CN103254736A - Polyaniline powder paint with acid-resistant self-repair function and preparation method thereof - Google Patents
Polyaniline powder paint with acid-resistant self-repair function and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyaniline powder paint with acid-resistant self-repair function, which is prepared from the following components in parts by weight: 450-550 parts of special-type epoxy resin, 80-140 parts of curing agent, 5-100 parts of polyaniline, 200-250 parts of pigment and filler and 30-50 parts of assistant. The coating of the powder paint containing a certain amount of polyaniline is subjected to anodization reaction under acidic conditions, and quickly recovers the surface passivation layer; even if corrosive substances permeate, the passivation layer can be used as a second barrier to inhibit the corrosion, thereby ensuring the corrosion resistance and self-repair property of the coating; and the powder paint has the characteristics of obviously higher bending resistande and flexibility, high corrosion resistance and high scratch resistance. By organically combining the isolation property of a common paint and the self-repair passivation characteristic of polyaniline, the powder paint implements thick coating at one time, is simple for construction, and avoids the hidden danger of spot corrosion from the damaged point after the coated workpiece is damaged in the construction process; and the adhesive force and corrosion resistance of the coating satisfy the correlation detection in Chinese Standard.
Description
Technical field
The invention belongs to paint field, relate to decorative powder coatings, especially a kind of polyaniline powder coating with acid resistance self-repair function and preparation method thereof.
Background technology
1985, DeBerry finds, in acidic medium, can make the stainless steel surface active passivation and anticorrosion with the synthetic polyaniline film of electrochemical process, these characteristics have caused people's attention, and from then on people have begun the applied research of conducting polymer film in the corrosion prevention field.
1991, the Los Alamos National Laboratories of the U.S. (IANL) and NASA (NASA) have reported that conductive polyaniline is to the soft steel preservative activity, kennedy's space launching center of NASA is located in the coastal region of seriously corroded, there was dampness in the air in the there, salt air corrosion is serious, and each rocket launching all will produce nearly 13 tons high temperature HC1 gas, have a strong impact on launcher and other facility work-ing life.They find, polyaniline is coated in the inwall of rocket launching tower, can avoid the high temperature acid mist to the corrosion of launching tower, and effect is very good.Kennedy's space launching center and GeoTech company are signatory, authorize the polyaniline anti-corrosive paint of GeoTech manufacturer product Catiz by name.The commercial value of anticorrosive polyaniline performance is seen some from this.
The antiseptic property of polyaniline is not only a simple passivation layer, at the interface of polyaniline and iron redox reaction takes place, and generates the compound of a kind of Fe-PANI; The oxidizing potential of this compound is higher than the oxidizing potential of independent PANI, promotes the reduction of oxygen with katalysis, thereby has compensated the electric charge that the dissolving because of iron consumes, and the current potential of iron is stabilized in passivation region, can reduce the dissolution rate of metal.
Polyaniline makes its solvability extreme difference owing to strong rigidity and the strong interaction of interchain of its chain, is dissolved in any solvent hardly, and pure polyaniline is very poor to the cohesiveness of metal.These shortcomings have greatly limited polyaniline application technically.
Common protective system only is that corrosive medium and metal base are isolated, and the blocking-up corrosive deposit contacts with metal, thereby reaches anticorrosion purpose.Yet its preservative effect must be subjected to the influence of quality and the coating density of pre-treatment, and common coating presents loose and porous structure mostly under electron microscope, and corrosive medium tends to from than immersing the macrovoid, thus the corroding metal base material.
By retrieval, do not find the patent publication us relevant with patent application of the present invention as yet.
At present, the domestic powder coating product of not finding to meet above-mentioned functions as yet.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part, a kind of high anticorrosive, scratch resistance ability is provided, strong adhesion have polyaniline powder coating of acid resistance self-repair function and preparation method thereof, this preparation method's method is simple, easy to operate, save production cost, improved economic benefit of enterprises.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of polyaniline powder coating with acid resistance self-repair function, its raw material constitutes component and parts by weight are respectively:
And, described specific epoxy resin is the mixture that modified bisphenol A type Resins, epoxy, bisphenol A-type high molecular solid epoxy and o-cresol formaldehyde epoxy resin are formed, modified bisphenol A type Resins, epoxy: bisphenol A-type high molecular solid epoxy: the mass ratio of o-cresol formaldehyde epoxy resin is: 280～320:130～180:30～50.
And described modified bisphenol A type Resins, epoxy: bisphenol A-type high molecular solid epoxy: the mass ratio of o-cresol formaldehyde epoxy resin is 300:150:35.
And described auxiliary agent is the mixture of flow agent, brightening agent, defoamer, and its parts by weight are as follows:
Flow agent: 16～22 parts;
Anti-interference agent: 10～20 parts;
Pore eliminator: 4～8 parts.
And the mass ratio of the mixture of described flow agent, brightening agent, defoamer is 9:7:3.
And described polyaniline molecule structural formula is:
。
And described solidifying agent is imidazoles or phenols curing agent.
And described solidifying agent is for being the linear resin of end group with glyoxal ethyline, dihydroxyphenyl propane.
And described color stuffing is one or more the mixture in common Rutile type Titanium Dioxide, carbon black, silicon powder or the process white.
Aforesaid preparation method with polyaniline powder coating of acid resistance self-repair function, it is characterized in that: step is as follows:
(1) preparation of polyaniline:
1. emulsion polymerization synthesized polyaniline technology: add in reactor by aniline: the ratio of the amount of substance of dodecylbenzene is that the ratio of 2:1 is adding aniline and dodecylbenzene, add water successively after mixing, dimethylbenzene, fully stir, till obtaining transparent emulsion;
2. then in the transparent emulsion in ammonium persulphate: the ratio of the amount of substance of aniline is that the ratio of 1:1 drips ammonium persulphate (NH
4)
2S
2O
8The aqueous solution, the system color slowly deepens, and keeps 0～20 ℃ of system temperature, continues to stir 30 minutes, during static storing 24 after, add the acetone breakdown of emulsion then, with ethanol or acetone repetitive scrubbing 3～4 times, remove ethanol or acetone, filter precipitation;
3. water, dodecylbenzenesulfonic acid solution washing precipitation are colourless substantially to filtrate successively, 40 ℃ of following vacuum-drying 48h, the polyaniline powder that obtains mixing;
(2) preparation of powder coating:
It is accurate that polyaniline powder synthetic in the step (1) and specific epoxy, solidifying agent, auxiliary agent, color stuffing are pressed the formula rate weighing, stir, again through twin screw extruder extrude 80～90 ℃ of extrusion temperatures, compressing tablet, micro mist are broken, sieve, and namely get the polyaniline powder coating with acid resistance self-repair function.
Advantage of the present invention and positively effect are:
1, powder coating of the present invention contains the coating of a certain amount of polyaniline, under acidic conditions, anodic oxidation reactions takes place, recover surface passivation layer fast, even if corrosive deposit immerses, passivation layer can be as second barrier, also can hinder the generation of corrosion, guaranteed antiseptic property and the self-healing properties of coating, warping resistance, snappiness significantly improve, and have the characteristic of high anticorrosive, scratch resistance ability; This powder coating combines the barrier property of common coating and the selfreparing passive behavior of polyaniline, realize once getting final product thick being coated with, construction is simple, workpiece after having avoided applying is in construction process after the breakage, from the hidden danger of breaking point starting point corrosion, adhesive force of coatings, corrosion resistance have also passed through the GB correlation detection.
2, powder coating of the present invention adopts the oblong link epoxy resins of repeating unit 4～7, the mean polymerisation degree control of contained Resins, epoxy is between 4～9, the epoxy-resin systems that multiple molecular structure is different, collocation is by a certain percentage used, macromole complementary networks structure, form fine and close coating, be equipped with heavy anti-corrosive type o-cresol formaldehyde resin, replace the liquid epoxy that paint adopts and added the polyamine curing system, not only containing more phenyl ring and hydroxyl in the novolac epoxy molecular structure, and long flexible chain is arranged, is to aim at the double antiseptic powder coating design, fabulous intermiscibility is arranged, the reactive behavior height has very strong adhesive power, but fast setting, the cross-linking density height, filming has remarkable rigidity and humidity resistance, chemical-resistant, solvent resistance, anti-cathodic disbonding, levelling property and snappiness, mechanical propertys such as shock resistance.
3, powder coating of the present invention adopts phenolic hydroxyl group long-chain solidifying agent, with the modified imidazole catalytic curing in the hope of reaching quick-setting target; Coatings additive(s) is 788 flow agents, 701B brightening agent, benzoic mixture, is more conducive to form fine and close smooth surface, reduces coating porosity; It is linear resin (the appearance white crystal of end group that solidifying agent adopts glyoxal ethyline, dihydroxyphenyl propane, fusing point ℃ 143.0～146.0, content % 〉=99.5), purpose is for making coating low temperature fast setting and having heavy anti-corrosion function, to improve film flexibility, increase the probability of winding, embedding, the poly-hydroxy structure that the while solidifying agent has has also improved the sticking power to base material.
4, powder coating color stuffing of the present invention is only used for color matching, antiseptic property is not produced critical influence, the different coating color adopts different pigment collocation, pigment variety also changes thereupon, color stuffing adopts one or more in common Rutile type Titanium Dioxide, carbon black, torispherical silicon powder or the process white, cheap and easy to get, also have concurrently and improve coatingsurface hardness, the effect that improves resistance to marring.
5, the polymerization yield rate of the polyaniline that the explained hereafter of synthesized polyaniline obtains among the preparation method of powder coating of the present invention is greater than 80%, the specific conductivity of polyaniline is greater than 1S/cm, and, emulsion polymerization rate of polymerization height, molecular weight of product height, have preferably plurality of advantages such as thermostability and product particle diameter be even, method is simple, easy to operate, save production cost, improved economic benefit of enterprises.
Description of drawings
Fig. 1 damages and self-regeneration figure (Original: the original state of testing plate for floating coat of the present invention; SI: testing plate is through 12% salt solution, 75 ℃ of states that soak after 290 hours; Ov: testing plate is through the state of 80 ℃ of bakings after 72 hours); (low frequency, namely X-coordinate is that-1 o'clock the preservative effect of the more high coating of resistance is more good).
Wherein, Fig. 1-1 is common coating and contains the polyaniline coating initial state; Wherein, Fig. 1-2 is that common coating begins a bit corrosion appearance after 3 days; Fig. 1-3 is that common coating is by thorough corrosion failure after 12 days, and Fig. 1-4 is oven dry after 15 days, and it is good to contain the polyaniline coating self-regeneration, and common coating can't be repaired.
Embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Employed method is ordinary method if no special instructions among the present invention; Employed reagent is conventional reagent if no special instructions among the present invention.
The principle that powder coating of the present invention has the self-regeneration function is:
Electrically conductive polyaniline has excellent environmental stability, higher electroconductibility, polyaniline paint can form oxide compound in the metallic surface, when coatingsurface has cut or cavity, polyaniline can be repaired the chemical aging between metal or the oxide compound, the coating at exposed position still has good preservative effect, and this characteristic has the incomparable advantage of other coating; Under acid (acid rain) environment, the coating that polyaniline arranged exceeds 100 times than the corrosion resistance coating of this component not.Electrically conductive polyaniline has become that industry generally acknowledges one of conducting polymer of application prospect most.
Powder coating of the present invention has certain conductive characteristic, when the coating of metallic surface has when damaged, polyaniline can play a kind of catalytic deactivation effect to this position, under acidic conditions, polyaniline brings out the iron passivation, and the interface of iron and polyaniline can produce an electric field, and the direction of this electric field is opposite with the electronics direction of transfer, hinder the transmission of electronics from metal to oxidizing substance, be equivalent to the barrier action that an electronics transmits; Polyaniline and metal form compound, and current potential is raise, thereby have promoted the reduction of oxygen, make because the dissolving of metal and the electric charge of loss is compensated, the metal current potential is stabilized in passivation region, has reduced the dissolution rate of metal, recover surface passivation layer fast, thus the preservative activity of playing.Conventional coating such as Resins, epoxy or urethane can not form this electric field, thereby do not have self-repair function.
The present invention adopts twin screw to extrude the internally mix technology in application process by mix in the emulsion polymerization process (mixing by Witco 1298 Soft Acid), when having promoted the conductivity of polyaniline, has also increased its intermiscibility.Employing joins polyaniline in the epoxide powder coating, by electrostatic spraying ,-60kV, 140 ℃ are toasted 20min down, and under hot salt condition, the test electrochemical impedance spectroscopy has been studied its Corrosion Protection, and has been made SaltSprayTest.Polyaniline blend coating is handled 1400h under 65 ℃ of hot salt conditions, do not change.Under the situation of artificial damage, this coating shows good self-reparing capability, even under the hot salt condition that continues, base material does not get rusty yet.This is because crosslinked isolating and protecting and the self-repairability of having improved of polyaniline stoped the corrosion of base material, the DSC(dsc) studies confirm that this explanation.
Employed specific epoxy resin adopts the oblong link epoxy resins of repeating unit 4～7 among the present invention, be the different epoxy-resin systems of multiple molecular structure, collocation is by a certain percentage used, macromole complementary networks structure, form fine and close coating, the mean polymerisation degree of contained Resins, epoxy should be controlled between 4～9, for example can for by modified bisphenol A type Resins, epoxy (as the CYD804L of Ba Ling petrochemical industry, dibasic alcohol modified bisphenol A type epoxy), the mixture that bisphenol A-type high molecular solid epoxy (as NPES-907) and o-cresol formaldehyde epoxy resin are formed, its parts by weight are as follows:
280～320 parts of modified bisphenol A type Resins, epoxy;
130～180 parts of bisphenol A-type high molecular solid epoxies;
30～50 parts of o-cresol formaldehyde epoxy resins.
Employed solidifying agent can be 2--phenylimidazole and linear phenolic solidifying agent (appearance white crystal, softening temperature is for 85～95, content % 〉=99.5)), for example 2-phenylimidazole, dihydroxyphenyl propane are the linear resin of end group, such as A-601, the V-205 of Shaanxi gold occasion chemical industry, the Amanda-969A of grand celebration celebrating Shandong chemical industry etc.
A kind of polyaniline powder coating with acid resistance self-repair function, its raw material constitutes component and parts by weight are respectively:
The preparation method's of above-mentioned polyaniline powder coating with acid resistance self-repair function step is as follows:
(1) preparation of polyaniline:
1. emulsion polymerization synthesized polyaniline technology: in reactor, add aniline and dodecylbenzene (ratio of the amount of substance of the two is 2:1), add water successively after mixing, dimethylbenzene (two all is solvent, do not participate in the reaction, get final product in right amount), fully stir, till obtaining transparent emulsion;
2. in transparent emulsion, drip ammonium persulphate (NH then
4)
2S
2O
8The aqueous solution (ammonium persulphate is 1:1 with the ratio of the amount of aniline), the system color slowly deepens, keep 0～20 ℃ of system temperature, continue to stir 30 minutes, after during static storing 24, add the proper amount of acetone breakdown of emulsion then, with adequate amount of ethanol or acetone repetitive scrubbing 3～4 times, remove ethanol or acetone, filter to such an extent that precipitate;
3. water, dodecylbenzenesulfonic acid solution washing precipitation are colourless substantially to filtrate successively, 40 ℃ of following vacuum-drying 48h, the polyaniline powder that obtains mixing; The molecular structural formula of preparation-obtained polyaniline is:
(2) preparation of powder coating:
It is accurate that polyaniline powder synthetic in the step (1) and specific epoxy, solidifying agent, auxiliary agent, color stuffing are pressed the formula rate weighing, pour high speed mixer into, after stirring, dry blending is added to forcing machine, carry out conventional fusion, mixing, cooling, compressing tablet through twin screw extruder 80～90 ℃ of extrusion temperatures again, again through pulverizer pulverizing, classification, sieve, pack, namely become the powder coating final product.
A kind of polyaniline powder coating with acid resistance self-repair function, its raw material constitutes component and parts by weight are respectively:
The preparation method of above-mentioned polyaniline powder coating with acid resistance self-repair function is with embodiment 1.
A kind of polyaniline powder coating with acid resistance self-repair function, its raw material constitutes component and parts by weight are respectively:
The preparation method of above-mentioned polyaniline powder coating with acid resistance self-repair function is with embodiment 1.
A kind of polyaniline powder coating with acid resistance self-repair function, its raw material constitutes component and parts by weight are respectively:
The preparation method of above-mentioned polyaniline powder coating with acid resistance self-repair function is with embodiment 1.
The practical application effect of powder coating of the present invention and test situation:
In acidic medium, there is the carbon steel of polyaniline rete to exceed 100 times than the solidity to corrosion that does not have rete; And in the pH value is 7 medium, there is the carbon steel of polyaniline rete only to exceed 2 times than the solidity to corrosion of going back ortho states; In the seawater of pH value 8.0～9.4, there is not evidence to show that polyaniline has good antiseptic property.This structure that can be interpreted as polyaniline is relevant with the pH value.So experiment conclusion shows that polyaniline coating only just can be put out its excellent antiseptic property to good use in sour environment, and in alkaline environment, mainly also by epoxy coat.
By different application modes and analysis test method (for example, among the ASTM to the examination criteria method of coating; Electrochemical test method is measured open circuit potential, corrosion potential, corrosion current and polarization impedance etc.; Structure and the chemical ingredients of methods analyst such as XPS and SEM matallic surface layer) studied anticorrosion ability and the protection against corrosion mechanism of polyaniline paint to metal (mainly being ferrous metals), The experimental results has proved that the polyaniline compound protective system compares with conventional protective system, and antiseptic property has had significant raising.
The factor that influences polyaniline anticorrosion is a lot, as: surface treatment of the content of oxygen and matrix etc. in polyaniline structure, corrosive environment, coating system and the corrosive medium.Its main application fields comprises: boats and ships, port and pier equipment, ocean containers. warship, amphibious plate armour, chemical industry equipment, high voltage iron tower, weather resistance impregnating material such as transmitting and transforming equipment, railroad bridge.
The various experimental performance parameters of powder coating of the present invention:
(1) functional experiment of self-regeneration:
Polyaniline can the oxidized metal forms fine and close metal oxide layer and stops metal further to corrode in the powder coating of the present invention.This functional materials can also transmit oxidizing medium such as oxygen simultaneously and constantly arrive the metallic surface, the dense coating of formation is constantly increased, up to holding together.Therefore, even coating defectiveness or scuffing, part metals exposes, and where this tight zone is just to developing, up to repairing fully.Therefore, this coating has the function of self-regeneration, asks for an interview Fig. 1 (low frequency, namely X-coordinate is that-1 o'clock the preservative effect of the more high coating of resistance is more good), as can be seen from Figure 1: common coating after 3 days common coating begin a bit that corrosion occurs, it is still fine to contain the polyaniline coating impedance; Common coating is by thorough corrosion failure after 12 days, and it is better to contain polyaniline coating; Oven dry after 15 days, it is good to contain the polyaniline coating self-regeneration, and common coating can't be repaired.
(2) salt soaks experiment: salt soaks experiment and is exactly testing plate inserted in the high temperature salt solution of ventilation and tests, purpose be simulation under operating mode coating to the Metal Protection ability.
The condition that this experiment is used is: will have the coating testing plate to insert in 75 ℃ the salt solution of blowing air, certain hour takes out and measures resistance value at interval.Then, insert again, take out again behind the certain hour and survey.The result shows that coating has excellent antiseptic property, coating none damage in 20 days immersion process (being equivalent to salt-fog test at least 15000 hours).
Claims (10)
1. polyaniline powder coating with acid resistance self-repair function is characterized in that: its raw material constitutes component and parts by weight are respectively:
2. powder coating according to claim 1, it is characterized in that: described specific epoxy resin is the mixture that modified bisphenol A type Resins, epoxy, bisphenol A-type high molecular solid epoxy and o-cresol formaldehyde epoxy resin are formed, modified bisphenol A type Resins, epoxy: bisphenol A-type high molecular solid epoxy: the mass ratio of o-cresol formaldehyde epoxy resin is: 280 ~ 320:130 ~ 180:30 ~ 50.
3. powder coating according to claim 2, it is characterized in that: described modified bisphenol A type Resins, epoxy: bisphenol A-type high molecular solid epoxy: the mass ratio of o-cresol formaldehyde epoxy resin is 300:150:35.
4. powder coating according to claim 1, it is characterized in that: described auxiliary agent is the mixture of flow agent, brightening agent, defoamer, and its parts by weight are as follows:
Flow agent: 16 ~ 22 parts;
Anti-interference agent: 10 ~ 20 parts;
Pore eliminator: 4 ~ 8 parts.
5. powder coating according to claim 1, it is characterized in that: the mass ratio of the mixture of described flow agent, brightening agent, defoamer is 9:7:3.
6. powder coating according to claim 1, it is characterized in that: described polyaniline molecule structural formula is:
7. powder coating according to claim 1, it is characterized in that: described solidifying agent is imidazoles or phenols curing agent.
8. powder coating according to claim 1 is characterized in that: described solidifying agent is for being the linear resin of end group with glyoxal ethyline, dihydroxyphenyl propane.
9. powder coating according to claim 1 is characterized in that: described color stuffing is one or more the mixture in common Rutile type Titanium Dioxide, carbon black, silicon powder or the process white.
10. one kind as each described preparation method with polyaniline powder coating of acid resistance self-repair function of claim 1 to 9, and it is characterized in that: step is as follows:
⑴ the preparation of polyaniline:
1. emulsion polymerization synthesized polyaniline technology: add in reactor by aniline: the ratio of the amount of substance of dodecylbenzene is that the ratio of 2:1 is adding aniline and dodecylbenzene, add water successively after mixing, dimethylbenzene, fully stir, till obtaining transparent emulsion;
2. then in the transparent emulsion in ammonium persulphate: the ratio of the amount of substance of aniline is that the ratio of 1:1 drips ammonium persulphate (NH
4)
2S
2O
8The aqueous solution, the system color slowly deepens, and keeps 0～20 ℃ of system temperature, continues to stir 30 minutes, during static storing 24 after, add the acetone breakdown of emulsion then, with ethanol or acetone repetitive scrubbing 3 ~ 4 times, remove ethanol or acetone, filter precipitation;
3. water, dodecylbenzenesulfonic acid solution washing precipitation are colourless substantially to filtrate successively, 40 ℃ of following vacuum-drying 48h, the polyaniline powder that obtains mixing;
⑵ the preparation of powder coating:
It is accurate that polyaniline powder synthetic among the step ⑴ and specific epoxy, solidifying agent, auxiliary agent, color stuffing are pressed the formula rate weighing, stir, again through twin screw extruder extrude 80 ~ 90 ℃ of extrusion temperatures, compressing tablet, micro mist are broken, sieve, and namely get the polyaniline powder coating with acid resistance self-repair function.
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| CN104893494A (en) * | 2015-05-13 | 2015-09-09 | 国润恒科（天津）防腐工程技术有限公司 | Powder coating used for heavy-duty corrosion-resistant high-bounding stress double-coating thin layer steel bar, heavy-duty corrosion-resistant high-bounding stress double-coating thin layer steel bar, and manufacturing method and applications of heavy-duty corrosion-resistant high-bounding stress double-coating thin layer steel bar |
| CN107141967A (en) * | 2017-06-26 | 2017-09-08 | 浙江工业大学 | A kind of powdery paints of graphene-containing/polyaniline compounded mix and preparation method thereof |
| EP3388462A1 (en) | 2017-04-12 | 2018-10-17 | TIGER Coatings GmbH & Co. KG | Powder coating composition |
| CN109535945A (en) * | 2018-12-21 | 2019-03-29 | 六安科瑞达新型材料有限公司 | A kind of open air salt spray resistance powdery paints |
| CN115584188A (en) * | 2022-12-14 | 2023-01-10 | 佛山市涂亿装饰材料科技有限公司 | Preparation method of powder coating and marbleized powder spraying coating |
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| CN104893494A (en) * | 2015-05-13 | 2015-09-09 | 国润恒科（天津）防腐工程技术有限公司 | Powder coating used for heavy-duty corrosion-resistant high-bounding stress double-coating thin layer steel bar, heavy-duty corrosion-resistant high-bounding stress double-coating thin layer steel bar, and manufacturing method and applications of heavy-duty corrosion-resistant high-bounding stress double-coating thin layer steel bar |
| EP3388462A1 (en) | 2017-04-12 | 2018-10-17 | TIGER Coatings GmbH & Co. KG | Powder coating composition |
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| CN107141967A (en) * | 2017-06-26 | 2017-09-08 | 浙江工业大学 | A kind of powdery paints of graphene-containing/polyaniline compounded mix and preparation method thereof |
| CN109535945A (en) * | 2018-12-21 | 2019-03-29 | 六安科瑞达新型材料有限公司 | A kind of open air salt spray resistance powdery paints |
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| CN115584188A (en) * | 2022-12-14 | 2023-01-10 | 佛山市涂亿装饰材料科技有限公司 | Preparation method of powder coating and marbleized powder spraying coating |
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