A polymer self-cleaning coating spraying material and its preparation process

Abstract

The raw materials for preparing a polymer self-cleaning coating spraying material include: silica, tetraethyl orthosilicate, hexadecyltrimethylsilane, polytetrafluoroethylene, aluminum tripolyphosphate, sodium silicate, modified MOF, and modified polysulfamide. The beneficial effects of this invention are: the self-cleaning coating prepared by this invention exhibits excellent performance in mesh testing, impact resistance testing, abrasion resistance testing, and cleanliness. In particular, after temperature rise treatment from -30℃ to 40℃, the performance of the self-cleaning coating prepared by this invention does not change significantly. The modified MOF and modified polysulfamide added in this invention ensure the coating's self-cleaning ability, flexibility, and adhesion.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating, in particular to a high-molecular self-cleaning coating spraying material and preparation process. BACKGROUND

[0002] Self-cleaning coating is a special surface coating, and the outer silica gel layer can improve the surface properties through nano-level structure and chemical composition, form a force field that interacts with pollutants, and keep the surface clean. Self-cleaning coating has wide application in the fields of building, automobile, home, etc., can maintain the aesthetics and durability of buildings, reduce cleaning cost and time cost, and improve the quality of life and reduce cleaning cost.

[0003] In terms of organic high-molecular materials, commonly used are polyacrylate, polyvinyl alcohol, polyfluoroethylene, etc. These high-molecular materials have good flexibility and adhesion, and can be well combined with various substrates. Among them, polyacrylate and polyvinyl alcohol have good self-cleaning effect, but poor weather resistance and stability, and are prone to aging. Polyfluoroethylene has good weather resistance and stability, but has high preparation cost and certain pollution to the environment. SUMMARY

[0004] The present application solves the above problems and invents a high-molecular self-cleaning coating spraying material and preparation process.

[0005] A high-molecular self-cleaning coating spraying material, the preparation raw materials of the self-cleaning coating include: silicon dioxide, tetraethyl orthosilicate, hexadecyl trimethyl silane, polytetrafluoroethylene, aluminum tripolyphosphate and sodium silicate, modified MOF, and modified polysulfamide.

[0006] Preferably, the preparation raw materials and components of the self-cleaning coating include: 10-20 parts of silicon dioxide, 5-15 parts of tetraethyl orthosilicate, 5-15 parts of hexadecyl trimethyl silane, 5-15 parts of polytetrafluoroethylene (concentration of 10-30%), 2-8 parts of aluminum tripolyphosphate and 3-10 parts of sodium silicate, 3-10 parts of modified MOF, and 2-8 parts of modified polysulfamide.

[0007] Preferably, the raw materials and components of the modified MOF include:

[0008]

[0009] Preferably, the preparation steps of the modified MOF include:

[0010] A1: weigh appropriate amounts of N,N-dimethylformamide DMF, formic acid, trimesic acid, ZrOCl2.8H2O, tert-butyl cumyl peroxide, and chitin;

[0011] A2: Put DMF, formic acid and trimesic acid into the reaction kettle, and put trimesic acid, set condition 1, form solution 1;

[0012] A3: Add ZrOCl2.8H2O, aluminum triphosphate, tert-butyl cumyl peroxide and aluminum triphosphate, set condition 2, form modified MOF.

[0013] Preferably, the condition 1 is that the temperature is 30-80°C, and the mixture is uniform; the condition 2 is that the temperature is 60-100°C, and the time is 1-20h.

[0014] Preferably, the raw materials and components of the modified polysulfamide include

[0015]

[0016] Preferably, the preparation steps of the modified polysulfamide include:

[0017] B1: Take appropriate amount of sulfur, 1,6-hexanediamine, N,N-dimethylformamide, p-phenylenediacetic acid, dimethyl sulfoxide and carbon fiber

[0018] B2: Put sulfuric acid, 1,6-hexanediamine, 1,4-p-phenylenediacetic acid and 1 / 2 into the reaction kettle, and add dimethyl sulfoxide, set condition 3, get intermediate product 1;

[0019] B3: Add 1 / 2 carbon fiber and N,N-dimethylformamide, set condition 4, and put in methanol to get modified polysulfamide.

[0020] Preferably, the condition 3 is a nitrogen protection environment, the temperature is 60-120°C, the reaction time is 1-20h, and the stirring speed is 10-30r / min; the condition 4 is 60-120°C, and the reaction time is 1-5h.

[0021] A preparation process of a high-molecular self-cleaning coating spraying material, the steps of the preparation process include:

[0022] Preparation of modified MOF:

[0023] C1: Take appropriate amount of N,N-dimethylformamide DMF, formic acid, trimesic acid H3BTC, ZrOCl2.8H2O, tert-butyl cumyl peroxide and chitin;

[0024] C2: Put DMF, formic acid and trimesic acid into the reaction kettle, and put trimesic acid, the temperature is 30-80°C, mix well, form solution 1;

[0025] C3: adding ZrOCl2.8H2O, aluminum tripolyphosphate, t-butyl peroxide isopropyl benzene and chitin, the temperature is 60-100 DEG C, the treatment time is 1-20h, forming modified MOF;

[0026] Preparation of modified polysulfur amide:

[0027] C1: weighing appropriate amount of sulfur, 1, 6-hexanediamine, N, N-dimethylamide, p-phenylenediacetic acid, dimethyl sulfoxide and carbon fiber;

[0028] C2: sulfuric acid, 1, 6-hexanediamine, 1, 4-p-phenylenediacetic acid and 1 / 2 carbon fiber are put into the reaction kettle, dimethyl sulfoxide is added, the temperature is 60-120 DEG C, the reaction is 1-20h, and the intermediate product 1 is obtained by stirring at a speed of 10-30r / min;

[0029] C3: adding 1 / 2 carbon fiber and N, N-dimethylformamide, the temperature is 60-120 DEG C, the reaction is 1-5h, and methanol is put in to obtain modified polysulfur amide.

[0030] Preparation of self-cleaning coating spraying material:

[0031] C1: weighing appropriate amount of modified MOP, modified polysulfur amide, silicon dioxide, tetraethyl orthosilicate, hexadecyl trimethyl silane, polytetrafluoroethylene, aluminum tripolyphosphate, sodium silicate and ethanol.

[0032] C2: tetraethyl orthosilicate, silicon dioxide, modified polysulfur amide, ethanol and hexadecyl trimethoxysilane are put into the reaction kettle, the temperature is 60-120 DEG C, and the intermediate product 1 is obtained;

[0033] C3: polytetrafluoroethylene solution (mass fraction is 40-70%), intermediate product 1, aluminum tripolyphosphate (mass fraction is 10-40%), modified MOF and sodium silicate are put into the high-speed dispersion machine, the rotating speed of the high-temperature dispersion machine is 500-1500r / min, the temperature is 60-80 DEG C, the treatment time is 5-20min, and the self-cleaning coating spraying material is obtained.

[0034] The beneficial effects of the application are:

[0035] The self-cleaning coating prepared by the application has excellent performance in the aspects of grid experiment, impact resistance test, wear resistance test and cleanliness, especially after the temperature rise treatment from-30 DEG C to 40 DEG C, the performance of the self-cleaning coating prepared by the application changes little, and the modified MOF and the modified polysulfur amide added in the application can ensure the self-cleaning ability, flexibility and adhesion of the coating. Specific implementation

[0036] Example 1

[0037] First step, preparation of modified MOF:

[0038] C1: take appropriate amount of N, N-dimethylformamide 10 parts, formic acid 10 parts, benzene-1, 3, 5-tricarboxylic acid H3BTC 5 parts, ZrOCl2.8H2O 3 parts, tert-butyl cumene peroxide 1 part and chitin 2 parts, aluminum triphosphate 1 part;

[0039] C2: put DMF, formic acid and benzene-1, 3, 5-tricarboxylic acid into the reaction kettle, and put benzene-1, 3, 5-tricarboxylic acid, the temperature is 30°C, mix evenly, form solution 1;

[0040] C3: add ZrOCl2.8H2O, aluminum triphosphate, tert-butyl cumene peroxide and chitin, the temperature is 60°C, the treatment time is 1h, form modified MOF;

[0041] Second step, preparation of modified polysulfamide:

[0042] C1: take appropriate amount of sulfur 1 part, N, N-dimethylamide 5 parts, 1, 6-hexanediamine 2 parts, p-phenylenediacetic acid 10 parts, dimethyl sulfoxide 3 parts and carbon fiber 0.1 part;

[0043] C2: put sulfuric acid, 1, 6-hexanediamine, 1, 4-p-phenylenediacetic acid and 1 / 2 carbon fiber into the reaction kettle, and add dimethyl sulfoxide, the temperature is 60°C, react for 1h, and stir at a speed of 10r / min to obtain intermediate product 1;

[0044] C3: add 1 / 2 carbon fiber and N, N-dimethylformamide, the temperature is 60°C, react for 1h, and put in methanol to obtain modified polysulfamide.

[0045] Third step, preparation of self-cleaning coating spraying material:

[0046] C1: 10 parts of silicon dioxide, 5 parts of tetraethyl orthosilicate, 5 parts of hexadecyl trimethyl silane, 5 parts of polytetrafluoroethylene (concentration of 10%), 2 parts of aluminum tripolyphosphate and 3 parts of sodium silicate, 3 parts of modified MOF, 2 parts of modified polysulfamide, 10 parts of ethanol (mass fraction of 40%).

[0047] C2: put tetraethyl orthosilicate, silicon dioxide, modified polysulfamide, ethanol and hexadecyl trimethoxysilane into the reaction kettle, the temperature is 60°C, to obtain intermediate product 1;

[0048] C3: put polytetrafluoroethylene solution (mass fraction of 40%), intermediate product 1, aluminum tripolyphosphate (mass fraction of 10%), modified MOF and sodium silicate into the high-speed disperser, the speed of high-temperature disperser is 500r / min, the temperature is 60°C, the treatment time is 5min, to obtain self-cleaning coating spraying material.

[0049] Example 2:

[0050] First step, preparation of modified MOF:

[0051] C1: take appropriate amount of N, N-dimethylformamide 30 parts, formic acid 30 parts, trimesic acid H3BTC 15 parts, ZrOCl2.8H2O 10 parts, tert-butyl cumene peroxide 3 parts and chitin 5 parts, aluminum triphosphate 3 parts;

[0052] C2: put DMF, formic acid and trimesic acid into the reaction kettle, and put trimesic acid, the temperature is 80°C, mix evenly, form solution 1;

[0053] C3: add ZrOCl2.8H2O, aluminum triphosphate, tert-butyl cumene peroxide and chitin, the temperature is 100°C, the treatment time is 20h, form modified MOF;

[0054] Second step, preparation of modified polysulfamide:

[0055] C1: take appropriate amount of sulfur 2 parts, N, N-dimethylamide 10 parts, 1, 6-hexanediamine 5 parts, p-phenylenediacetic acid 20 parts, dimethyl sulfoxide 5 parts and carbon fiber 0.5 parts;

[0056] C2: put sulfuric acid, 1, 6-hexanediamine, 1, 4-p-phenylenediacetic acid and 1 / 2 carbon fiber into the reaction kettle, and add dimethyl sulfoxide, the temperature is 120°C, react for 20h, and stir at a speed of 30r / min to obtain intermediate product 1;

[0057] C3: add 1 / 2 carbon fiber and N, N-dimethylformamide, the temperature is 120°C, react for 5h, and put in methanol to obtain modified polysulfamide.

[0058] Third step, preparation of self-cleaning coating spraying material:

[0059] C1: 20 parts of silicon dioxide, 15 parts of tetraethyl orthosilicate, 15 parts of hexadecyl trimethyl silane, 15 parts of polytetrafluoroethylene (concentration of 30%), 8 parts of aluminum tripolyphosphate and 10 parts of sodium silicate, 10 parts of modified MOF, 8 parts of modified polysulfamide, 20 parts of ethanol (mass fraction of 60%).

[0060] C2: put tetraethyl orthosilicate, silicon dioxide, modified polysulfamide, ethanol and hexadecyl trimethoxysilane into the reaction kettle, the temperature is 120°C, obtain intermediate product 1;

[0061] C3: Put the polytetrafluoroethylene solution (mass fraction 70%), intermediate product 1, aluminum triphosphate (mass fraction 40%), modified MOF and sodium silicate into a high-speed disperser, the rotating speed of the high-temperature disperser is 1500 r / min, the temperature is 80°C, and the processing time is 20 min to obtain a self-cleaning coating spraying material.

[0062] Example 3:

[0063] First step, preparation of modified MOF:

[0064] C1: Take appropriate amounts of N,N-dimethylformamide 20 parts, formic acid 20 parts, benzene-1,3,5-tricarboxylic acid H3BTC 10 parts, ZrOCl2.8H2O 8 parts, tert-butyl cumene peroxide 2 parts and chitin 4 parts, aluminum triphosphate 2 parts;

[0065] C2: Put DMF, formic acid and benzene-1,3,5-tricarboxylic acid into a reaction kettle, and put benzene-1,3,5-tricarboxylic acid, the temperature is 60°C, mix well to form solution 1;

[0066] C3: Add ZrOCl2.8H2O, aluminum triphosphate, tert-butyl cumene peroxide and chitin, the temperature is 80°C, and the processing time is 10 h to form a modified MOF;

[0067] Second step, preparation of modified polysulfamide:

[0068] C1: Take appropriate amounts of sulfur 1.2 parts, N,N-dimethylamide 8 parts, 1,6-hexanediamine 4 parts, p-phenylenediacetic acid 15 parts, dimethyl sulfoxide 4 parts and carbon fiber 0.4 parts;

[0069] C2: Put sulfuric acid, 1,6-hexanediamine, 1,4-p-phenylenediacetic acid and 1 / 2 carbon fiber into a reaction kettle, and add dimethyl sulfoxide, the temperature is 100°C, react for 10 h, and stir at a speed of 25 r / min to obtain intermediate product 1;

[0070] C3: Add 1 / 2 carbon fiber and N,N-dimethylformamide, the temperature is 80°C, react for 2 h, and put in methanol to obtain a modified polysulfamide.

[0071] Third step, preparation of self-cleaning coating spraying material:

[0072] C1: 13 parts of silicon dioxide, 11 parts of tetraethyl orthosilicate, 12 parts of hexadecyltrimethylsilane, 8 parts of polytetrafluoroethylene (concentration 20%), 6 parts of aluminum tripolyphosphate and 7 parts of sodium silicate, 7 parts of modified MOF, 5 parts of modified polysulfamide, 12 parts of ethanol (mass fraction 50%).

[0073] C2: Put tetraethyl orthosilicate, silicon dioxide, modified polysulfamide, ethanol and hexadecyl trimethoxysilane into the reaction kettle, the temperature is 100°C, and the intermediate product 1 is obtained;

[0074] C3: Put polytetrafluoroethylene solution (mass fraction 60%), intermediate product 1, aluminum triphosphate (mass fraction 30%), modified MOF and sodium silicate into the high-speed disperser, the speed of the high-temperature disperser is 1200r / min, the temperature is 70°C, the processing time is 12min, and the self-cleaning coating spraying material is obtained.

[0075] Comparative example 1:

[0076] First step, preparation of modified MOF:

[0077] C1: Take appropriate amount of N,N-dimethylformamide 20 parts, formic acid 20 parts, benzene-1,3,5-tricarboxylic acid H3BTC 10 parts, ZrOCl2.8H2O 8 parts;

[0078] C2: Put DMF, formic acid and benzene-1,3,5-tricarboxylic acid into the reaction kettle, and put benzene-1,3,5-tricarboxylic acid, the temperature is 60°C, mix well, and form solution 1;

[0079] C3: Add ZrOCl2.8H2O, the temperature is 80°C, and the processing time is 10h, and the modified MOF is formed;

[0080] Second step, preparation of modified polysulfamide:

[0081] C1: Take appropriate amount of sulfur 1.2 parts, N,N-dimethylformamide 8 parts, 1,6-hexanediamine 4 parts, p-phenylenediacetic acid 15 parts, dimethyl sulfoxide 4 parts and carbon fiber 0.4 parts;

[0082] C2: Put sulfuric acid, 1,6-hexanediamine, 1,4-p-phenylenediacetic acid and 1 / 2 carbon fiber into the reaction kettle, and add dimethyl sulfoxide, the temperature is 100°C, react for 10h, and stir at a speed of 25r / min to obtain intermediate product 1;

[0083] C3: Add 1 / 2 carbon fiber and N,N-dimethylformamide, the temperature is 80°C, react for 2h, and put in methanol to obtain modified polysulfamide.

[0084] Third step, preparation of self-cleaning coating spraying material:

[0085] C1: 13 parts of silicon dioxide, 11 parts of tetraethyl orthosilicate, 12 parts of hexadecyl trimethylsilane, 8 parts of polytetrafluoroethylene (concentration 20%), 6 parts of aluminum tripolyphosphate and 7 parts of sodium silicate, 7 parts of modified MOF, 5 parts of modified polysulfamide, 12 parts of ethanol (mass fraction 50%).

[0086] C2: Put tetraethyl orthosilicate, silicon dioxide, modified polysulfamide, ethanol and hexadecyl trimethoxysilane into the reaction kettle, the temperature is 100°C, to obtain intermediate product 1;

[0087] C3: Put polytetrafluoroethylene solution (mass fraction 60%), intermediate product 1, aluminum triphosphate (mass fraction 30%), modified MOF and sodium silicate into the high-speed disperser, the speed of the high-temperature disperser is 1200r / min, the temperature is 70°C, the processing time is 12min, to obtain the self-cleaning coating spraying material.

[0088] Comparative example 2:

[0089] First step, preparation of modified MOF:

[0090] C1: Take appropriate amount of N,N-dimethylformamide 20 parts, formic acid 20 parts, trimesic acid H3BTC 10 parts, ZrOCl2.8H2O 8 parts, tert-butyl cumyl peroxide 2 parts and chitin 4 parts, aluminum triphosphate 2 parts;

[0091] C2: Put DMF, formic acid and trimesic acid into the reaction kettle, and put trimesic acid, the temperature is 60°C, mix evenly to form solution 1;

[0092] C3: Add ZrOCl2.8H2O, aluminum triphosphate, tert-butyl cumyl peroxide and chitin, the temperature is 80°C, the processing time is 10h, to form modified MOF;

[0093] Second step, preparation of modified polysulfamide:

[0094] C1: Take appropriate amount of sulfur 1.2 parts, N,N-dimethylamide 8 parts, 1,6-hexanediamine 4 parts, p-phenylenediacetic acid 15 parts, dimethyl sulfoxide 4 parts;

[0095] C2: Put sulfuric acid, 1,6-hexanediamine, 1,4-p-phenylenediacetic acid and 1 / 2 carbon fiber into the reaction kettle, and add dimethyl sulfoxide, the temperature is 100°C, react for 10h, and stir at a speed of 25r / min to obtain intermediate product 1;

[0096] C3: Add N,N-dimethylformamide, the temperature is 80°C, react for 2h, and put in methanol to obtain modified polysulfamide.

[0097] Third step, preparation of self-cleaning coating spraying material:

[0098] C1: 13 parts of silica, 11 parts of tetraethyl orthosilicate, 12 parts of hexadecyl trimethyl silane, 8 parts of polytetrafluoroethylene (concentration of 20%), 6 parts of aluminum tripolyphosphate and 7 parts of sodium silicate, 7 parts of modified MOF, 5 parts of modified polysulfuramide, 12 parts of ethanol (mass fraction of 50%).

[0099] C2: Tetraethyl orthosilicate, silica, modified polysulfuramide, ethanol and hexadecyl trimethoxysilane were put into a reaction kettle, the temperature was 100°C, and intermediate product 1 was obtained;

[0100] C3: The polytetrafluoroethylene solution (mass fraction of 60%), intermediate product 1, aluminum tripolyphosphate (mass fraction of 30%), modified MOF and sodium silicate were put into a high-speed disperser, the rotation speed of the high-temperature disperser was 1200 r / min, the temperature was 70°C, the processing time was 12 min, and a self-cleaning coating spraying material was obtained.

[0101] Comparative Example 3:

[0102] First step, preparation of modified MOF:

[0103] C1: An appropriate amount of N,N-dimethylformamide 20 parts, formic acid 20 parts, trimesic acid H3BTC 10 parts, ZrOCl2.8H2O 8 parts, tert-butyl cumyl peroxide 2 parts and chitin 4 parts, aluminum tripolyphosphate 2 parts;

[0104] C2: DMF, formic acid and trimesic acid were put into a reaction kettle, and trimesic acid was put into the reaction kettle, the temperature was 60°C, and the mixture was uniformly mixed to form solution 1;

[0105] C3: ZrOCl2.8H2O, aluminum tripolyphosphate, tert-butyl cumyl peroxide and chitin were added, the temperature was 80°C, the processing time was 10h, and the modified MOF was formed;

[0106] Second step, preparation of modified polysulfuramide:

[0107] C1: An appropriate amount of sulfur 1.2 parts, N,N-dimethylamide 8 parts, 1,6-hexanediamine 4 parts, terephthalic acid 15 parts, dimethyl sulfoxide 2 parts and carbon fiber 0.4 parts;

[0108] C2: Sulfuric acid, 1,6-hexanediamine, 1,4-terephthalic acid and 1 / 2 carbon fiber were put into a reaction kettle, and dimethyl sulfoxide was added, the temperature was 100°C, the reaction was carried out for 10h, and the mixture was stirred at a speed of 25 r / min to obtain intermediate product 1;

[0109] C3: 1 / 2 carbon fiber and N,N-dimethylformamide were added, the temperature was 80°C, the reaction was carried out for 2h, and methanol was added to obtain the modified polysulfuramide.

[0110] Third step, preparation of self-cleaning coating spraying material:

[0111] C1: 13 parts of silica, 11 parts of tetraethyl orthosilicate, 12 parts of hexadecyl trimethyl silane, 8 parts of polytetrafluoroethylene (concentration of 20%), 6 parts of aluminum tripolyphosphate and 7 parts of sodium silicate, 7 parts of modified MOF, 5 parts of modified polysulfamide, 12 parts of ethanol (mass fraction of 50%).

[0112] C2: Put tetraethyl orthosilicate, silica, modified polysulfamide, ethanol and hexadecyl trimethoxysilane into the reaction kettle, the temperature is 100℃, and the intermediate product 1 is obtained;

[0113] C3: Put the polytetrafluoroethylene solution (mass fraction of 60%), the intermediate product 1, the aluminum tripolyphosphate (mass fraction of 30%), the modified MOF and the sodium silicate into the high-speed disperser, the rotating speed of the high-temperature disperser is 1200r / min, the temperature is 70℃, and the processing time is 12min, and the self-cleaning coating spraying material is obtained

[0114] Test test:

[0115] ①Conventional test: the self-cleaning coating spraying material prepared by examples 1-3 and comparative examples 1-2 is sprayed on the surface of smooth pp plate using pneumatic spray gun, the spraying distance is 10cm, and after spraying, the self-cleaning coating spraying material prepared by examples 1-3 and comparative examples 1-2 is sprayed on the surface of smooth pp plate using pneumatic spray gun, the spraying distance is 10cm, and after spraying.

[0116] ②Temperature rise test: the self-cleaning coating spraying material prepared by examples 1-3 and comparative examples 1-2 is sprayed on the surface of smooth pp plate using pneumatic spray gun, the spraying distance is 10cm, and after spraying, the temperature rise test is carried out, the temperature is increased by 5℃ from-30℃, -25℃, -20℃, to 40℃, and each temperature is kept for 30min, and after the temperature rise test, the treated pp plate is subjected to grid test, impact resistance test, wear resistance test and cleanliness test.

[0117] The samples prepared by ① conventional test and ② temperature rise test are subjected to the following tests:

[0118] Grid test: according to GB / T 9286, the surface of the pp plate sprayed with the coating is cut into a grid of 1mm*1mm with a wallpaper knife, the adhesive tape is pressed, and the adhesion is divided into 1st, 2nd and 3rd grades according to the degree of coating peeling.

[0119] Impact resistance test: according to GB / T 1732, a 1kg weight is impacted on the pp plate sprayed with the coating at different heights, and whether there is crack is observed.

[0120] Abrasion test: rub the surface of the coated pp plate with 120 mesh sandpaper for 5 times with the same force, and observe the changes on the surface of the coating.

[0121] Cleanliness:

[0122] A, pour edible oil on top of the coated pp plate, reciprocate for 20 min, and observe the surface of the coating.

[0123] B, rub the surface of the coated pp plate with 120 mesh sandpaper for 5 times with the same force, and pour edible oil on top of the coated pp plate, reciprocate for 20 min, and observe the surface of the coating.

[0124] Table 1 experimental results

[0125]

[0126] From the results, it can be seen that the grid experiments of examples 1-3 are all level 1 after test ① and test ②, and no peeling phenomenon is found, while comparative examples 1-3 all have peeling phenomenon after temperature rise treatment, and even comparative example 2 has level 3; from the impact resistance test, it can be seen that in the conventional experiment, only comparative example 1 of examples 1-3 and comparative examples 1-3 has bubbles, and the rest of the examples and comparative examples have no cracks, but after the temperature rise test treatment, examples 1-3 still have no crack phenomenon, while comparative examples 1-3 all have blistering phenomenon; similarly, from the abrasion test, it can be seen that in the conventional experiment, examples 1-3 and comparative examples 1-3 all have slight scratches, while after the temperature rise test treatment, examples 1-3 still have slight scratches, while comparative examples 2 and 3 have more scratches.

[0127] Table 2 experimental results of cleanliness test

[0128]

[0129] From the cleanliness test, it can be seen that after the conventional test ① without friction test pretreatment, examples 1-3 and comparative examples 2-3 after 20 min treatment with edible oil, no marks appear, but after the temperature rise test treatment, examples still have no marks, comparative example 1 has more oil stains, and comparative examples 2 and 3 have relatively slight oil stains.

[0130] After friction pretreatment, examples 1-3 have no marks in the conventional test ①, comparative examples 1-3 have slight oil stains, while after the temperature rise test treatment, examples 1-2 begin to have point marks, example 3 still has no marks, but comparative examples 1-3 change more obviously, and more oil stains are attached.

[0131] The self-cleaning coating prepared by the application has excellent performance in the grid experiment, impact resistance test, wear resistance test and cleanliness, and especially after temperature rise treatment from-30 DEG C to 40 DEG C, the performance of the self-cleaning coating prepared by the application changes little, and the modified MOF and the polymeric thioamide added in the application can ensure the self-cleaning ability, flexibility and adhesion of the coating.

[0132] The preferred embodiments disclosed above are only used to help illustrate the application. The preferred embodiments do not describe all the details and limit the application to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of the specification. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A high molecular self-cleaning coating spray material, characterized by, The raw materials for preparing the self-cleaning coating include: Silicon dioxide, tetraethyl orthosilicate, hexadecyl trimethyl silane, polytetrafluoroethylene, aluminum tripolyphosphate and sodium silicate, modified MOF, modified polysulfuramide; The raw materials and components of the modified MOF include: N,N-dimethylformamide DMF 10-30 parts; Formic acid 10-30 parts; Trimesic acid H3BTC 5-15 parts; ZrOCl2.8H2O 3-10 parts; Tert-butyl cumyl peroxide 1-3 parts; Chitin 2-5 parts; Aluminum triphosphate 1-3 parts; The preparation steps of the modified MOF include: A1: weigh appropriate amounts of N,N-dimethylformamide DMF, formic acid, trimesic acid, ZrOCl2.8H2O, catalyst and modifier; A2: Put DMF, formic acid and trimesic acid into the reaction kettle, and put in trimesic acid, set condition 1, form solution 1; A3: Add ZrOCl2.8H2O, aluminum triphosphate, tert-butyl cumyl peroxide and chitin, set condition 2, form modified MOF; The raw materials and components of the modified polysulfuramide include: Sulfur 1-3 parts; 1,6-hexanediamine 2-5 parts; p-Phthalic acid 10-20 parts; Dimethyl sulfoxide 3-5 parts; N,N-dimethylamide 5-10 parts; Carbon fiber 0.1-0.5 parts; The preparation steps of the modified polysulfuramide include: B1: weigh appropriate amounts of sulfur, 1,6-hexanediamine, p-phenylenediacetic acid, dimethyl sulfoxide and carbon fiber B2: Put sulfuric acid, 1,6-hexanediamine, 1,4-p-phenylenediacetic acid and 1 / 2 into the reaction kettle, and add dimethyl sulfoxide, set condition 3, get intermediate product 1; B3: Add 1 / 2 carbon fiber and N,N-dimethylformamide, set condition 4, and put in methanol, get modified polysulfuramide.

2. The polymer self-cleaning coating spray material according to claim 1, wherein, The condition 1 is that the temperature is 30-80℃, and the mixture is uniformly mixed; the condition 2 is that the temperature is 60-100℃, and the reaction time is 1-20h.

3. The polymer self-cleaning coating spray material according to claim 1, wherein, The condition 3 is that the nitrogen protection environment, the temperature is 60-120℃, the reaction time is 1-20h, and the stirring speed is 10-30r / min; the condition 4 is that the temperature is 60-120℃, and the reaction time is 1-5h.

4. A process for preparing a high molecular self-cleaning coating spray material, characterized by, The steps of the preparation process include: Preparation of modified MOF: C1: weigh appropriate amounts of N,N-dimethylformamide DMF, formic acid, trimesic acid, ZrOCl2.8H2O, tert-butyl cumyl peroxide and chitin; C2: Put DMF, formic acid and trimesic acid into the reaction kettle, and put in trimesic acid, the temperature is 30-80℃, and the mixture is uniformly mixed, form solution 1; C3: Add ZrOCl2.8H2O, tert-butyl cumyl peroxide and chitin, the temperature is 60-100℃, and the treatment time is 1-20h, form modified MOF; Preparation of modified polysulfuramide: C1: weigh appropriate amounts of sulfur, 1,6-hexanediamine, p-phenylenediacetic acid, dimethyl sulfoxide and carbon fiber C2: Put sulfuric acid, 1,6-hexanediamine, 1,4-p-phenylenediacetic acid and 1 / 2 carbon fiber into the reaction kettle, and add dimethylsulfoxide, the temperature is 60-120℃, react for 1-20h, and stir at a speed of 10-30r / min to obtain intermediate product 1; C3: Add 1 / 2 carbon fiber and N,N-dimethylformamide, the temperature is 60-120℃, react for 1-5h, and put in methanol to obtain modified polysulfamide; Preparation of self-cleaning coating spraying material: C1: Take appropriate amount of modified MOP, modified polysulfamide, silicon dioxide, tetraethyl orthosilicate, hexadecyl trimethyl silane, polytetrafluoroethylene, aluminum tripolyphosphate, sodium silicate, ethanol; C2: Put tetraethyl orthosilicate, silicon dioxide, modified polysulfamide, ethanol and hexadecyl trimethoxysilane into the reaction kettle, the temperature is 60-120℃, to obtain intermediate product 1; C3: Put polytetrafluoroethylene solution, intermediate product 1, aluminum tripolyphosphate, modified MOF and sodium silicate into the high-speed disperser, the speed of high-temperature disperser is 500-1500r / min, the temperature is 60-80℃, the processing time is 5-20min, to obtain self-cleaning coating spraying material.

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