CN110373096B - Environment-friendly energy-saving powder coating and preparation method and application thereof - Google Patents
Environment-friendly energy-saving powder coating and preparation method and application thereof Download PDFInfo
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- CN110373096B CN110373096B CN201910740553.3A CN201910740553A CN110373096B CN 110373096 B CN110373096 B CN 110373096B CN 201910740553 A CN201910740553 A CN 201910740553A CN 110373096 B CN110373096 B CN 110373096B
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/80—Processes for incorporating ingredients
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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- Materials Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses an environment-friendly energy-saving powder coating and a preparation method and application thereof, wherein the preparation method comprises the following steps: 50-70 parts of composite polyester resin A; 3-10 parts of curing agent and 10-30 parts of other auxiliary agents. The preparation method comprises the steps of uniformly mixing the polyester resin A and the modified catalyst, performing melt extrusion by a double-screw extruder, cooling and tabletting to normal temperature, and crushing to obtain the composite polyester resin A; and putting the composite polyester resin A, the curing agent and other additives into a premixing cylinder, uniformly mixing, then carrying out melt extrusion by a double-screw extruder, cooling and tabletting to normal temperature, and finally crushing and grading by a high-speed crusher to prepare powder with the particle size of 30-35 um. The invention firstly melts and activates the polyester resin A and the modified catalyst, and then mixes and extrudes the polyester resin A and other materials such as the curing agent, and the like, finally prepares the environment-friendly and energy-saving product which can greatly reduce the curing temperature, has excellent physical and chemical properties and wide application field, can be used for the industries such as buildings, general industries, home appliances and furniture, communication equipment, automobile accessories, and the like, and is suitable for indoor and outdoor powder coating.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to an environment-friendly energy-saving powder coating as well as a preparation method and application thereof.
Background
Since the 21 st century, the powder coating and coating have the characteristics of resource and energy conservation, no pollution, high labor production efficiency, convenience for realizing automatic coating and the like, and quickly become a new product and a new process representative of the coating industry. At present, the powder coating becomes a recognized 4E coating product which meets the requirements of high production efficiency, excellent coating performance, ecological environment protection and economy, and becomes the coating which develops the fastest in the variety of environment-friendly coatings, but the curing temperature of the conventional powder coating is generally 200 ℃ or more, so that a large amount of energy is consumed at high temperature, and the market trend of energy conservation and emission reduction is not met; the low temperature curing (130 ℃) products which are already put out on the market cannot be used on a large scale due to the problems of formula cost, process limitation, transportation and storage and the like.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the environment-friendly and energy-saving powder coating, which can greatly reduce the curing temperature, control the formula cost, and facilitate production, transportation and storage, so that the powder coating can be used on a large scale and achieves the purposes of energy conservation and emission reduction.
The invention also aims to provide a preparation method of the environment-friendly and energy-saving powder coating.
The invention also aims to provide application of the environment-friendly and energy-saving powder coating.
The invention is realized by the following technical scheme:
an environment-friendly energy-saving powder coating comprises the following components in parts by weight:
50-70 parts of composite polyester resin A;
3-10 parts of a curing agent;
10-30 parts of other auxiliary agents;
the composite polyester resin A comprises the following components in parts by weight:
90-100 parts of polyester resin A;
0.5-6 parts of modified catalyst;
the acid value of the polyester resin A is 45-70 mgKOH/g; the particle size of the composite polyester resin A is 25um-30 um.
The acid value of the polyester resin A is 45-70 mgKOH/g, and too low acid value can cause too low reaction speed, so that the coating is incompletely cured at 160 ℃ to influence the product performance; the particle size of the composite polyester resin A is 25-30 um, and if the particle size is larger than 30um, the dispersion of the composite polyester resin A in the subsequent process extrusion can be influenced, so that the product performance can be influenced due to insufficient curing of a coating at 160 ℃.
Preferably, the curing agent is one or a mixture of two of triglycidyl isocyanurate and hydroxyalkyl amide.
Preferably, the modified catalyst is selected from one or a mixture of modified 2-methylimidazole, modified 2-phenylimidazoline or modified triphenylphosphine. The modified catalyst is prepared by micronizing the procatalyst and diluting it with fumed silica by means conventional in the art.
Preferably, the polyester resin A is carboxyl-terminated polyester resin, and the acid value of the polyester resin A is 50-60 mgKOH/g; the molecular weight of the polyester resin A is 3000-5000; the particle size of the composite polyester resin A is 25um-30 um.
The modified catalyst can reduce the reaction temperature of a coating, but the reduction amplitude is smaller (not more than 10 ℃), and in the invention, the modified catalyst and polyester resin are melted, mixed and sheared under the high-temperature condition, so that the modified catalyst can be activated initially, and is dispersed more uniformly with polyester, the activity of the modified catalyst is further improved after secondary melting extrusion, and the curing temperature can be reduced.
According to the invention, researches show that the matching proportion of the polyester resin A and the modified catalyst has a great influence on the performance of the coating, and when the dosage of the polyester resin A is too high, the coating is not completely cured, and the physical performance is obviously deteriorated; the polyester resin A is used in an excessively low amount, and the performance is affected because the activity of the catalyst is excessively high and chemical reaction is easily caused during secondary extrusion to enable the coating to be partially gelatinized. Therefore, it is preferable that the mass ratio of the polyester resin a to the modification catalyst is 20: 1-50: 1.
according to actual needs, other auxiliary agents are properly added into the environment-friendly and energy-saving powder coating, and the other auxiliary agents are selected from one or more of the following: leveling agent, defoaming agent, brightening agent and pigment and filler. The amount thereof is appropriately added according to the actual situation.
The leveling agent is one or a mixture of a plurality of polyacrylate, silicon-containing acrylate or hydrogenated castor oil;
the defoaming agent is one or a mixture of benzoin and dimethyl polysiloxane;
the brightener is one or a mixture of acrylate copolymer or silicon-containing acrylate copolymer.
The pigment filler is one or a mixture of more of barium sulfate or calcium carbonate, titanium dioxide or ferric oxide.
The invention also provides a preparation method of the environment-friendly energy-saving powder coating, which comprises the following steps:
a. uniformly mixing the polyester resin A and the modified catalyst, then carrying out melt extrusion by a double-screw extruder, tabletting, cooling to normal temperature, and crushing to obtain a composite polyester resin A;
b. putting the composite polyester resin A, the curing agent and other additives into a premixing cylinder according to a certain proportion, uniformly mixing, performing melt extrusion by a double-screw extruder, tabletting, cooling to normal temperature, and crushing and grading by a high-speed crusher to prepare powder with the particle size of 30-35 um.
Preferably, in the step a, the melt extrusion temperature of the twin-screw extruder is 130-160 ℃.
Preferably, in the step b, the melt extrusion temperature of the twin-screw extruder is 80-120 ℃.
The preparation process of the invention adopts the steps of firstly preparing the composite polyester resin A, then melting and extruding the composite polyester resin A and other components,
the activity of the modified catalyst can be greatly improved, and the modified catalyst and the specific polyester can be finally cured at low temperature of 160 ℃.
The invention also provides application of the environment-friendly and energy-saving powder coating in the industries of buildings, general industry, household appliances, furniture, communication equipment, automobile accessories and the like, wherein the coating thickness of the environment-friendly and energy-saving powder coating is 50-120 um, and preferably 60-80 um.
Preferably, the environment-friendly and energy-saving powder coating is applied to coating building materials, general industries, household appliances, furniture, communication equipment and automobile accessories, and the curing temperature of the environment-friendly and energy-saving powder coating is 160 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1) the polyester resin A and the modified catalyst are firstly melted and extruded at high temperature, the modified catalyst is primarily activated, and then the modified catalyst and other additives are melted and extruded for the second time, so that the curing temperature of the coating is greatly reduced by improving the activity of the modified catalyst, the low-temperature curing at 160 ℃ is realized, and energy can be greatly saved compared with the conventional product cured at 200 ℃;
2) the invention realizes the low-temperature curing at 160 ℃ mainly through the modification of raw materials and a special process, so the formula and the process cost are greatly reduced, and compared with a low-temperature curing product at 130 ℃, the invention has very great cost advantage and can be produced in large scale.
3) The invention has zero VOC emission in the whole production and construction process, greatly reduces the curing temperature, and belongs to a new generation of energy-saving and environment-friendly product;
4) the preparation method is simple and convenient to use.
Detailed Description
The following examples are given to specifically describe the present invention, but are not limited thereto.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
polyester resin A: the acid value is 45-70 mgKOH/g, and the catalyst is commercially available;
modifying the catalyst: purchasing in market;
the curing agent is hydroxyalkyl amide and is commercially available;
the flatting agent is polyacrylate and is commercially available;
the defoaming agent is benzoin which is commercially available;
the brightener is an acrylate copolymer and is commercially available;
the pigment and filler is barium sulfate and is commercially available.
Examples 1-6 and comparative examples 1-4:
a. uniformly mixing the polyester resin A and the modified catalyst according to the proportion shown in the table 1, and then carrying out melt extrusion by a double-screw extruder, wherein the melt extrusion temperature of the double-screw extruder is 150 ℃, tabletting, cooling to normal temperature, and crushing to obtain the composite polyester resin A with the particle size of 25-30 um;
b. putting the composite polyester resin A, the curing agent, the leveling agent, the defoaming agent, the brightening agent and the pigment filler into a premixing cylinder according to the proportion shown in the table 2, uniformly mixing, carrying out melt extrusion by a double-screw extruder at the melt extrusion temperature of 100 ℃, tabletting, cooling to normal temperature, and finally crushing and grading by a high-speed crusher to prepare powder with the particle size of 30-35 um.
Example 7:
the procedure of example 1 was repeated except that the composite polyester resin A having a particle size of 60 to 70um was obtained by crushing.
Comparative example 5:
and (2) putting the polyester resin A, the modified catalyst, the curing agent, the flatting agent, the defoaming agent, the brightening agent and the pigment filler into a premixing cylinder, uniformly mixing, grinding, dispersing by a dispersion machine, and preparing into powder with the particle size of 30-35 um, wherein the content of each component is the same as that in example 1.
Application example 1
The powder prepared by the method is sprayed on a tin plate through an electrostatic gun, is melted and solidified into a film under the baking condition of 160 ℃ for 8 minutes, the thickness of the dry film is 60-80 mu m, the performances of the coating such as impact resistance, pencil hardness, adhesive force, bending resistance, neutral salt spray resistance and the like are detected, and the specific detection standards and results are shown in Table 3.
Table 1: composition of composite polyester resin A (parts by weight)
TABLE 2 concrete proportions (in parts by weight) of the components in the examples and comparative examples
TABLE 3 Performance test data for each of the examples and comparative examples
From the results in Table 3, it is clear that the eco-friendly and energy-saving powder coatings of examples 1 to 6 have good impact resistance, pencil hardness, adhesion, bending resistance, neutral salt spray, and the like at a curing temperature of 160 ℃. However, as can be seen from comparative examples 1 and 2, the particle size of the composite polyester resin a has a significant influence on various performance indexes of the powder coating, specifically, the particle size of comparative example 1 is large, and the reactivity during curing is not enough, so that the coating is not completely cured, and the salt spray performance is poor; the particle size of the comparative example 2 is small,
the reactivity is so strong that it is already partly reacted during the production process that the coating is very brittle and has poor physical properties.
From comparative examples 3 and 4, it can be seen that the acid value of the polyester resin A has a significant influence on various performance indexes of the powder coating, specifically, the acid value of comparative example 3 is small, the crosslinking density is too small when the coating is cured, and the comprehensive mechanical properties are not good; comparative example 4 has a large acid value and the crosslinking density is too high upon curing to deteriorate the flexibility of the coating.
From example 1 and comparative example 5, it can be seen that the polyester resin A and the modified catalyst are melted, mixed and sheared at high temperature, so that the modified catalyst is activated primarily, and is dispersed more uniformly with the polyester, and the activity of the modified catalyst is further improved after the secondary melt extrusion, so that the curing temperature can be reduced.
From examples 1 and 7, it is understood that when the particle diameter of the composite polyester resin A is 60um to 70um, the curing of the system is insufficient and the overall performance is not in an optimum state.
The environment-friendly energy-saving powder can be used in the industries of buildings, general industries, home appliances, furniture, communication equipment, automobile accessories and the like on a large scale.
Application example 2
Preferably, the embodiment 2 is performed, and the process conditions with good performance and the lowest curing temperature are selected by baking at different temperatures:
table 4 performance test data for example 2 at different cure conditions
The experimental results in Table 4 show that the energy-saving powder can be completely cured at 160 ℃ X8, and has excellent comprehensive physical, chemical and corrosion resistance properties. Incomplete curing at the temperature of below 160 ℃, poor comprehensive performance and unsuitability for practical application; the curing agent can be completely cured at the temperature of above 160 ℃, has good performances in all aspects, but wastes resources in comparison, does not meet the requirements of energy conservation and emission reduction, so the optimal curing condition of 160 ℃ X8min is realized, the perfect combination of comprehensive performance and energy conservation and consumption reduction is realized, and the curing agent is suitable for large-scale popularization and application.
Claims (9)
1. The environment-friendly energy-saving powder coating is characterized by comprising the following components in parts by weight:
50-70 parts of composite polyester resin A;
3-10 parts of a curing agent;
10-30 parts of other auxiliary agents;
the composite polyester resin A comprises the following components in parts by weight:
90-100 parts of polyester resin A;
0.5-6 parts of modified catalyst;
the acid value of the polyester resin A is 45-70 mgKOH/g; the particle size of the composite polyester resin A is 25-30 μm;
the mass ratio of the polyester resin A to the modified catalyst is 20: 1-50: 1;
the preparation method of the environment-friendly energy-saving powder coating comprises the following steps:
a. uniformly mixing the polyester resin A and the modified catalyst, then carrying out melt extrusion by a double-screw extruder, tabletting, cooling to normal temperature, and crushing to obtain a composite polyester resin A;
b. uniformly mixing the composite polyester resin A, the curing agent and other additives in proportion, then carrying out melt extrusion by a double-screw extruder, tabletting, cooling to normal temperature, and then crushing and grading to prepare powder with the particle size of 30 micrometers-35 micrometers, thus obtaining the composite polyester resin A;
in the step a, the melt extrusion temperature of a double-screw extruder is 130-160 ℃; in the step b, the melt extrusion temperature of the double-screw extruder is 80-120 ℃;
the modified catalyst is selected from one or a mixture of more of modified 2-methylimidazole, modified 2-phenylimidazoline or modified triphenylphosphine.
2. The environment-friendly and energy-saving powder coating as claimed in claim 1, wherein the curing agent is one or a mixture of triglycidyl isocyanurate and hydroxyalkylamide.
3. The environment-friendly energy-saving powder coating as claimed in claim 1, wherein the polyester resin A is carboxyl-terminated polyester resin, and the acid value of the polyester resin A is 50-60 mgKOH/g; the molecular weight of the polyester resin A is 3000-5000; the particle size of the composite polyester resin A is 25-30 μm.
4. The environment-friendly energy-saving powder coating as claimed in claim 1, wherein the other auxiliary agents are selected from one or more of the following: leveling agent, defoaming agent, brightening agent and pigment and filler.
5. The environment-friendly energy-saving powder coating as claimed in claim 4, wherein the leveling agent is one or a mixture of polyacrylate, silicon-containing acrylate or hydrogenated castor oil; the defoaming agent is one or a mixture of benzoin and dimethyl polysiloxane; the brightener is one or a mixture of more of acrylate copolymer or silicon-containing acrylate copolymer; the pigment filler is one or a mixture of more of barium sulfate or calcium carbonate, titanium dioxide or ferric oxide.
6. The method for preparing environment-friendly and energy-saving powder coating according to any one of claims 1 to 5, characterized by comprising the following steps:
a. uniformly mixing the polyester resin A and the modified catalyst, then carrying out melt extrusion by a double-screw extruder, tabletting, cooling to normal temperature, and crushing to obtain a composite polyester resin A;
b. uniformly mixing the composite polyester resin A, the curing agent and other additives in proportion, then carrying out melt extrusion by a double-screw extruder, tabletting, cooling to normal temperature, and then crushing and grading to prepare powder with the particle size of 30-35 mu m.
7. The preparation method of the environment-friendly and energy-saving powder coating as claimed in claim 6, wherein in the step a, the melt extrusion temperature of the twin-screw extruder is 130-160 ℃; in the step b, the melt extrusion temperature of the double-screw extruder is 80-120 ℃.
8. Use of the environmental protection and energy saving powder coating according to any one of claims 1 to 5 for coating building materials, general industries, home appliances, furniture, communication equipment, and automobile parts.
9. The use of the environmental friendly energy saving powder coating of claim 8 for coating building materials, general industries, home appliances, furniture, communication equipment, auto parts, wherein the curing temperature of the environmental friendly energy saving powder coating is 160 ℃.
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| CN111253841A (en) * | 2020-03-11 | 2020-06-09 | 浙江绿环新材料科技有限公司 | Low-temperature curing outdoor super-weather-resistant and corrosion-resistant powder coating and preparation method thereof |
| CN112852256B (en) * | 2021-01-04 | 2022-05-20 | 海隆石油产品技术服务（上海）有限公司 | Powder coating composition prepared by coating epoxy powder waste in ultrafine drill pipe and oil pipe |
| CN112876951B (en) * | 2021-01-18 | 2022-06-24 | 广东歌丽斯化学有限公司 | Heat-insulating powder coating and preparation method and application thereof |
| CN112876952B (en) * | 2021-01-18 | 2022-04-12 | 广东歌丽斯化学有限公司 | Imitation leather handfeel powder coating and preparation method and application thereof |
| CN115558384B (en) * | 2022-11-02 | 2023-12-08 | 广东睿智环保科技股份有限公司 | Low-temperature-cured high-corner-coverage powder coating and preparation method thereof |
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