CN117844349B - Wear-resistant weather-resistant titanium-containing powder coating capable of increasing hardness of coating and preparation method thereof - Google Patents
Wear-resistant weather-resistant titanium-containing powder coating capable of increasing hardness of coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 84
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 239000000843 powder Substances 0.000 title claims abstract description 66
- 239000010936 titanium Substances 0.000 title claims abstract description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 26
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 22
- 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 22
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 229920001225 polyester resin Polymers 0.000 claims abstract description 15
- 239000004645 polyester resin Substances 0.000 claims abstract description 15
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- 235000019382 gum benzoic Nutrition 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WDNYOQDNYCWKPU-UHFFFAOYSA-N [4-(4-hydroxybenzoyl)oxyphenyl] 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OC(C=C1)=CC=C1OC(=O)C1=CC=C(O)C=C1 WDNYOQDNYCWKPU-UHFFFAOYSA-N 0.000 claims description 7
- 238000005299 abrasion Methods 0.000 claims description 7
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical group NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 6
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 229960004337 hydroquinone Drugs 0.000 claims description 3
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- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000004576 sand Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
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- 230000006750 UV protection Effects 0.000 description 3
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- 238000009830 intercalation Methods 0.000 description 3
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- 230000004224 protection Effects 0.000 description 3
- SJYCSJZAHCXAEH-UHFFFAOYSA-N 2-[4-(2-carboxy-5-hydroxyphenyl)phenyl]-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1C1=CC=C(C=2C(=CC=C(O)C=2)C(O)=O)C=C1 SJYCSJZAHCXAEH-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000005034 decoration Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
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Abstract
The invention discloses a titanium-containing powder coating capable of increasing the hardness, wear resistance and weather resistance of a coating and a preparation method thereof. The wear-resistant weather-resistant titanium-containing powder coating for increasing the hardness of the coating comprises the following components in parts by weight: 70-75 parts of polyester resin, 6-8 parts of epoxy resin E, 6-8 parts of liquid crystal epoxy monomer, 28-32 parts of modified titanium dioxide, 14-16 parts of barium sulfate, 1-2 parts of modified auxiliary agent, 0.5-0.7 part of curing agent, 1-1.3 parts of flatting agent and 0.3-0.5 part of benzoin. The titanium-containing powder coating with increased coating hardness, wear resistance and weather resistance is prepared by partially replacing epoxy resin with liquid crystal epoxy monomer and simultaneously adding epoxy resin modified titanium dioxide and modified auxiliary agent.
Description
Technical Field
The invention belongs to the technical field of powder coating preparation, and particularly relates to a titanium-containing powder coating capable of increasing hardness, wear resistance and weather resistance of a coating and a preparation method thereof.
Background
The powder coating is 100% solid green powder coating formed by melt mixing resin, a curing agent and pigment filler, accords with the principle of '4E' (environmental protection, high efficiency, ecology and economy) of current environmental protection, and is widely applied to the fields of construction, industry, automobile home appliances and the like as a substrate surface coating. Most types of powder coatings still stay on the substrate protection and decoration level, the adhesion of the powder coating to the substrate is poor and the micro-pores inevitably generated during the curing process of the coating lead to local corrosion and reduced mechanical resistance, which greatly limit the application field of the powder coating.
Disclosure of Invention
The invention aims to provide a titanium-containing powder coating with increased hardness, wear resistance and weather resistance and a preparation method thereof, which are used for solving the technical problems of poor hardness, wear resistance and weather resistance of the powder coating in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the technical scheme provided by the invention is as follows:
In a first aspect, the invention provides a titanium-containing powder coating for increasing the hardness, wear resistance and weather resistance of a coating, which comprises the following components in parts by weight: 70-75 parts of polyester resin, 6-8 parts of epoxy resin E, 6-8 parts of liquid crystal epoxy monomer, 28-32 parts of modified titanium dioxide, 14-16 parts of barium sulfate, 1-2 parts of modified auxiliary agent, 0.5-0.7 part of curing agent, 1-1.3 parts of flatting agent and 0.3-0.5 part of benzoin.
Preferably, the polyester resin is a carboxyl polyester resin having an acid value of 30 to 35mg KOH/g; the leveling agent is BYK-368P; the curing agent is adipic dihydrazide.
Preferably, the preparation method of the liquid crystal epoxy monomer comprises the following steps:
a1, dissolving 7-14g of 1, 4-phenylene bis (4-hydroxybenzoate) and 8-16g of undecylenic acid in 160-320mL of dichloromethane, adding 9-18g of N, N' -dicyclohexylcarbodiimide and 0.2-0.4g of 4-dimethylaminopyridine, stirring at normal temperature for 12-36h, then distilling at 165-175 ℃ to remove impurities, and washing the residual organic solution with methanol for 3-5 times to obtain an intermediate;
A2, adding 12-24g of intermediate into 120-240mL of dichloromethane, adding 8-16g of m-chloroperoxybenzoic acid under stirring, refluxing at 40-50 ℃ for 36-60h, cooling to room temperature, washing with 180mL, 5wt% of Na 2SO3 aqueous solution, 180mL, 35wt% of NaHCO 3 aqueous solution and 135mL of saturated NaCl solution in sequence, drying the lower organic layer on MgSO 4 for 12-24h, evaporating at 50-60 ℃ to remove impurities, adding 40-60mL of ethyl acetate for recrystallization, and filtering to obtain the liquid crystal epoxy monomer.
Preferably, the epoxy number EN of the liquid crystalline epoxy monomer is=0.278 mol/100g.
The structural formula of the liquid crystal epoxy monomer is as follows:
Preferably, the preparation method of the 1, 4-phenylene bis (4-hydroxybenzoate) comprises the following steps:
13-26g of 4-hydroxybenzoic acid, 0.8-1.6g of p-toluenesulfonic acid, 22-44g of 1, 4-benzenediol and 12-24mL of toluene are mixed, heated and refluxed for 2-3 hours at 118-126 ℃, and after heat preservation for 0.5-1.5 hours, cooled to room temperature, and alternately washed with saturated saline solution and saturated sodium carbonate solution until the lower organic layer is neutral, thus obtaining 1, 4-phenylenebis (4-hydroxybenzoate).
Preferably, the preparation method of the modifying auxiliary agent comprises the following steps:
S1, adding 10-20g of Ti 3AlC2 powder into 60-120mL of 5wt% hydrofluoric acid aqueous solution, etching for 20-28h, centrifugally washing with water for 5-7 times under the conditions of rotating speed of 3000-4000rpm and time of 3-7min, vacuum filtering with a nylon filter membrane with pore diameter of 0.22 mu m, re-washing with water for 1-3 times, and finally drying at 75-85 ℃ for 12-18h to obtain Ti 3C2 -MXene powder;
S2, adding 5-10g of Ti 3C2 -MXene powder into 200-400mL of 25wt% tetramethyl ammonium hydroxide aqueous solution, stirring at room temperature for 20-28h, centrifuging at 3000-4000rpm for 3-7min, washing with water for 5-7 times, and finally vacuum drying at 115-125 ℃ for 12-36h to obtain intercalated MXene powder;
s3, adding 23-46g of oxidant ammonium persulfate into 200-400mL of 3.6wt% HCl solution to obtain oxidant mixed solution;
S4, adding 3-6g of montmorillonite into 300-600g of water, soaking for 12-20h at room temperature, then adding 19-38g of aniline and 13-26g of intercalated MXene powder, stirring for 30-60min, then dropwise adding the oxidant mixed solution obtained by S3 at 0-5 ℃, stirring for 12-36h, centrifuging, washing, and vacuum drying for 12-36h at 55-65 ℃ to obtain the modified auxiliary agent.
Preferably, the preparation method of the modified titanium dioxide comprises the following steps:
Mixing 40-60g of titanium dioxide and 450-650g of epoxy resin, stirring for 10-15min, and grinding with sand in an oil bath at 110-130 ℃ at 1700-2300rpm for 2-4h to obtain treated titanium dioxide; adding the treated titanium dioxide into 200-300mL of mixed solution of dimethylbenzene and n-butanol with the mass ratio of 7:3, centrifuging for 4-6 times, and finally drying for 10-14h at 25-35 ℃ to obtain the modified titanium dioxide.
In the above process, the epoxy resin molecules are grafted onto the surface of TiO 2 by using a high-temperature mechanical force modification method.
In a second aspect, the invention also provides a preparation method of the titanium-containing powder coating for increasing the hardness, wear resistance and weather resistance of the coating, which comprises the following steps:
70-75 parts of polyester resin, 6-8 parts of epoxy resin E12,6-8 parts of liquid crystal epoxy monomer, 28-32 parts of modified titanium dioxide, 14-16 parts of barium sulfate, 1-2 parts of modified auxiliary agent, 0.5-0.7 part of curing agent, 1-1.3 parts of leveling agent and 0.3-0.5 part of benzoin are uniformly mixed, melted, extruded, tabletted and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the coating hardness-increasing wear-resistant weather-resistant titanium-containing powder coating.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. according to the invention, the liquid crystal epoxy monomer is used for replacing part of E12 epoxy resin, the modification auxiliary agent is added to increase the crosslinking degree of the powder coating, the epoxy resin is used for modifying silicon dioxide to improve the compatibility with the coating, the defects of coating pores and coating are reduced cooperatively, the epoxy modified titanium dioxide and the liquid crystal epoxy monomer improve the hydrophobicity and ultraviolet resistance of the powder coating, and the epoxy modified titanium dioxide and the liquid crystal epoxy monomer are matched cooperatively with barium sulfate, a flatting agent and benzoin to increase the wear resistance, the hardness, the adhesive force and the weather resistance of the powder coating, so that the powder coating has good scratch resistance effect and corrosion resistance, and has good application prospect.
2. The liquid crystal epoxy monomer contains a rigid epoxy group for crosslinking reaction, can form more crosslinking bonds after the powder coating is cured, forms a polymer crosslinking network, and enhances the wear resistance and the hardness; the liquid crystal epoxy monomer enhances the compatibility with polyester resin through ester groups, and meanwhile, the aliphatic section in the liquid crystal epoxy monomer increases the fluidity and the hydrophobicity of the powder coating.
3. The oxygen group of the intercalation MXene and the N-H group of the polyaniline molecule form a hydrogen bond, so that aniline is polymerized on the surface of the intercalation MXene in situ, and montmorillonite is deposited on the surface of the intercalation MXene; modified MXene improves dispersibility and exposes additional active sites, and interaction between the surface functional groups and carboxyl-terminated polyester constrains movement of molecular chains to slight deformation, forming a highly crosslinked rigid structure; the modified auxiliary agent eliminates the defects of the pores and the coating of the coating, and improves the wear resistance and the hardness of the powder coating; the polyaniline modified MXene and montmorillonite have a synergistic barrier effect, remarkably block the diffusion of corrosive media, and enhance the corrosion resistance of the powder coating.
4. In the invention, the epoxy resin and the titanium dioxide are bonded in a mode of combining mechanical energy and heat energy, so that the compatibility with the powder coating is enhanced, the coating defect is reduced, the corrosion resistance is improved, and meanwhile, the hydrophobicity of the titanium dioxide is improved by the epoxy resin; the evenly distributed modified titanium dioxide enhances the adhesive force and mechanical property between the coating and the interface of the substrate, and simultaneously utilizes the ultraviolet resistance of the titanium dioxide to improve the ultraviolet resistance of the coating.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a process for preparing the titanium-containing powder coating with increased hardness, abrasion resistance and weather resistance of the coating;
FIG. 2 is a graph of the hardness line of the titanium-containing powder coating of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment discloses a preparation method of a liquid crystal epoxy monomer, which comprises the following steps:
A1, dissolving 10.5g of 1, 4-phenylene bis (4-hydroxybenzoate) and 12g of undecylenic acid in 240mL of dichloromethane, adding 13.5g of N, N' -dicyclohexylcarbodiimide and 0.3g of 4-dimethylaminopyridine, stirring at normal temperature for 24 hours, then distilling at 170 ℃ to remove impurities, and washing the residual organic solution with methanol for 4 times to obtain an intermediate;
A2, adding 18g of intermediate into 180mL of dichloromethane, adding 12g of m-chloroperoxybenzoic acid under stirring, refluxing at 45 ℃ for 48h, cooling to room temperature, washing with 180mL of 5wt% of Na 2SO3 aqueous solution, 180mL of 35wt% of NaHCO 3 aqueous solution and 135mL of saturated NaCl solution in sequence, drying the lower organic layer on MgSO 4 for 12-24h, evaporating at 50-60 ℃ to remove impurities, adding 40-60mL of ethyl acetate, recrystallizing, and filtering to obtain the liquid crystal epoxy monomer.
The preparation method of the 1, 4-phenylene bis (4-hydroxybenzoate) comprises the following steps:
19.5g of 4-hydroxybenzoic acid, 1.2g of p-toluenesulfonic acid, 334g of 1, 4-benzenediol and 18mL of toluene were mixed, heated under reflux at 122℃for 2.5 hours, incubated for 1 hour, cooled to room temperature, and alternately washed with saturated brine and saturated sodium carbonate solution until the lower organic layer was neutral to give 1, 4-phenylenebis (4-hydroxybenzoate).
Example 2
The embodiment discloses a preparation method of a modification auxiliary agent, which comprises the following steps:
S1, adding 15g of Ti 3AlC2 powder into 90mL of 5wt% hydrofluoric acid aqueous solution, etching for 24 hours, centrifugally washing with water for 6 times under the conditions of 3500rpm and 5min, vacuum filtering with a nylon filter membrane with the pore diameter of 0.22 mu m, washing with water for 2 times again, and finally drying at 80 ℃ for 16 hours to obtain Ti 3C2 -MXene powder;
S2, adding 7.5g of Ti 3C2 -MXene powder into 300mL of 25wt% tetramethyl ammonium hydroxide aqueous solution, stirring at room temperature for 24h, centrifuging at 3500rpm for 5min, washing with water for 6 times, and finally drying at 120 ℃ in vacuum for 24h to obtain intercalated MXene powder;
S3, adding 34.5g of oxidant ammonium persulfate into 300mL of 3.6wt% HCl solution to obtain oxidant mixed solution;
S4, adding 4.5g of montmorillonite into 450g of water, soaking for 16 hours at room temperature, then adding 28.5g of aniline and 19.5g of intercalated MXene powder, stirring for 45 minutes, then dropwise adding the oxidant mixed solution obtained in S3 at 2 ℃, stirring for 24 hours, centrifuging, washing, and vacuum drying for 24 hours at 60 ℃ to obtain the modified auxiliary agent.
Example 3
The embodiment discloses a preparation method of modified titanium dioxide, which comprises the following steps:
Mixing 50g of titanium dioxide and 550g of epoxy resin, stirring for 12min, and grinding with sand in an oil bath at 120 ℃ at a rotating speed of 2000rpm for 3h to obtain treated titanium dioxide; adding the treated titanium dioxide into 250mL of mixed solution of dimethylbenzene and n-butanol with the mass ratio of 7:3, centrifuging for 5 times, and finally drying at 30 ℃ for 10-14h to obtain the modified titanium dioxide.
Example 4
Referring to fig. 1, this embodiment discloses a method for preparing titanium-containing powder coating with increased hardness, wear resistance and weather resistance, which comprises the following steps:
72g of polyester resin, 7g of epoxy resin E12,7g of liquid crystal epoxy monomer, 30g of modified titanium dioxide, 15g of barium sulfate, 1.5g of modified auxiliary agent, 0.6g of curing agent adipic dihydrazide, 1.2g of flatting agent BYK-365P and 0.4g of benzoin are uniformly mixed, melted, extruded, pressed into tablets and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the wear-resistant weather-resistant titanium-containing powder coating with increased coating hardness.
Example 5
Referring to fig. 1, this embodiment discloses a method for preparing titanium-containing powder coating with increased hardness, wear resistance and weather resistance, which comprises the following steps:
70g of polyester resin, 8g of epoxy resin E12,6g of liquid crystal epoxy monomer, 32g of modified titanium dioxide, 14g of barium sulfate, 2g of modified auxiliary agent, 0.5g of curing agent adipic dihydrazide, 1.3g of flatting agent BYK-365P and 0.3g of benzoin are uniformly mixed, melted, extruded, pressed into tablets and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the wear-resistant weather-resistant titanium-containing powder coating with increased coating hardness.
Example 6
Referring to fig. 1, this embodiment discloses a method for preparing titanium-containing powder coating with increased hardness, wear resistance and weather resistance, which comprises the following steps:
75g of polyester resin, 6g of epoxy resin E12,8g of liquid crystal epoxy monomer, 28g of modified titanium dioxide, 16g of barium sulfate, 1g of modified auxiliary agent, 0.7g of curing agent adipic dihydrazide, 1g of flatting agent BYK-365P and 0.5g of benzoin are uniformly mixed, melted, extruded, tabletted and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the titanium-containing powder coating with increased coating hardness, wear resistance and weather resistance.
Example 7
Referring to fig. 1, this embodiment discloses a method for preparing titanium-containing powder coating with increased hardness, wear resistance and weather resistance, which comprises the following steps:
70g of polyester resin, 6g of epoxy resin E12,8g of liquid crystal epoxy monomer, 32g of modified titanium dioxide, 15g of barium sulfate, 1.5g of modified auxiliary agent, 0.7g of curing agent adipic dihydrazide, 1.3g of flatting agent BYK-365P and 0.3g of benzoin are uniformly mixed, melted, extruded, pressed into tablets and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the wear-resistant weather-resistant titanium-containing powder coating with increased coating hardness.
Example 8
Referring to fig. 1, this embodiment discloses a method for preparing titanium-containing powder coating with increased hardness, wear resistance and weather resistance, which comprises the following steps:
75g of polyester resin, 8g of epoxy resin E12,7g of liquid crystal epoxy monomer, 30g of modified titanium dioxide, 14g of barium sulfate, 2g of modified auxiliary agent, 0.5g of curing agent adipic dihydrazide, 1g of flatting agent BYK-365P and 0.4g of benzoin are uniformly mixed, melted, extruded, tabletted and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the titanium-containing powder coating with increased coating hardness, wear resistance and weather resistance.
Comparative example 1
Comparative example 1 in comparison with example 4, in comparative example 1, no liquid crystal epoxy monomer was added during the preparation of the coating hardness-increasing abrasion-resistant weather-resistant titanium-containing powder coating, and other conditions were unchanged.
Comparative example 2
Comparative example 2 in comparison with example 4, comparative example 2 was prepared without adding modified titanium dioxide during the preparation of the coating hardness-increasing abrasion-resistant weather-resistant titanium-containing powder coating, and the other conditions were unchanged.
Comparative example 3
Comparative example 3 in comparison with example 4, comparative example 3 was prepared without adding a modifying auxiliary agent during the preparation of the coating hardness-increasing abrasion-resistant weather-resistant titanium-containing powder coating, and the other conditions were unchanged.
Experimental example
The titanium-containing powder coatings with increased hardness, wear resistance and weather resistance prepared in examples 4-8 and comparative examples 1-3 were sprayed and cured on steel plates of the same type (the curing conditions were uniformly selected to be 170 ℃ C. @20 min) to obtain cured coatings, respectively, and the coatings were subjected to performance tests: test reference standards and test results are shown in table 1:
TABLE 1
As can be seen from the test results in Table 1, the titanium-containing powder coatings with increased hardness, abrasion resistance and weather resistance prepared in examples 4 to 8 of the present invention have good mechanical properties and weather resistance. As can be seen from comparison of comparative example 1 and examples 4-8, the titanium-containing powder coating prepared by adding the liquid crystal epoxy monomer has good mechanical properties and weather resistance; as is clear from comparison of comparative example 2 and examples 4 to 8, the titanium-containing powder coating material prepared by adding the modified titanium dioxide has good mechanical properties and weather resistance; as is evident from the comparison of comparative example 3 and examples 4-8, the titanium-containing powder coating prepared by adding the modifying auxiliary agent has good mechanical properties and weather resistance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (4)
1. The wear-resistant and weather-resistant titanium-containing powder coating for increasing the hardness of the coating is characterized by comprising the following components in parts by weight: 70-75 parts of polyester resin, 6-8 parts of epoxy resin E, 6-8 parts of liquid crystal epoxy monomer, 28-32 parts of modified titanium dioxide, 14-16 parts of barium sulfate, 1-2 parts of modified auxiliary agent, 0.5-0.7 part of curing agent, 1-1.3 parts of flatting agent and 0.3-0.5 part of benzoin;
the polyester resin is carboxyl polyester resin with an acid value of 30-35mg KOH/g;
the preparation method of the liquid crystal epoxy monomer comprises the following steps:
a1, dissolving 7-14g of 1, 4-phenylene bis (4-hydroxybenzoate) and 8-16g of undecylenic acid in 160-320mL of dichloromethane, adding 9-18g of N, N' -dicyclohexylcarbodiimide and 0.2-0.4g of 4-dimethylaminopyridine, stirring at normal temperature for 12-36h, then distilling at 165-175 ℃ to remove impurities, and washing the residual organic solution with methanol for 3-5 times to obtain an intermediate;
A2, adding 12-24g of intermediate into 120-240mL of dichloromethane, adding 8-16g of m-chloroperoxybenzoic acid under stirring, refluxing at 40-50 ℃ for 36-60h, cooling to room temperature, washing with 180mL, 5wt% of Na 2SO3 aqueous solution, 180mL, 35wt% of NaHCO 3 aqueous solution and 135mL of saturated NaCl solution in sequence, drying the lower organic layer on MgSO 4 for 12-24h, evaporating at 50-60 ℃ to remove impurities, adding 40-60mL of ethyl acetate for recrystallization, and filtering to obtain a liquid crystal epoxy monomer;
the preparation method of the 1, 4-phenylene bis (4-hydroxybenzoate) comprises the following steps:
13-26g of 4-hydroxybenzoic acid, 0.8-1.6g of p-toluenesulfonic acid, 22-44g of 1, 4-benzenediol and 12-24mL of toluene are mixed, heated and refluxed for 2-3 hours at 118-126 ℃, and after heat preservation for 0.5-1.5 hours, cooled to room temperature, and alternately washed with saturated saline solution and saturated sodium carbonate solution until the lower organic layer is neutral, thus obtaining 1, 4-phenylene bis (4-hydroxybenzoate);
The preparation method of the modified auxiliary agent comprises the following steps:
S1, adding 10-20g of Ti 3AlC2 powder into 60-120mL of 5wt% hydrofluoric acid aqueous solution, etching for 20-28h, centrifugally washing with water for 5-7 times under the conditions of rotating speed of 3000-4000rpm and time of 3-7min, vacuum filtering with a nylon filter membrane with pore diameter of 0.22 mu m, re-washing with water for 1-3 times, and finally drying at 75-85 ℃ for 12-18h to obtain Ti 3C2 -MXene powder;
S2, adding 5-10g of Ti 3C2 -MXene powder into 200-400mL of 25wt% tetramethyl ammonium hydroxide aqueous solution, stirring at room temperature for 20-28h, centrifuging at 3000-4000rpm for 3-7min, washing with water for 5-7 times, and finally vacuum drying at 115-125 ℃ for 12-36h to obtain intercalated MXene powder;
s3, adding 23-46g of oxidant ammonium persulfate into 200-400mL of 3.6wt% HCl solution to obtain oxidant mixed solution;
S4, adding 3-6g of montmorillonite into 300-600g of water, soaking for 12-20h at room temperature, then adding 19-38g of aniline and 13-26g of intercalated MXene powder, stirring for 30-60min, then dropwise adding the oxidant mixed solution obtained by S3 at 0-5 ℃, stirring for 12-36h, centrifuging, washing, and vacuum drying for 12-36h at 55-65 ℃ to obtain a modified auxiliary agent;
The preparation method of the modified titanium dioxide comprises the following steps:
Mixing 40-60g of titanium dioxide and 450-650g of epoxy resin, stirring for 10-15min, and grinding with sand in an oil bath at 110-130 ℃ at 1700-2300rpm for 2-4h to obtain treated titanium dioxide; adding the treated titanium dioxide into 200-300mL of mixed solution of dimethylbenzene and n-butanol with the mass ratio of 7:3, centrifuging for 4-6 times, and finally drying for 10-14h at 25-35 ℃ to obtain the modified titanium dioxide.
2. The titanium-containing powder coating with increased hardness, abrasion resistance and weather resistance according to claim 1, wherein the leveling agent is BYK-368P; the curing agent is adipic dihydrazide.
3. The titanium-containing powder coating of claim 1, wherein the liquid crystalline epoxy monomer has an epoxy number en=0.278 mol/100g.
4. A method of preparing a titanium-containing powder coating of increased hardness, abrasion resistance and weatherability of the coating according to any one of claims 1 to 3, comprising the steps of:
70-75 parts of polyester resin, 6-8 parts of epoxy resin E12,6-8 parts of liquid crystal epoxy monomer, 28-32 parts of modified titanium dioxide, 14-16 parts of barium sulfate, 1-2 parts of modified auxiliary agent, 0.5-0.7 part of curing agent, 1-1.3 parts of leveling agent and 0.3-0.5 part of benzoin are uniformly mixed, melted, extruded, tabletted and cooled, and then coarse crushing, fine grinding and sieving are sequentially carried out to obtain the coating hardness-increasing wear-resistant weather-resistant titanium-containing powder coating.
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| KR20100067973A (en) * | 2008-12-12 | 2010-06-22 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
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| CN110669529A (en) * | 2019-09-10 | 2020-01-10 | 苏州大学 | Color liquid crystal material and application thereof |
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| CN1939951A (en) * | 2006-09-01 | 2007-04-04 | 新乡市瑞丰化工有限责任公司 | Production of aryl-alkyl-substituted hydroxy-benzoic acid resin multivalent metal salt |
| KR20100067973A (en) * | 2008-12-12 | 2010-06-22 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| CN109796584A (en) * | 2018-12-26 | 2019-05-24 | 万华化学集团股份有限公司 | A kind of preparation system and preparation method of aromatic series thermotropic liquid crystal polymer |
| CN110669529A (en) * | 2019-09-10 | 2020-01-10 | 苏州大学 | Color liquid crystal material and application thereof |
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