crystallizing the material to be a milky white solid for later use, wherein the resin F is numbered.
TABLE 1 index of the finished polyester resin synthesized in the example
Preparation of matt powder coatings: a. weighing and uniformly mixing high-crystallinity bifunctional polyester (A-F), TGIC (triglycidyl isocyanurate), Yingchuang B1530, titanium dioxide (R982), 44HB (pentahydrate), a leveling agent (GLP588), benzoin, 701B, carbon black and a flatting agent M70 according to a powder preparation formula shown in table 2, melting and extruding the premixed powder through an extruder, c, naturally cooling, d, breaking the extruded material cooled to room temperature, crushing in a coffee mill, sieving through a 180-mesh sieve to obtain powder with a certain particle size distribution, and bagging for later use.
Electrostatic spraying: spraying the prepared powder onto the pretreated steel plate by using an electrostatic spray gun, wherein the voltage is 60-80 KV.
Baking: placing the sprayed plate into an oven for baking, wherein the conditions are as follows: 170 ℃ for 15 min. After baking is completed, the relevant performance can be tested after the plate is cooled.
TABLE 2 formulation for high crystallinity difunctional polyester powder processing
From the above table results, it can be seen that: the high-crystallinity bifunctional polyester resin synthesized by the invention is suitable for the field of low-temperature curing extinction powder coatings, and has the characteristics of excellent leveling property, good mechanical property, low extinction gloss and high board surface fineness.
Claims (10)
1. The high-crystallinity bifunctional polyester resin for the low-temperature curing extinction powder coating and the synthesis method thereof are characterized in that the high-crystallinity bifunctional polyester resin for the powder coating comprises the following raw materials in parts by mass:
40-55 wt% of terephthalic acid, 30-50 wt% of 1, 6-hexanediol, 5-25 wt% of adipic acid, 0.05-0.2 wt% of esterification catalyst, 0-7 wt% of terephthalic acid, 0-9 wt% of ethylene glycol, 0-6 wt% of butanediol, 0-10 wt% of sebacic acid, 0-20 wt% of lauric acid, 0.05-0.12 wt% of esterification antioxidant and 0.02-0.2 wt% of curing accelerator.
2. The high crystallinity difunctional polyester resin for low temperature curing matting powder coating according to claim 1 characterized in that the ratio of the total moles of carboxyl groups of all carboxylic acids to the total moles of hydroxyl groups of all alcohols is 1.0270-1.0360.
3. The high-crystallinity bifunctional polyester resin for low-temperature-curable extinction powder coatings as claimed in claim 1, wherein the theoretical average functionality calculated from the formula monomers is 2, and the number average molecular weight is 2000-3000.
4. The high-crystallinity bifunctional polyester resin for low-temperature-curable matting powder coating material as claimed in claim 1, wherein the polyester resin is simultaneously end-capped with a large number of carboxyl groups and hydroxyl groups, and has an acid value of 30-36mgKOH/g, a hydroxyl value of 18-23mgKOH/g, a viscosity of 3000-6000mpa.s/160 ℃.
5. The high-crystallinity bifunctional polyester resin for low-temperature-curing extinction powder coatings according to claim 1, characterized in that the polyester resin structure consists of amorphous parts and crystalline parts, the crystallinity is 60-90%, and the DSC melting point is 90-120 ℃.
6. The high crystallinity difunctional polyester resin for low temperature curing matting powder coating according to claim 1 characterized in that the esterification catalyst is one of n-propyl zirconate or isopropyl zirconate.
7. The high-crystallinity bifunctional polyester resin for low-temperature-curing extinction powder coatings according to claim 1, characterized in that the esterification antioxidant is 70% phosphorous acid aqueous solution.
8. The high-crystallinity bifunctional polyester resin for low-temperature curing extinction powder coating of claim 1, wherein the curing accelerator is one or a combination of more than two of 18-crown-6, 15-crown-5, N-bromosuccinimide, quaternary ammonium salt, quaternary phosphonium salt and tertiary amine.
Specifically, the quaternary ammonium salt comprises tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, methyltriethylammonium chloride and tetrabutylammonium diacetate; the quaternary phosphonium salts include triphenylethylphosphonium bromide, triphenylbutylphosphonium bromide, and triphenylpropylphosphonium bromide, and the tertiary amines include octadecyl dimethyl tertiary amine, and dodecyl dimethyl tertiary amine.
9. A process for preparing a high crystallinity difunctional polyester resin for low temperature curing matting powder coatings as described in any one of claims 1 to 8, characterized in that said process comprises the steps of:
(1) feeding: according to the formula amount, alcohol is put into a reaction kettle in sequence, stirred, heated and melted until the temperature of the materials is more than 60 ℃, acid and catalyst are slowly added, and the temperature is raised.
(2) Heating esterification: the temperature of the top of the tower is controlled to be less than or equal to 102 ℃ in the esterification, wherein the temperature is increased from 60 ℃ to 80 ℃ to 170 ℃ at the heating rate of 8 ℃/10min, then the temperature is increased to 220 ℃ at the heating rate of 0.5-1 ℃/20min, the temperature is kept until the reaction system is clear and transparent, and the esterification antioxidant is added.
(3) Adding a second step of material esterification: after the step (2) is finished, adding dihydric alcohol or acid, preserving the heat at 220 ℃ for esterification for 30min-60min, and sampling to test indexes, namely an acid value of 41-44mgKOH/g and a hydroxyl value of 28-32 mgKOH/g.
(4) Vacuum esterification: the polycondensation temperature is 220 ℃, the vacuum degree is less than minus 0.052MPa, the vacuum polycondensation is carried out, the reaction time is 10 to 20min, the sampling test shows that the acid value is 30 to 36mgKOH/g, the hydroxyl value is 18 to 23mgKOH/g, and the vacuum is stopped.
(5) Cooling and discharging: and (3) cooling the material to below 180 ℃, discharging the solidified accelerant, and slowly cooling and crystallizing the material to be a milky solid for later use.
10. The high crystallinity difunctional polyester resin for low temperature curing matting powder coating according to claim 1 characterized in that it is mainly used for curing under 170 ℃ 15min of TGIC-B1530 system.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995743A (en) * | 2020-08-20 | 2020-11-27 | 浙江传化天松新材料有限公司 | Silsesquioxane modified bifunctional polyester resin and preparation method thereof |
| CN112409908A (en) * | 2020-10-11 | 2021-02-26 | 芜湖市森沐知识产权科技服务有限公司 | Polyurethane extinction powder coating and synthesis method thereof |
| CN113201126A (en) * | 2021-05-27 | 2021-08-03 | 黄山佳杰新材料科技有限公司 | Semi-crystalline polyester resin and powder coating |
| CN115572523A (en) * | 2022-10-19 | 2023-01-06 | 擎天材料科技有限公司 | Polyester resin composition, coating and application |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067066A (en) * | 2006-05-05 | 2007-11-07 | 罗门哈斯公司 | Acid functional phosphorus-containing polyester powder compositions and powder coatings made therefrom |
| JP2009013364A (en) * | 2007-07-09 | 2009-01-22 | Kansai Paint Co Ltd | Powder coating composition |
| CN102942837A (en) * | 2012-11-15 | 2013-02-27 | 山东海冠化工科技有限公司 | Polyester resin for one-step method low light powder paint and preparation method of polyester resin |
| CN103483565A (en) * | 2013-07-31 | 2014-01-01 | 广州擎天材料科技有限公司 | Semicrystalline polyester resin for TGIC-cured high-leveling powdery paint and synthetic method thereof |
| CN104119781A (en) * | 2013-04-28 | 2014-10-29 | 广东兴发铝业有限公司 | Low temperature curing thermosetting polyester powder coating and preparation method thereof |
| CN106085157A (en) * | 2016-06-30 | 2016-11-09 | 广东伊诗德新材料科技有限公司 | A kind of method preparing cryogenic curing resin |
| CN107189045A (en) * | 2017-06-23 | 2017-09-22 | 浙江光华材料科技有限公司 | A kind of TGIC systems powdery paints saturated polyester resin of the extra-weather-proof warping resistance of low temperature and preparation method thereof |
| CN107254240A (en) * | 2017-04-20 | 2017-10-17 | 浙江传化天松新材料有限公司 | A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof |
| CN108084415A (en) * | 2017-12-22 | 2018-05-29 | 安徽神剑新材料股份有限公司 | A kind of terminal hydroxy group-carboxyl difunctional saturated polyester resin and preparation method thereof |
| CN108752572A (en) * | 2018-05-22 | 2018-11-06 | 浙江光华科技股份有限公司 | A kind of preparation method of hypocrystalline high-melting-point hydroxyl telechelic polyester resin |
| CN108948826A (en) * | 2018-07-18 | 2018-12-07 | 浙江超浪新材料有限公司 | A kind of terminal carboxyl polyester resin and preparation method thereof |
| CN109054003A (en) * | 2018-08-23 | 2018-12-21 | 广州擎天材料科技有限公司 | A kind of TGIC solidification extinction powder coating polyester resin and preparation method thereof |
| CN109293905A (en) * | 2018-09-04 | 2019-02-01 | 广州擎天材料科技有限公司 | A kind of difunctional polyester resin and the preparation method and application thereof that extinction performance is good |
| CN109337528A (en) * | 2018-09-04 | 2019-02-15 | 广州擎天材料科技有限公司 | A kind of open air low brightness paint powder and preparation method thereof |
| CN109762148A (en) * | 2018-12-21 | 2019-05-17 | 佛山市科顺建筑材料有限公司 | A kind of indoor low temperature cured powder coating polyester resin and preparation method thereof |
-
2020
- 2020-01-15 CN CN202010041877.0A patent/CN111234185A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101067066A (en) * | 2006-05-05 | 2007-11-07 | 罗门哈斯公司 | Acid functional phosphorus-containing polyester powder compositions and powder coatings made therefrom |
| JP2009013364A (en) * | 2007-07-09 | 2009-01-22 | Kansai Paint Co Ltd | Powder coating composition |
| CN102942837A (en) * | 2012-11-15 | 2013-02-27 | 山东海冠化工科技有限公司 | Polyester resin for one-step method low light powder paint and preparation method of polyester resin |
| CN104119781A (en) * | 2013-04-28 | 2014-10-29 | 广东兴发铝业有限公司 | Low temperature curing thermosetting polyester powder coating and preparation method thereof |
| CN103483565A (en) * | 2013-07-31 | 2014-01-01 | 广州擎天材料科技有限公司 | Semicrystalline polyester resin for TGIC-cured high-leveling powdery paint and synthetic method thereof |
| CN106085157A (en) * | 2016-06-30 | 2016-11-09 | 广东伊诗德新材料科技有限公司 | A kind of method preparing cryogenic curing resin |
| CN107254240A (en) * | 2017-04-20 | 2017-10-17 | 浙江传化天松新材料有限公司 | A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof |
| CN107189045A (en) * | 2017-06-23 | 2017-09-22 | 浙江光华材料科技有限公司 | A kind of TGIC systems powdery paints saturated polyester resin of the extra-weather-proof warping resistance of low temperature and preparation method thereof |
| CN108084415A (en) * | 2017-12-22 | 2018-05-29 | 安徽神剑新材料股份有限公司 | A kind of terminal hydroxy group-carboxyl difunctional saturated polyester resin and preparation method thereof |
| CN108752572A (en) * | 2018-05-22 | 2018-11-06 | 浙江光华科技股份有限公司 | A kind of preparation method of hypocrystalline high-melting-point hydroxyl telechelic polyester resin |
| CN108948826A (en) * | 2018-07-18 | 2018-12-07 | 浙江超浪新材料有限公司 | A kind of terminal carboxyl polyester resin and preparation method thereof |
| CN109054003A (en) * | 2018-08-23 | 2018-12-21 | 广州擎天材料科技有限公司 | A kind of TGIC solidification extinction powder coating polyester resin and preparation method thereof |
| CN109293905A (en) * | 2018-09-04 | 2019-02-01 | 广州擎天材料科技有限公司 | A kind of difunctional polyester resin and the preparation method and application thereof that extinction performance is good |
| CN109337528A (en) * | 2018-09-04 | 2019-02-15 | 广州擎天材料科技有限公司 | A kind of open air low brightness paint powder and preparation method thereof |
| CN109762148A (en) * | 2018-12-21 | 2019-05-17 | 佛山市科顺建筑材料有限公司 | A kind of indoor low temperature cured powder coating polyester resin and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 李小强等: "双官能团聚酯粉末涂料消光性能的研究", 《涂料工业》 * |
| 林锡恩等: "固化促进剂在聚酯/TGIC热转印粉末涂料中的应用研究", 《合成材料老化与应用》 * |
| 褚海涛等: "TGIC体系粉末涂料低温超耐候柔性聚酯树脂的合成与研究", 《2017中国粉末涂料与涂装行业年会论文集》 * |
| 许国徽等: "超柔性后冲折环保体系用聚酯树脂的研究", 《2017中国粉末涂料与涂装行业年会论文集》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111995743A (en) * | 2020-08-20 | 2020-11-27 | 浙江传化天松新材料有限公司 | Silsesquioxane modified bifunctional polyester resin and preparation method thereof |
| CN112409908A (en) * | 2020-10-11 | 2021-02-26 | 芜湖市森沐知识产权科技服务有限公司 | Polyurethane extinction powder coating and synthesis method thereof |
| CN113201126A (en) * | 2021-05-27 | 2021-08-03 | 黄山佳杰新材料科技有限公司 | Semi-crystalline polyester resin and powder coating |
| CN115572523A (en) * | 2022-10-19 | 2023-01-06 | 擎天材料科技有限公司 | Polyester resin composition, coating and application |
| CN115572523B (en) * | 2022-10-19 | 2023-10-20 | 擎天材料科技有限公司 | Polyester resin composition, coating and application |
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