Preparation method of alkyd resin composite material and application of alkyd resin composite material in ultra-clean viscous wiping material

Abstract

The invention belongs to the technical field of high-molecular compound composite materials, and particularly relates to a preparation method of an alkyd resin composite material and application of the alkyd resin composite material in an ultra-clean viscous wiping material. The alkyd resin composite material is prepared by using aminated mesoporous silica to prepare the alkyd resin and cooperating with the modified chlorinated paraffin and the epoxy modified rosin resin, and the alkyd resin composite material is applied to an ultra-clean viscous wiping material, so that the wiping efficiency of the material is remarkably improved, the wear-resistant frequency is increased, and the wear resistance of the material is improved. Meanwhile, good transverse breaking strength is obtained.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer composite materials, and particularly relates to a preparation method of an alkyd resin composite material and its application in a super-clean sticky wiping material. Background Art

[0002] With the development of society and the progress of technology, electronic products have become increasingly popular. In the processing of high-precision electronic products such as chip production and packaging, the requirements for wiping materials are getting higher and higher. They not only need to absorb moisture and remove dirt, be easy to wash and dry quickly, but also be soft enough not to cause fine damage to the product during use, and the fibers should not fall off. Alkyd resin is an oil-modified polyester, which is a kind of synthetic resin material obtained by polycondensation polymerization of polyols, polyacids and fatty acids or oils. Alkyd resin has air-drying property, can self-oxidize and crosslink into a film, and has the advantages of low surface tension, strong wetting ability, good leveling property, and excellent adhesion to a variety of substrates. Therefore, using alkyd resin in wiping materials has good application prospects.

[0003] Chinese Patent (Publication No. CN114835883B) discloses a carboxylated micro-nano cellulose-based alkyd resin and its preparation method. The alkyd resin of this invention uses cellulose, a natural polymer material with rich reserves, as the raw material, which has the advantages of low production cost, environmental friendliness, safety and non-toxicity. At the same time, the carboxylated cellulose molecular chain contains multiple carboxyl groups, which can form a network crosslink with polyols, effectively improving the film-forming stability of the alkyd resin. However, this patent does not solve the problems of low wiping efficiency, few wear-resistant times, and low transverse fracture strength when the existing alkyd resin composite material is applied to wiping materials, seriously affecting its actual use.

[0004] Therefore, how to modify the composition of alkyd resin, cooperate with other functional components, prepare an alkyd resin composite material and use it in wiping materials to effectively improve the wiping efficiency of the material, increase the wear-resistant times, and at the same time obtain better transverse fracture strength has become the key direction to be overcome. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a preparation method of an alkyd resin composite material and its application in a super-clean sticky wiping material, aiming to solve the problems of low wiping efficiency, few wear-resistant times, and low transverse fracture strength when the existing alkyd resin composite material is applied to wiping materials.

[0006] The present invention prepares alkyd resin by using amino mesoporous silica, and uses modified chlorinated paraffin and epoxy modified rosin resin together to prepare alkyd resin composite material, and applies the alkyd resin composite material to ultra-clean viscous wiping material, thereby significantly improving the wiping efficiency of the material, increasing the number of wear resistance, and obtaining good transverse rupture strength.

[0007] The technical solution of the present invention is as follows: A first aspect of the present invention provides a method for preparing an alkyd resin composite material, comprising the following steps: Step S1: by weight, 4 to 8 parts of mesoporous silica and 4 to 8 parts of 3-aminopropyltriethoxysilane are mixed, heated to reflux, centrifuged, washed with toluene, and dried to obtain amino mesoporous silica; Step S2: by weight, 32-36 parts of coconut oil, 24-30 parts of polyacid, 16-20 parts of polyol, 4-8 parts of 2,2-dimethylolpropionic acid and 4-12 parts of toluene are mixed for esterification reaction, and distilled under reduced pressure, and 10-14 parts of propylene glycol methyl ether acetate are first added, and then 12-16 parts of the amino silica are added and stirred evenly to obtain an alkyd resin; Step S3: By weight, 30 to 40 parts of the alkyd resin, 4 to 6 parts of chlorinated paraffin, 8 to 12 parts of rosin resin, 4 to 6 parts of vaseline and 6 to 10 parts of cosolvent are stirred and mixed to obtain an alkyd resin composite material. As a preferred technical solution of the present invention, the weight parts of the alkyd resin can be 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts, etc.

[0008] As a preferred technical solution of the present invention, the weight proportion of the chlorinated paraffin can be 4 parts, 4.5 parts, 5 parts, 5.5 parts or 6 parts.

[0009] As a preferred technical solution of the present invention, the weight proportion of the rosin resin can be 8 parts, 9 parts, 10 parts, 11 parts or 12 parts.

[0010] As a preferred technical solution of the present invention, the weight proportions of the vaseline can be 4 parts, 4.5 parts, 5 parts, 5.5 parts or 6 parts.

[0011] As a preferred technical solution of the present invention, the weight proportion of the co-solvent can be 6 parts, 7 parts, 34 parts, 8 parts, 9 parts or 10 parts.

[0012] As a preferred technical solution of the present invention, the conditions of the esterification reaction include: reacting at 160-180° C. for 2-4 hours under a nitrogen atmosphere, and then heating to 220-230° C. for 4-6 hours.

[0013] As a preferred technical solution of the present invention, the conditions for stirring and mixing include: adjusting the pH to 9 - 10 with a sodium hydroxide solution, stirring for 1 - 2 h at a temperature of 90 - 100 °C, and drying.

[0014] As a preferred technical solution of the present invention, the polybasic acid is adipic acid and isophthalic acid; the mass ratio of adipic acid to isophthalic acid is (1 - 2):1.

[0015] As a preferred technical solution of the present invention, the polyol is selected from any one or a combination of at least two of ethylene glycol, glycerol, and 1,3 - butanediol; the co - solvent is selected from any one or a combination of at least two of ethylene glycol monobutyl ether, propylene glycol monobutyl ether, and sec - butanol.

[0016] As a preferred technical solution of the present invention, the preparation method of the mesoporous silica includes: by weight, adding 6 - 10 parts of triethylamine to 180 - 200 parts of deionized water and mixing evenly, then adding 4 - 8 parts of cetyltrimethylammonium bromide and 1 - 3 parts of sodium salicylate, and then adding 30 - 40 parts of tetraethyl orthosilicate for stirring reaction, washing with water, drying to obtain an intermediate product; mixing 500 - 600 parts of absolute ethanol and 6 - 10 parts of hydrochloric acid evenly, then adding 2 - 4 parts of the intermediate product for full immersion, centrifuging, washing with absolute ethanol, drying, and grinding to obtain mesoporous silica.

[0017] As a preferred technical solution of the present invention, the conditions for the stirring reaction include: the stirring speed is 100 - 120 r / min, the temperature is 80 - 90 °C, and the time is 100 - 120 min.

[0018] On the one hand, the amino - functionalized mesoporous silica can neutralize the excess carboxyl groups in the carboxyl group and act as a neutralizing agent; on the other hand, the mesoporous silica has a large specific surface area and porosity, and when it is added to the alkyd resin, it can provide more active sites for adsorbing and capturing stains, thereby increasing the viscosity of the wiping material and significantly improving the wiping efficiency.

[0019] As a preferred technical solution of the present invention, the chlorinated paraffin is modified chlorinated paraffin; the preparation method of the modified chlorinated paraffin includes: by weight, adding 40 - 50 parts of chlorinated paraffin to 400 - 500 parts of acetone and stirring to dissolve, then adding 30 - 40 parts of thiosalicylic acid and 40 - 44 parts of potassium carbonate for a substitution reaction, placing it under nitrogen protection, reacting at 50 - 54 °C for 10 - 12 h, and after the reaction is completed, performing extraction and vacuum drying to obtain modified chlorinated paraffin.

[0020] The modified chlorinated paraffin introduces a benzene ring through thiosalicylic acid. The presence of the benzene ring increases the intermolecular interaction force, which helps to form a denser and stronger network structure. Through this structure, not only the hardness of the material is improved, but also the toughness is enhanced, making the wiping material less likely to be damaged when subjected to friction or scratching, and thus increasing the number of wear-resistant times.

[0021] As a preferred technical solution of the present invention, the rosin resin is an epoxy-modified rosin resin; the preparation method of the epoxy-modified rosin resin includes: by weight, heating and dissolving 60-70 parts of rosin resin, introducing nitrogen for protection, and then adding 10-20 parts of phenol, 0.8-1.6 parts of zinc oxide and 8-16 parts of formaldehyde for reflux reaction. After the reaction is completed, 50-60 parts of epichlorohydrin and 0.4-0.8 parts of magnesium oxide are added for epoxidation reaction. After the reaction ends, it is washed with water until neutral, and evaporated under reduced pressure to obtain the epoxy-modified rosin resin.

[0022] As a preferred technical solution of the present invention, the conditions of the epoxidation reaction include: heating at 86-90 °C for 1-3 h, and then cooling to 50-54 °C, adding 10-16 parts of sodium hydroxide and stirring for 5-7 h.

[0023] The epoxy-modified rosin resin reacts with the hydroxyl groups in the alkyd resin through epoxy groups, increasing the crosslinking density inside the material. The high crosslinking density helps to improve the overall strength and rigidity of the material, effectively increasing the transverse fracture strength.

[0024] In the second aspect, the present invention provides an application of an alkyd resin composite material prepared by the method described in the first aspect in a super-clean sticky wiping material. The wiping material includes a base cloth and an alkyd resin composite material; wherein, the base cloth is impregnated in the alkyd resin composite material and the wiping material is obtained by heat drying and moisture setting, specifically as follows: Step (1): Prepare an alkyd resin composite material according to the method described in the first aspect; Step (2): Transfer the base cloth to a material tank filled with the alkyd resin composite material for impregnation treatment; Step (3): After impregnation, perform heat drying treatment to obtain a super-clean sticky wiping material.

[0025] Compared with the prior art, the present invention has the following beneficial effects: (1) In the alkyd resin of the present invention, aminated mesoporous silica is used as a neutralizing agent. At the same time, aminated mesoporous silica has a large specific surface area and porosity, and can be used as a carrier for modified chlorinated paraffin and epoxy-modified rosin resin. In addition, mesoporous silica can not only react with the carboxyl group in the modified chlorinated paraffin through the amino group, but also combine with the epoxy-modified rosin resin. Based on aminated mesoporous silica, a three-dimensional network structure is constructed, significantly improving the wiping efficiency of the alkyd resin wiping material, increasing the number of wear-resistant times, and at the same time enhancing the transverse fracture strength.

[0026] (2) On the one hand, the aminated mesoporous silica of the present invention can neutralize the excess carboxyl groups in the carboxyl group through the amino group, acting as a neutralizing agent; on the other hand, mesoporous silica has a large specific surface area and porosity, and when it is added to the alkyd resin, it can provide more active sites for adsorbing and capturing stains, thereby increasing the viscosity of the wiping material and significantly improving the wiping efficiency.

[0027] (3) The modified chlorinated paraffin of the present invention introduces a benzene ring through thiosalicylic acid. The presence of the benzene ring increases the intermolecular interaction force, which helps to form a more dense and firm network structure. Through this structure, not only the hardness of the material is improved, but also the toughness is improved, making the wiping material less likely to be damaged when subjected to friction or scratching, and thus increasing the number of wear-resistant times.

[0028] (4) The epoxy-modified rosin resin of the present invention reacts with the hydroxyl group in the alkyd resin through the epoxy group, increasing the crosslinking density inside the material. Through the high crosslinking density, it helps to improve the overall strength and rigidity of the material, effectively increasing the transverse fracture strength. Detailed implementation method

[0029] To facilitate the understanding of the present invention, the following examples are listed for the present invention. Those skilled in the art should understand that the said examples are only to help understand the present invention and should not be regarded as specific limitations on the present invention.

[0030] The sources of some components in the examples and comparative examples are as follows: Coconut oil, product number C113014, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Adipic acid, CAS number 124-04-9, purchased from Sinopharm Chemical Reagent Co., Ltd.; Isophthalic acid, CAS number 121-91-5, purchased from Sinopharm Chemical Reagent Co., Ltd.; Ethylene glycol, CAS number 107-21-1, purchased from Sinopharm Chemical Reagent Co., Ltd.; Glycerol, CAS number 56-81-5, purchased from Sinopharm Chemical Reagent Co., Ltd.; 1,3-Butanediol, with CAS number 107-88-0, was purchased from Shanghai Macklin Biochemical Co., Ltd.; 2,2-Bis(hydroxymethyl)propionic acid, with CAS number 4767-03-7, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Toluene, with CAS number 108-88-3, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Propylene glycol methyl ether acetate, with CAS number 108-65-6, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Silica, with product number S118568, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Chlorinated paraffin, with CAS number 63449-39-8, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Rosin resin, with grade number 110, was purchased from Zhengzhou Cyber Chemical Products Co., Ltd.; Vaseline, with CAS number 8009-03-8, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Ethylene glycol monobutyl ether, with CAS number 111-76-2, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Propylene glycol monobutyl ether, with CAS number 29387-86-8, was purchased from Shanghai Macklin Biochemical Co., Ltd.; sec-Butyl alcohol, with CAS number 78-92-2, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Triethylamine, with CAS number 121-44-8, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Cetyltrimethylammonium bromide, with CAS number 57-09-0, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Sodium salicylate, with CAS number 54-21-7, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Tetraethyl orthosilicate, with CAS number 78-10-4, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Absolute ethanol, with CAS number 64-17-5, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Hydrochloric acid, with CAS number 7647-01-0, was purchased from Sinopharm Chemical Reagent Co., Ltd.; 3-Aminopropyltriethoxysilane, with CAS number 919-30-2, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Acetone, with CAS number 67-64-1, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Thiosalicylic acid, with CAS number 147-93-3, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Potassium carbonate, with CAS number 584-08-7, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Phenol, CAS No. 108-95-2, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Zinc oxide, CAS No. 1314-13-2, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Formaldehyde, CAS No. 8013-13-6, was purchased from Sinopharm Chemical Reagent Co., Ltd.; Epichlorohydrin, CAS No. 106-89-8, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Magnesium oxide, CAS No. 1309-48-4, was purchased from Shanghai Macklin Biochemical Co., Ltd.; Sodium hydroxide, CAS No. 1310-73-2, was purchased from Sinopharm Chemical Reagent Co., Ltd. Example 1

[0031] This example provides a method for preparing an alkyd resin composite material, which includes the following steps: Step S1: By weight, 8 parts of mesoporous silica and 8 parts of 3-aminopropyltriethoxysilane were mixed, heated under reflux, centrifuged, washed with toluene, and dried to obtain amino-functionalized mesoporous silica; Step S2: By weight, 36 parts of coconut oil, 24 parts of polybasic acid (16 parts of adipic acid and 8 parts of isophthalic acid), 20 parts of ethylene glycol, 8 parts of 2,2-dimethylolpropionic acid, and 12 parts of toluene were mixed for an esterification reaction. Placed in a nitrogen atmosphere, the reaction was carried out at 180 °C for 2 h, then the temperature was raised to 230 °C and kept warm for 4 h, and then vacuum distilled. First, 14 parts of propylene glycol methyl ether acetate were added, and then 16 parts of the amino-functionalized silica were added and stirred evenly to obtain an alkyd resin; Step S3: By weight, 40 parts of the alkyd resin, 6 parts of modified chlorinated paraffin, 12 parts of epoxy-modified rosin resin, 6 parts of petrolatum, and 10 parts of co-solvent ethylene glycol monobutyl ether were stirred and mixed. The pH was adjusted to 10 with a sodium hydroxide solution, and the mixture was stirred at 100 °C for 1 h and then dried to obtain an alkyd resin composite material.

[0032] The preparation of the mesoporous silica: By weight, 10 parts of triethylamine were added to 200 parts of deionized water and mixed evenly. Then, 8 parts of cetyltrimethylammonium bromide and 3 parts of sodium salicylate were added, and then 40 parts of tetraethyl orthosilicate were added for stirring reaction (stirring speed: 120 r / min, temperature: 90 °C, time: 100 min). After washing with water and drying, an intermediate product was obtained; 600 parts of absolute ethanol and 10 parts of hydrochloric acid were mixed evenly, and then 4 parts of the intermediate product were added and soaked thoroughly, centrifuged, washed with absolute ethanol, dried, and ground to obtain mesoporous silica.

[0033] Preparation of the modified chlorinated paraffin: By weight, 50 parts of chlorinated paraffin are added to 500 parts of acetone and stirred until dissolved. Then, 40 parts of thiosalicylic acid and 44 parts of potassium carbonate are added for a substitution reaction. Under nitrogen protection, the reaction is carried out at 54 °C for 10 h. After the reaction is completed, extraction is carried out, followed by vacuum drying to obtain the modified chlorinated paraffin.

[0034] Preparation of the epoxy-modified rosin resin: By weight, 70 parts of rosin resin are heated and dissolved, and nitrogen is introduced for protection. Then, 20 parts of phenol, 1.6 parts of zinc oxide, and 16 parts of formaldehyde are added for a reflux reaction. After the reaction is completed, 60 parts of epichlorohydrin and 0.8 part of magnesium oxide are added for an epoxidation reaction. The mixture is heated at 90 °C for 1 h, then cooled to 54 °C, and 16 parts of sodium hydroxide are added and stirred for 5 h. After the reaction ends, it is washed with water until neutral, and then evaporated under reduced pressure to obtain the epoxy-modified rosin resin. Example 2

[0035] This example provides a preparation method of an alkyd resin composite material, which includes the following steps: Step S1: By weight, 4 parts of mesoporous silica and 4 parts of 3-aminopropyltriethoxysilane are mixed and heated under reflux, centrifuged, washed with toluene, and dried to obtain amino-functionalized mesoporous silica. Step S2: By weight, 32 parts of coconut oil, 30 parts of polybasic acid (15 parts of adipic acid and 15 parts of isophthalic acid), 16 parts of glycerol, 4 parts of 2,2-dimethylolpropionic acid, and 4 parts of toluene are mixed for an esterification reaction. Under a nitrogen atmosphere, the reaction is carried out at 160 °C for 4 h, then the temperature is raised to 220 °C and held for 6 h. After vacuum distillation, first 10 parts of propylene glycol methyl ether acetate are added, and then 12 parts of the amino-functionalized silica are added and stirred evenly to obtain an alkyd resin. Step S3: By weight, 30 parts of the alkyd resin, 4 parts of the modified chlorinated paraffin, 8 parts of the epoxy-modified rosin resin, 4 parts of petrolatum, and 6 parts of the co-solvent propylene glycol butyl ether are stirred and mixed. The pH is adjusted to 10 with a sodium hydroxide solution, and the mixture is stirred at 90 °C for 2 h and then dried to obtain the alkyd resin composite material.

[0036] Preparation of the mesoporous silica: By weight, 6 parts of triethylamine are added to 180 parts of deionized water and mixed evenly. Then, 4 parts of cetyltrimethylammonium bromide and 1 part of sodium salicylate are added, and then 30 parts of tetraethyl orthosilicate are added for stirring reaction (stirring speed: 100 r / min, temperature: 80 °C, time: 120 min). After washing with water and drying, an intermediate product is obtained. 500 parts of absolute ethanol and 6 parts of hydrochloric acid are mixed evenly, and then 2 parts of the intermediate product are added and soaked thoroughly. After centrifugation, it is washed with absolute ethanol, dried, and ground to obtain mesoporous silica.

[0037] Preparation of the modified chlorinated paraffin: By weight, 40 parts of chlorinated paraffin are added to 400 parts of acetone and stirred until dissolved. Then, 30 parts of thiosalicylic acid and 40 parts of potassium carbonate are added for a substitution reaction. Under nitrogen protection, the reaction is carried out at 50 °C for 12 h. After the reaction is completed, extraction is carried out, followed by vacuum drying to obtain the modified chlorinated paraffin.

[0038] Preparation of the epoxy-modified rosin resin: By weight, 60 parts of rosin resin are heated and dissolved, and nitrogen is introduced for protection. Then, 10 parts of phenol, 0.8 part of zinc oxide, and 8 parts of formaldehyde are added for a reflux reaction. After the reaction is completed, 50 parts of epichlorohydrin and 0.4 part of magnesium oxide are added for an epoxidation reaction. The reaction is heated at 86 °C for 3 h, and then cooled to 50 °C. 10 parts of sodium hydroxide are added and stirred for 7 h. After the reaction ends, it is washed with water until neutral, and then evaporated under reduced pressure to obtain the epoxy-modified rosin resin. Example 3

[0039] This example provides a preparation method of an alkyd resin composite material, which includes the following steps: Step S1: By weight, 4 parts of mesoporous silica and 4 parts of 3-aminopropyltriethoxysilane are mixed and heated under reflux, centrifuged, washed with toluene, and dried to obtain amino-functionalized mesoporous silica. Step S2: By weight, 32 parts of coconut oil, 28 parts of polybasic acid (16 parts of adipic acid and 12 parts of isophthalic acid), 18 parts of 1,3-butanediol, 6 parts of 2,2-dimethylolpropionic acid, and 8 parts of toluene are mixed for an esterification reaction. Under a nitrogen atmosphere, the reaction is carried out at 170 °C for 3 h, then heated to 225 °C and held for 5 h, followed by vacuum distillation. First, 12 parts of propylene glycol methyl ether acetate are added, and then 14 parts of the amino-functionalized silica are added and stirred evenly to obtain an alkyd resin. Step S3: By weight, 35 parts of the alkyd resin, 5 parts of the modified chlorinated paraffin, 10 parts of the epoxy-modified rosin resin, 5 parts of petrolatum, and 8 parts of the co-solvent sec-butyl alcohol are stirred and mixed. The pH is adjusted to 9.6 with a sodium hydroxide solution, and the mixture is stirred at 95 °C for 1.5 h and then dried to obtain the alkyd resin composite material.

[0040] Preparation of the mesoporous silica: By weight, 8 parts of triethylamine are added to 190 parts of deionized water and mixed evenly. Then, 6 parts of cetyltrimethylammonium bromide and 2 parts of sodium salicylate are added, and then 35 parts of tetraethyl orthosilicate are added for a stirring reaction (stirring speed: 110 r / min, temperature: 85 °C, time: 110 min). After washing with water and drying, an intermediate product is obtained. 550 parts of absolute ethanol and 8 parts of hydrochloric acid are mixed evenly, and then 3 parts of the intermediate product are added and soaked thoroughly. After centrifugation, it is washed with absolute ethanol, dried, and ground to obtain the mesoporous silica.

[0041] Preparation of the modified chlorinated paraffin: By weight, 45 parts of chlorinated paraffin are added to 450 parts of acetone and stirred until dissolved, then 35 parts of thiosalicylic acid and 42 parts of potassium carbonate are added for substitution reaction. Under nitrogen protection, the reaction is carried out at 52 °C for 11 h. After the reaction is completed, extraction is carried out and vacuum drying is performed to obtain the modified chlorinated paraffin.

[0042] Preparation of the epoxy-modified rosin resin: By weight, 65 parts of rosin resin are heated and dissolved, and nitrogen is introduced for protection. Then 15 parts of phenol, 1.2 parts of zinc oxide and 12 parts of formaldehyde are added for reflux reaction. After the reaction is completed, 55 parts of epichlorohydrin and 0.6 part of magnesium oxide are added for epoxidation reaction. The reaction is heated at 88 °C for 2 h, then cooled to 52 °C and 14 parts of sodium hydroxide are added and stirred for 6 h. After the reaction ends, it is washed with water until neutral and evaporated under reduced pressure to obtain the epoxy-modified rosin resin.

[0043] Comparative Example 1 This comparative example provides a preparation method of an alkyd resin composite material, which is different from Example 1 in that commercially available silica (product number S118568) is used to replace the aminated mesoporous silica.

[0044] Comparative Example 2 This comparative example provides a preparation method of an alkyd resin composite material, which is different from Example 1 in that the dosage of adipic acid in the polybasic acid is changed to 20 parts and the dosage of isophthalic acid is changed to 4 parts.

[0045] Comparative Example 3 This comparative example provides a preparation method of an alkyd resin composite material, which is different from Example 1 in that the dosage of adipic acid in the polybasic acid is changed to 8 parts and the dosage of isophthalic acid is changed to 16 parts.

[0046] Comparative Example 4 This comparative example provides a preparation method of an alkyd resin composite material, which is different from Example 1 in that commercially available chlorinated paraffin (CAS No. 63449-39-8) is used to replace the modified chlorinated paraffin.

[0047] Comparative Example 5 This comparative example provides a preparation method of an alkyd resin composite material, which is different from Example 1 in that commercially available rosin resin (grade 110) is used to replace the epoxy-modified rosin resin.

[0048] Application Example The alkyd resin composite materials prepared in the above examples and comparative examples are respectively applied to the ultra-clean sticky wiping material. The wiping material includes a base cloth and an alkyd resin composite material; wherein, the base cloth is impregnated in the alkyd resin composite material and the wiping material is obtained by hot drying and moisture setting, specifically as follows: Step (1): Prepare the alkyd resin composite material according to the methods described in the examples and comparative examples. Step (2): Transfer the base fabric to a material tank containing the alkyd resin composite material for impregnation treatment. Step (3): After impregnation, perform heat drying treatment to obtain a super-clean sticky wiping material.

[0049] Test the performance of the wiping material provided in the above application example. The test method is as follows: (1) Wiping efficiency test: Conduct the test with reference to the requirements of "SJ / T 11480-2014 General Specification for Anti-static Dust-free Wiping Cloths".

[0050] (2) Abrasion resistance test: Conduct the test with reference to the requirements of "SJ / T 11480-2014 General Specification for Anti-static Dust-free Wiping Cloths".

[0051] (3) Transverse breaking strength test: Conduct the test with reference to the requirements of "FZ / T 64056-2015 Wiping Cloths for Clean Rooms".

[0052] The above performance test data are shown in Table 1.

[0053] Table 1 Performance Test Results

[0054] As can be seen from the above content, in the present invention, the alkyd resin is prepared by using amino-functionalized mesoporous silica, and at the same time, the combined use of modified chlorinated paraffin and epoxy-modified rosin resin is coordinated to prepare an alkyd resin composite material, which is applied to the super-clean sticky wiping material (Application Example 1 to Application Example 3); its wiping efficiency is 94.1% - 94.8%, the abrasion resistance is 515 - 522 times, and the transverse breaking strength is 14.8 - 15.4 N.

[0055] Compared with Application Example 1, when using commercially available silica (product number S118568) to replace the aminated mesoporous silica, the wiping efficiency is reduced, the number of abrasion resistance times is decreased, and the transverse fracture strength becomes poor (Application Comparative Example 1); compared with Application Example 1, when the dosage of adipic acid in the polybasic acid is changed to 20 parts and the dosage of isophthalic acid is changed to 4 parts, due to the excessive dosage of adipic acid and poor compounding effect, the wiping efficiency is reduced, the number of abrasion resistance times is decreased, and the transverse fracture strength becomes poor (Application Comparative Example 2); compared with Application Example 1, when the dosage of adipic acid in the polybasic acid is changed to 8 parts and the dosage of isophthalic acid is changed to 16 parts, due to the insufficient dosage of adipic acid and poor compounding effect, the wiping efficiency is reduced, the number of abrasion resistance times is decreased, and the transverse fracture strength becomes poor (Application Comparative Example 3); compared with Application Example 1, when using commercially available chlorinated paraffin (CAS number 63449-39-8) to replace the modified chlorinated paraffin, the wiping efficiency is reduced, the number of abrasion resistance times is decreased, and the transverse fracture strength becomes poor (Application Comparative Example 4); compared with Application Example 1, when using commercially available rosin resin (grade 110) to replace the epoxy-modified rosin resin, the wiping efficiency is reduced, the number of abrasion resistance times is decreased, and the transverse fracture strength becomes poor (Application Comparative Example 5).

[0056] In summary, by using aminated mesoporous silica to prepare alkyd resin, and simultaneously cooperating with the common use of modified chlorinated paraffin and epoxy-modified rosin resin, the alkyd resin composite material is prepared and applied to the ultra-clean sticky wiping material, which significantly improves the wiping efficiency of the material, increases the number of abrasion resistance times, and simultaneously obtains good transverse fracture strength.

Claims

1. A method for preparing an alkyd resin composite material, characterized in that: The following steps are involved: Step S1: by weight, 4 to 8 parts of mesoporous silica and 4 to 8 parts of 3-aminopropyltriethoxysilane are mixed, heated to reflux, centrifuged, washed with toluene, and dried to obtain amino mesoporous silica; Step S2: by weight, 32-36 parts of coconut oil, 24-30 parts of polyacid, 16-20 parts of polyol, 4-8 parts of 2,2-dimethylolpropionic acid and 4-12 parts of toluene are mixed for esterification reaction, and distilled under reduced pressure, and 10-14 parts of propylene glycol methyl ether acetate are first added, and then 12-16 parts of the amino silica are added and stirred evenly to obtain an alkyd resin; Step S3: by weight, 30 to 40 parts of the alkyd resin, 4 to 6 parts of chlorinated paraffin, 8 to 12 parts of rosin resin, 4 to 6 parts of vaseline and 6 to 10 parts of a solvent are stirred and mixed to obtain an alkyd resin composite material.

2. The method for preparing an alkyd resin composite material according to claim 1, characterized in that: The conditions of the esterification reaction include: reacting at 160-180° C. for 2-4 hours under a nitrogen atmosphere, and then heating to 220-230° C. and keeping the temperature for 4-6 hours.

3. The method for preparing an alkyd resin composite material according to claim 1, characterized in that: The polyacid is adipic acid and isophthalic acid; the mass ratio of adipic acid to isophthalic acid is (1-2):

1.

4. The method for preparing an alkyd resin composite material according to claim 1, characterized in that: The polyol is selected from any one of ethylene glycol, propylene glycol, and 1,3-butanediol, or a combination of at least two thereof; The co-solvent is selected from any one of ethylene glycol butyl ether, propylene glycol butyl ether, and sec-butyl alcohol, or a combination of at least two of them.

5. The method for preparing an alkyd resin composite material according to claim 1, characterized in that: The preparation method of the mesoporous silica comprises: adding 6 to 10 parts of triethylamine to 180 to 200 parts of deionized water by weight and mixing them evenly, then adding 4 to 8 parts of hexadecyltrimethylammonium bromide and 1 to 3 parts of sodium salicylate, and then adding 30 to 40 parts of tetraethyl orthosilicate for stirring reaction, washing with water, and drying to obtain an intermediate product; mixing 500 to 600 parts of anhydrous ethanol and 6 to 10 parts of hydrochloric acid evenly, then adding 2 to 4 parts of the intermediate product for full immersion, centrifuging, washing with anhydrous ethanol, drying, and grinding to obtain the mesoporous silica.

6. The method for preparing an alkyd resin composite material according to claim 5, characterized in that: The stirring reaction conditions include: a stirring speed of 100-120 r / min, a temperature of 80-90° C., and a time of 100-120 min.

7. The method for preparing an alkyd resin composite material according to claim 1, characterized in that: The chlorinated paraffin is a modified chlorinated paraffin; The preparation method of the modified chlorinated paraffin comprises: adding 40 to 50 parts of chlorinated paraffin to 400 to 500 parts of acetone by weight, stirring and dissolving, then adding 30 to 40 parts of thiosalicylic acid and 40 to 44 parts of potassium carbonate to carry out a substitution reaction, reacting at 50 to 54° C. for 10 to 12 hours under nitrogen protection, extracting after the reaction is completed, and vacuum drying to obtain the modified chlorinated paraffin.

8. The method for preparing an alkyd resin composite material according to claim 1, characterized in that: The rosin resin is epoxy modified rosin resin; The preparation method of the epoxy modified rosin resin comprises: heating and dissolving 60-70 parts of rosin resin by weight, introducing nitrogen for protection, then adding 10-20 parts of phenol, 0.8-1.6 parts of zinc oxide and 8-16 parts of formaldehyde for reflux reaction, adding 50-60 parts of epichlorohydrin and 0.4-0.8 parts of magnesium oxide for epoxidation reaction after the reaction is completed, washing with water to neutrality after the reaction is completed, and evaporating under reduced pressure to obtain the epoxy modified rosin resin.

9. The method for preparing an alkyd resin composite material according to claim 8, characterized in that: The epoxidation reaction conditions include: heating at 86-90° C. for 1-3 hours, then cooling to 50-54° C., adding 10-16 parts of sodium hydroxide and stirring for 5-7 hours.

10. An application of an alkyd resin composite material in an ultra-clean viscous wiping material, characterized in that: The wiping material comprises a base fabric and an alkyd resin composite material; wherein the base fabric is impregnated in the alkyd resin composite material, and the wiping material is obtained by heat drying and moisture fixation, as follows: Step (1): preparing an alkyd resin composite material according to the method of claims 1-9; Step (2): transferring the base fabric to a material tank containing an alkyd resin composite material for impregnation treatment; Step (3): After the impregnation, a heat baking treatment is performed to obtain an ultra-clean sticky wiping material.

Images