CN115011220B - Impact-resistant powder coating and preparation method thereof - Google Patents
Impact-resistant powder coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 239000000843 powder Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001225 polyester resin Polymers 0.000 claims abstract description 10
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- 239000003822 epoxy resin Substances 0.000 claims abstract description 8
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- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
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- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 238000000034 method Methods 0.000 claims description 3
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
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- 239000004431 polycarbonate resin Substances 0.000 description 2
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- 239000011145 styrene acrylonitrile resin Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an impact-resistant powder coating and a preparation method thereof, belonging to the technical field of powder coatings, wherein the powder coating comprises the following raw materials: polyester resin, epoxy resin and modified nano TiO 2 Toughening assistant, flatting agent, benzoin and pigment and filler. The toughening auxiliary agent is a thermoplastic elastomer material, can greatly improve the flexibility of the coating, and modifies the nano TiO 2 The toughening effect of the inorganic nano particles is exerted, the toughening of the elastomer and the strengthening and toughening of the inorganic nano particles are combined to generate a multiphase composite system, and the impact resistance of the coating is improved from multiple aspects; and the invention is through to nanometer TiO 2 The modification can solve the problem of nano TiO 2 The acting force and the agglomeration problem with the resin matrix are solved, and the molecular dynamic toughening effect is improved on the basis of exerting the toughening and the reinforcement of the inorganic nano particles; the powder coating prepared by the invention has good impact resistance and can effectively expand the application range.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to an impact-resistant powder coating and a preparation method thereof.
Background
The powder coating is in a completely different form from general coating, and it exists in a state of fine powder. Since no solvent is used, it is called a powder coating. The powder coating has the characteristics of harmlessness, high efficiency, resource saving and environmental protection. The existing powder coating has weak impact resistance and adhesive force, and the phenomenon of serious powder falling is easy to occur after the coating is used for painting the wall surface.
Chinese patent application No. 202010481882.3 discloses an impact-resistant adhesion-type powder coating and a preparation method thereof, wherein the impact-resistant adhesion-type powder coating comprises, by weight, 100 parts of the total weight of the impact-resistant adhesion-type powder coating, 2-20 parts of modified epoxy resin, 12-15 parts of modified polyester resin, 13-15 parts of polycarbonate resin, 15-18 parts of styrene-acrylonitrile resin, 2-5 parts of curing agent, 3-5 parts of leveling agent and 35-40 parts of pigment; according to the patent, after the specific resin combination of modified epoxy resin, modified polyester resin, polycarbonate resin and styrene-acrylonitrile resin is combined with the curing agent, the leveling agent and the pigment according to a specific proportion, the obtained powder coating has good flexibility and high hardness, and has super-strong impact resistance and excellent adhesive force. In this patent, the purpose of improving the performance is achieved by combining a plurality of different types of resins, and although the plurality of resins can complement each other to some extent, the effect of improving the impact resistance is limited, and the accuracy and requirement of the amount of the compound are high, and therefore, further improvement is required.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an impact-resistant powder coating and a preparation method thereof.
The toughening auxiliary agent is a thermoplastic elastomer material, can greatly improve the flexibility of the coating, and modifies the nano TiO 2 The toughening effect of the inorganic nano particles is exerted, the toughening of the elastomer and the strengthening and toughening of the inorganic nano particles are combined to generate a multi-phase composite system, and the impact resistance of the coating is improved from multiple aspects; and the invention is through to nanometer TiO 2 Can solve the problem of nano TiO by modification 2 The problems of acting force and agglomeration of the (inorganic nano particles) and the resin matrix are solved, and the molecular dynamic toughening effect of the (inorganic nano particles) is improved on the basis of exerting toughening and reinforcing of the inorganic nano particles; therefore, the powder coating prepared by the invention has good impact resistance and can effectively expand the application range.
The purpose of the invention can be realized by the following technical scheme:
an impact-resistant powder coating comprises the following raw materials in parts by weight: 40-50 parts of polyester resin, 35-45 parts of epoxy resin and modified nano TiO 2 3-4 parts of toughening auxiliary agent, 0.2-0.3 part of leveling agent, 6-8 parts of benzoin and 40-50 parts of pigment and filler.
Furthermore, the toughening auxiliary agent is a thermoplastic elastomer, and the thermoplastic elastomer auxiliary agent forms a semi-interpenetrating network structure in a cross-linked network formed by the resin and the curing agent in the process of participating in a curing reaction, so that the flexibility of the coating is greatly improved.
Further, the leveling agent is an organic silicon leveling agent or a fluorocarbon leveling agent.
Further, modified nano TiO 2 Is prepared by the following steps:
mixing nanometer TiO 2 Ultrasonically dispersing in xylene, adding the dispersion and dodecenyl succinic anhydride into a three-neck flask with a mechanical stirring, ventilating and water separating device, and introducing N 2 Heating to 100 ℃, continuously stirring for 30min, then continuously heating to 160 ℃, adding a catalyst of monobutyl tin oxide, reacting for 2h, after the reaction is finished, carrying out suction filtration, repeatedly washing the obtained solid with acetone to remove unreacted dodecenyl succinic anhydride, washing with distilled water for 3-4 times, finally placing the product in a vacuum oven at 60 ℃ to dry to constant weight to obtain the modified nano TiO 2 ；
Nano TiO 2 2 The dosage ratio of the dimethylbenzene to the dodecenylsuccinic anhydride to the monobutyltin oxide is 1g.
Nano TiO 2 2 The surface contains-OH, and under the catalytic action of monobutyl tin oxide, the-OH and the dodecenyl succinic anhydride are subjected to chemical reaction, so that the dodecenyl succinic anhydride is grafted to the nano TiO in a ring-opening manner 2 A surface; on the one hand, in the nanometer TiO 2 Organic molecular chains are introduced to the surface of the nano TiO material, so that nano TiO can be improved 2 Agglomeration between particles promotes dispersion in the resin matrix; on the other hand, after the ring opening of the anhydride, naked-COOH and-COOH can be formed to participate in the formation of a curing and crosslinking network of the system, so that the toughness of the curing system is improved, and in addition, a dodecenyl molecular chain belongs to a long alkyl chain and can be wound with a polyester resin molecular chain, so that the toughening effect is achieved;
nano TiO 2 2 The coating has good heat resistance and ultraviolet resistance, is uniformly dispersed in a coating system, can not only exert the enhancement of heat resistance and ultraviolet resistance, but also effectively toughen, thereby improving the impact resistance of the coating.
A preparation method of an impact-resistant powder coating comprises the following steps:
firstly, weighing the raw materials according to the weight part ratio of the formula, and putting the raw materials into a high-speed mixer for mixing for 5-6min to obtain a premix;
setting the temperature of the double-screw extruder to be 100 ℃, putting the premix into a hopper of the extruder, maintaining constant speed for melting, mixing and extruding, and performing double-roller tabletting to obtain a mixture;
and thirdly, after cooling the mixture, grinding the mixture by using a high-speed grinding mill, and then sieving the mixture by using a 180-mesh sieve to prepare the impact-resistant powder coating.
The invention has the beneficial effects that:
the invention adds modified nanometer TiO into the powder coating 2 On the one hand, in the nano TiO 2 Organic molecular chains are introduced to the surface of the nano TiO material, so that nano TiO can be improved 2 The agglomeration phenomenon among the particles promotes the dispersion in the resin matrix; on the other hand, after the ring opening of the anhydride, naked-COOH and-COOH can be formed to participate in the formation of a system curing crosslinking network, so that the toughness of a curing system is improved, and in addition, a dodecenyl molecular chain belongs to a long alkyl chain and can be wound with a polyester resin molecular chain, so that the toughening effect is achieved;
the toughening auxiliary agent is a thermoplastic elastomer material, can greatly improve the flexibility of the coating, and modifies the nano TiO 2 The toughening effect of the inorganic nano particles is exerted, the toughening of the elastomer and the strengthening and toughening of the inorganic nano particles are combined to generate a multi-phase composite system, and the impact resistance of the coating is improved from multiple aspects; and the invention is through to nanometer TiO 2 Can solve the problem of nano TiO by modification 2 The problems of acting force and agglomeration of the (inorganic nano particles) and the resin matrix are solved, and the molecular dynamic toughening effect of the (inorganic nano particles) is improved on the basis of exerting toughening and reinforcing of the inorganic nano particles; therefore, the powder coating prepared by the invention has good impact resistance and can effectively expand the application range.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of modified nano TiO 2 ：
1g of nano TiO 2 Ultrasonically dispersing in 300mL of dimethylbenzene, adding the dispersion and 0.76g of dodecenyl succinic anhydride into a three-neck flask provided with a mechanical stirring, ventilating and water separating device, and introducing N 2 Heating to 100 ℃, continuously stirring for 30min, then continuously heating to 160 ℃, adding 0.6mg of catalyst of monobutyltin oxide, reacting for 2h, after the reaction is finished, performing suction filtration, repeatedly washing the obtained solid with acetone to remove unreacted dodecenylsuccinic anhydride, washing with distilled water for 3 times, finally placing the product in a vacuum oven at 60 ℃ to dry to constant weight to obtain the modified nano TiO 2 。
Example 2
Preparation of modified nano TiO 2 ：
2g of nano TiO 2 Ultrasonically dispersing in 600mL of dimethylbenzene, adding the dispersion and 1.52g of dodecenyl succinic anhydride into a three-neck flask provided with a mechanical stirring, ventilating and water separating device, and introducing N 2 Heating to 100 ℃, continuously stirring for 30min, continuously heating to 160 ℃, adding 1.2mg of catalyst of monobutyltin oxide, reacting for 2h, after the reaction is finished, performing suction filtration, repeatedly washing the obtained solid with acetone to remove unreacted dodecenylsuccinic anhydride, washing with distilled water for 4 times, finally placing the product in a vacuum oven at 60 ℃ to dry to constant weight, and obtaining the modified nano TiO 2 。
Example 3
An impact-resistant powder coating comprises the following raw materials: 40g of polyester resin, 35g of epoxy resin and modified nano TiO 2 3g, 0.2g of SBS, 6g of polydimethylsiloxane, 0.7g of benzoin and 40g of pigment and filler;
the preparation method of the impact-resistant powder coating comprises the following steps:
firstly, weighing the raw materials according to the weight part ratio of the formula, and putting the raw materials into a high-speed mixer for mixing for 5min to obtain a premix;
setting the temperature of the double-screw extruder to be 100 ℃, putting the premix into a hopper of the extruder, maintaining constant speed for melting, mixing and extruding, and performing double-roller tabletting to obtain a mixture;
and thirdly, after cooling the mixture, grinding the mixture by using a high-speed grinding mill, and then sieving the mixture by using a 180-mesh sieve to prepare the impact-resistant powder coating.
Example 4
An impact-resistant powder coating comprises the following raw materials: 45g of polyester resin, 40g of epoxy resin and modified nano TiO 2 3.5g, 0.25g of SIS, 7g of polymethylphenylsiloxane, 0.8g of benzoin and 45g of pigment and filler;
the preparation method of the impact-resistant powder coating comprises the following steps:
firstly, weighing the raw materials according to the weight part ratio of the formula, and putting the raw materials into a high-speed mixer for mixing for 6min to obtain a premix;
setting the temperature of the double-screw extruder to be 100 ℃, putting the premix into a hopper of the extruder, maintaining constant-speed melting, mixing and extruding, and performing double-roller tabletting to obtain a mixture;
and thirdly, after cooling the mixture, grinding the mixture by using a high-speed grinding mill, and then sieving the mixture by using a 180-mesh sieve to prepare the impact-resistant powder coating.
Example 5
An impact-resistant powder coating comprises the following raw materials: 50g of polyester resin, 45g of epoxy resin and modified nano TiO 2 4g of TPE, 0.3g of fluorocarbon leveling agent, 0.9g of benzoin and 50g of pigment filler;
the preparation method of the impact-resistant powder coating comprises the following steps:
firstly, weighing the raw materials according to the weight part ratio of the formula, and putting the raw materials into a high-speed mixer for mixing for 6min to obtain a premix;
setting the temperature of the double-screw extruder to be 100 ℃, putting the premix into a hopper of the extruder, maintaining constant-speed melting, mixing and extruding, and performing double-roller tabletting to obtain a mixture;
and thirdly, after cooling the mixture, grinding the mixture by using a high-speed grinding mill, and then sieving the mixture by using a 180-mesh sieve to obtain the impact-resistant powder coating.
Comparative example 1
Modified nano TiO in example 3 2 By replacing with ordinary TiO 2 The other raw materials and the preparation process are unchanged.
Comparative example 2
Modified nano TiO of example 3 2 The raw materials are removed, and the rest raw materials and the preparation process are unchanged.
The powder coatings obtained in examples 3 to 5 and comparative examples 1 to 2 were sprayed onto tin plate using an electrostatic spray gun, and the plate was then baked in a preheated electric oven for performance testing:
the impact resistance of the coating was tested with a paint film impactor, with reference to GB/T1732-1993; according to a method B in GB/T1733-1993, a sample plate is taken out after being immersed in boiling water for 2 hours, and the gloss retention rate of the coating after being boiled in water is measured;
the results obtained are shown in the following table:
from the data, the powder coating prepared by the invention has higher impact resistance, and the water resistance can meet the use requirement of the powder coating; in combination with the data of comparative example 1, it can be seen that nano TiO 2 After modification, the agglomeration and the binding force with a resin matrix can be improved, so that the toughness of the powder coating is improved; combining the data of comparative example 2, it can be seen that the nano TiO 2 After modification, the modified powder has a synergistic effect with the toughening additive, and the impact resistance of the powder can be improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (5)
1. The impact-resistant powder coating is characterized by comprising the following raw materials in parts by weight: 40-50 parts of polyester resin, 35-45 parts of epoxy resin and modified nano TiO 2 3-4 parts of toughening auxiliary agent, 0.2-0.3 part of leveling agent, 6-8 parts of benzoin and 40-50 parts of pigment and filler;
wherein the modified nano TiO 2 Is prepared by the following steps:
mixing nanometer TiO 2 Ultrasonically dispersing in xylene, adding the dispersion and dodecenyl succinic anhydride into a three-neck flask with a mechanical stirring, ventilating and water separating device, and introducing N 2 Heating to 100 ℃, continuously stirring for 30min, then continuously heating to 160 ℃, adding a catalyst of monobutyl tin oxide, reacting for 2h, after the reaction is finished, carrying out suction filtration, repeatedly washing the obtained solid with acetone to remove unreacted dodecenyl succinic anhydride, washing with distilled water for 3-4 times, finally placing the product in a vacuum oven at 60 ℃ to dry to constant weight to obtain the modified nano TiO 2 。
2. The impact-resistant powder coating of claim 1, wherein the toughening aid is a thermoplastic elastomer.
3. The impact-resistant powder coating as claimed in claim 1, wherein the leveling agent is an organosilicon-based leveling agent or a fluorocarbon-based leveling agent.
4. An impact-resistant powder coating composition as claimed in claim 1, whereinCharacterized in that the modified nano TiO 2 Nano TiO in the preparation process 2 The dosage ratio of the xylene, the dodecenyl succinic anhydride and the monobutyl tin oxide is 1 g.
5. The method of claim 1, comprising the steps of:
firstly, weighing the raw materials according to the weight part ratio of the formula, and putting the raw materials into a high-speed mixer to mix for 5-6min to obtain a premix;
setting the temperature of the double-screw extruder to be 100 ℃, putting the premix into a hopper of the extruder, maintaining constant-speed melting, mixing and extruding, and performing double-roller tabletting to obtain a mixture;
and thirdly, after cooling the mixture, grinding the mixture by using a high-speed grinding mill, and then sieving the mixture by using a 180-mesh sieve to prepare the impact-resistant powder coating.
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| CN115011220A CN115011220A (en) | 2022-09-06 |
| CN115011220B true CN115011220B (en) | 2023-02-28 |
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| CN116334925B (en) * | 2023-01-16 | 2023-09-15 | 江苏金呢工程织物股份有限公司 | Impact-resistant coating for impact-resistant forming net, preparation method and coating method thereof |
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