A dual parent modified silane coupling agent, a preparation method and application thereof

Abstract

The application provides a kind of parent modification silane coupling agent, preparation method and application, belong to material chemistry field.The application provides a kind of preparation method of parent modification silane coupling agent, comprising the following steps: in the presence of acid binding agent, first solvent, hydroxyl-containing hydrophilic polymer is reacted with halogenated acyl halide to obtain ATRP initiator;In the presence of metal salt catalyst, ligand and second solvent, ATRP initiator is reacted with acrylate monomer, to obtain active macromolecule containing double parent group;In the presence of base reagent and third solvent, active macromolecule containing double parent group is reacted with silane compound containing amino, to obtain parent modification silane coupling agent.The silane coupling agent provided by the application can be effectively applied in paint, not only can improve the interface performance between inorganic surface and organic paint, but also can effectively improve the tensile strength of coating, waterproof and stain resistance and the tensile strength after recoating.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of material chemistry, in particular to a kind of amphiphilic modified silane coupling agent, preparation method and application thereof. BACKGROUND

[0002] Silane coupling agent can simultaneously react with inorganic and organic materials, and is usually used to improve the interfacial adhesion between inorganic and organic materials, thereby improving the bonding strength between materials, which is very important for improving the adhesion of coating and the preparation of composite materials. Common silane coupling agents include vinyl coupling agents, chloroalkyl coupling agents, epoxy coupling agents, etc., and have very wide applications in many industrial fields such as coatings, adhesives, sealants, rubber products, plastic products, etc. Zhang Xiang et al. synthesized macromolecular silane coupling agents such as molecular formula (CH3O)2(CH3)Si(CH2) 10 CH2OOCCH(CH2)(CH3) in patent CN115073755A, and screened out a preparation scheme with less pollution. The bonding strength of the macromolecular silane coupling agent prepared by adding it in porcelain-resin and then aging was significantly improved. Weiwei et al. provided a silane coupling agent containing fluorine amphiphilic segment in patent CN107434843A, which had significant inhibition on biofilm and provided a basis for realizing non-toxic antifouling, but did not consider the coating and labor costs during use and maintenance.

[0003] Amphiphilic segment can make the target modified material obtain hydrophilic group and lipophilic group at the same time. The principle is to graft or copolymerize hydrophilic segment and lipophilic segment to the target modified material in sequence to obtain dendritic or star-shaped block copolymer. By adjusting the types and proportions of hydrophilic segment and lipophilic segment, the amphiphilic modification of polymer, coating or modified material can be carried out, and the antifouling property, recoatability, hydrophilicity and compatibility with water-based paint can be actively adjusted. Liu Min et al. in “Amphiphilic block copolymer modified nano-silica particles and their applications” combined ATRP and Click methods to synthesize μ-(PEG45-b-PS25-b-PIPSMA25) star-shaped heteroarm triblock copolymer with amphiphilicity for the first time, and found that the nano-silica modified by the copolymer had great improvement in the stability of Pickering emulsion. Liu Zhu et al. in “Synthesis of amphiphilic block copolymer and influence of mass ratio of hydrophilic segment and lipophilic segment on self-assembly morphology” successfully synthesized amphiphilic block copolymer PAA41-b-PMAEFcn by ATRP polymerization method, and explored the influence of mass ratio of hydrophilic segment and lipophilic segment on the self-assembly property of polymer in water.

[0004] Currently, the main method of modifying amphiphilic segments is to copolymerize or separately polymerize hydrophilic groups and lipophilic groups, then connect them, and then graft the obtained product with silane coupling agent. In Synthesis and characterization of nanocomposites from amphipathy polyester grafted modified sericite and methylsilicone resin, B Jiang et al. prepared an oligoester with amphiphilic properties with a molecular weight of 600 from sebacic acid and polyethylene glycol in toluene solution. In Synthesis of high density amphiphilic grafted polymer brushes and their self-assembly, Dang Jingya et al. prepared reaction monomers using LiAlH4, end methylene tetrahydrophthalic anhydride, and CHCl3, and successfully polymerized polymers containing amphiphilic segments.

[0005] However, the existing amphiphilic silane coupling agent has the problems of hydrophobicity, difficulty in re-coating the anti-fouling coating, poor adhesion of the re-coated coating, and the like. SUMMARY

[0006] The present application is to solve the above problems, and aims to provide an amphiphilic modified silane coupling agent, a preparation method thereof, and an application thereof, which has good compatibility in water, can improve the hydrophobicity, water resistance, and anti-fouling property of the coating, reduce the surface energy of the coating, and provide a hydrophilic anchoring site to effectively improve the re-coatability of the coating.

[0007] The present application provides a preparation method of an amphiphilic modified silane coupling agent, which has the following characteristics, comprising the following steps:

[0008] Step 1: reacting a hydrophilic polymer containing a hydroxyl group with a halogenated acyl halide in the presence of an acid binding agent and a first solvent to obtain an ATRP initiator;

[0009] Step 2: reacting the ATRP initiator with an acrylate monomer in the presence of a metal salt catalyst, a ligand, and a second solvent to obtain an active macromolecule containing amphiphilic groups;

[0010] Step 3: reacting the active macromolecule containing amphiphilic groups with a silane compound containing an amino group in the presence of a base reagent and a third solvent to obtain the amphiphilic modified silane coupling agent.

[0011] In the preparation method of the amphiphilic modified silane coupling agent provided by the present application, the hydrophilic polymer containing a hydroxyl group can be selected from any one or more of polyethylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol, and polypropylene glycol monobutyl ether.

[0012] In the method for preparing the dual parent modified silane coupling agent provided by the present application, it can also have the feature that in step 1, the molar ratio of the hydrophilic polymer containing hydroxyl groups, the halogenated acyl halide and the acid binding agent is 1: (0.25-3): (0.2-5), preferably 1: (0.5-2): (0.5-2).

[0013] In the method for preparing the dual parent modified silane coupling agent provided by the present application, it can also have the feature that in step 1, the reaction time is 4-24h, such as 4h, 6h, 8h, 12h, 16h, 20h or 24h, and the stirring speed is 200-600 rad / min.

[0014] In the method for preparing the dual parent modified silane coupling agent provided by the present application, it can also have the feature that the acrylic ester monomer is selected from any one or more of n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate or t-butyl methacrylate.

[0015] In the method for preparing the dual parent modified silane coupling agent provided by the present application, it can also have the feature that in step 2, the molar ratio of the ATRP initiator, the acrylic ester monomer, the metal salt catalyst and the ligand is 1: (0.2-5): (0.2-5): (0.6-1.8), preferably 1: (0.5-2): (0.5-2): (0.8-1.2).

[0016] In the method for preparing the dual parent modified silane coupling agent provided by the present application, it can also have the feature that in step 2, the reaction temperature is 80-150℃, such as 80℃, 90℃, 110℃, 130℃, 150℃, the reaction time is 1-8h, such as 1h, 1.5h, 2h, 3h, 4h, 5h, and the stirring speed is 200-600 rad / min.

[0017] In the preparation method of the parent modified silane coupling agent provided by the application, the amino-containing silane compound can be selected from any one or more of γ-aminopropyl triethoxysilane (cas number: 919-30-2, model KH550, structural formula NH2(CH2)3Si(OC2H5)3), N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane (cas number: 1760-24-3, model KH792, structural formula NH2(CH2)2NH(CH2)3Si(OCH3)3), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane (cas number: 3069-29-2, model KH602, structural formula NH2(CH2)2NH(CH2)3SiCH3(OCH3)2), γ-methacryloyloxypropyl trimethoxysilane (cas number: 2530-85-0, model KH570, structural formula CH2C(CH3)COO(CH2)3Si(OCH3)3), γ-methacryloyloxypropyl methyl dimethoxysilane (cas number: 14513-34-9, model KH572, structural formula CH2C(CH3)COO(CH2)3Si(OCH3)2CH3), and 3-(acryloyloxy)propyl trimethoxysilane (cas number: 4369-14-6, model KH5750, structural formula CH2CHCOO(CH2)3Si(OCH3)3).

[0018] In the preparation method of the parent modified silane coupling agent provided by the application, the molar ratio of the active macromolecule containing the parent group, the amino-containing silane compound, and the alkali reagent in step 3 can be (1-2):(1-10):(1-10), preferably 1:(2-5):(2-5).

[0019] In the preparation method of the parent modified silane coupling agent provided by the application, the reaction temperature in step 3 can be 60-150°C, the reaction time can be 6-24h, such as 6h, 8h, 10h, 12h, 15h, and the stirring speed can be 200-600rad / min.

[0020] In the preparation method of the parent modified silane coupling agent provided by the application, the preparation method can further comprise the following steps:

[0021] In step 1, the hydrophilic polymer containing a hydroxyl group is dissolved in a first solvent, halogen acyl halide and an acid binding agent are added under an ice water bath, and the reaction is carried out under an ice water bath and inert gas protection for 6-10h to obtain an ATRP initiator.

[0022] Step 2, the ATRP initiator is dissolved in a second solvent, an acrylate monomer is added, and after quick freezing and thawing, a metal salt catalyst and a ligand are added, and the temperature is raised to 110-150°C under inert gas protection for 2-5h, and then the product is post-processed to obtain an active macromolecule containing a double parent group;

[0023] Step 3, the active macromolecule containing a double parent group, the silane compound containing an amino group, the third solvent, and the base reagent are mixed, and the temperature is raised to 90-110°C for 18-36h, and then the product is post-processed to obtain the double parent modified silane coupling agent.

[0024] The application also provides a double parent modified silane coupling agent, which has the following characteristics and has the following structural formula:

[0025]

[0026] In the above formula, n:m=(1-5):(1-5), 7≤n≤90. Preferably, the double parent modified silane coupling agent is prepared by the preparation method of the double parent modified silane coupling agent described above.

[0027] The application also provides an application of the double parent modified silane coupling agent in a coating, which has the following characteristics, the coating comprises:

[0028] 70-80 parts by weight of a hydroxyl acrylic resin, 20-25 parts by weight of an isocyanate curing agent, 0.2-1 parts by weight of the double parent modified silane coupling agent of claim 9, 0.3-0.7 parts by weight of a dispersing agent, 0.3-0.7 parts by weight of an antifoaming agent, and 0.4-0.8 parts by weight of a leveling agent.

[0029] Effects and advantages of the application

[0030] According to the double parent modified silane coupling agent and the preparation method thereof, a hydrophilic polymer containing a hydroxyl group is selected to provide a hydrophilic group segment, and an acrylate monomer is selected to provide a hydrophobic segment, thereby preparing a new silane coupling agent with double parent macromolecular segments, so that the silane coupling agent can be effectively applied in a coating, which not only improves the interface performance between an inorganic surface and an organic coating, but also effectively improves the tensile strength, water resistance, and anti-pollution property of the coating. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 is an infrared spectrum of the ATRP initiator prepared in Example 1 of the application;

[0032] Figure 2 is a nuclear magnetic resonance spectrum of the active macromolecule containing a double parent group prepared in Example 1 of the application;

[0033] Figure 3Permeation gel chromatography of the active macromolecule containing two hydrophilic groups prepared in Example 1 of the present application;

[0034] Figure 4 Infrared spectrum of the amphiphilic modified silane coupling agent prepared in Example 1 of the present application;

[0035] Figure 5 Resulting graph of the water resistance test in Test Example 2 of the present application, wherein (a) is the resulting graph of the water resistance test of the coating prepared in Example 8, (b) is the resulting graph of the water resistance test of the coating prepared in Comparative Example 1, and (c) is the resulting graph of the water resistance test of the coating prepared in Comparative Example 2. DETAILED DESCRIPTION

[0036] In order to make the technical means, creative features, purposes and effects achieved by the present application easy to understand, the present application is specifically described below in combination with examples and drawings.

[0037] In the following examples, each reagent and equipment is a commercially available product unless otherwise specified.

[0038] In the following examples, the isocyanate curing agent used is Wuhan Shexing S-208, the leveling agent is Shendu SN-4034, the wetting agent is Shendu SN-3704, and the defoaming agent is Ona F291.

[0039] <Example 1>

[0040] An amphiphilic modified silane coupling agent

[0041] The present example provides an amphiphilic modified silane coupling agent and a preparation method thereof, and the reaction equation is as follows:

[0042]

[0043] comprising the following steps:

[0044] Step 1, a three-necked flask is used to prepare a 0.33 mol / L solution of 0.01 mol of polyethylene glycol monomethyl ether in dichloromethane, 0.01 mol of triethylamine and 0.013 mol of 2-bromoisobutyryl bromide are slowly added under ice water bath conditions, the mixture is uniformly stirred, and the synthesis is carried out under ice water bath and nitrogen environment, after 8 h of reaction, a white liquid is obtained, the sample is extracted 3-5 times with a saturated sodium bicarbonate solution and deionized water, and the macromolecular ATRP initiator (A) containing a hydrophilic group is obtained after rotary evaporation;

[0045] The obtained macromolecular ATRP initiator (A) containing a hydrophilic group is subjected to Fourier infrared (FTIR) test, and the test result is shown in Figure 1 .

[0046] AsFigure 1 stretching vibration absorption peak of C=O appeared; 1108 cm -1 stretching vibration absorption peak of C=O appeared; 1108 cm -1 stretching vibration absorption peak of C-O-C appeared, which can be observed to successfully synthesize ester group, representing the successful synthesis of target ATRP initiator (A).

[0047] Step 2, 0.005 mol of the above ATRP initiator (A) and anisole were added in a three-neck flask to prepare a 0.05 mol / L solution of ATRP initiator, and 0.005 mol of butyl acrylate was added to make the equation n:m=1:1, and the mixture was uniformly stirred, then it was frozen with liquid nitrogen and thawed after cooling, 0.005 mol of cuprous bromide was added and 0.005 mol of pentamethyldivinyltriamine was slowly added, and then the mixture was uniformly mixed and heated to 130℃ under nitrogen atmosphere, and reacted for 3h to obtain a dark yellow transparent liquid, which was co-precipitated with methanol solution and chromatographed, and then a yellow-brown viscous liquid was obtained by rotary evaporation, which was a macromolecular organic compound (B) containing double hydrophilic groups;

[0048] The macromolecular organic compound (B) containing double hydrophilic groups obtained was subjected to nuclear magnetic resonance hydrogen spectrum NMR-H test and permeation gel chromatography GPC test, and the test results are shown in Figures 2-3 .

[0049] As shown in Figure 2 , the O-CH2 absorption peak is at 3.72 ppm, and the CH2 absorption peak is at 1.57 ppm, combined with Figure 3 GPC number average molecular weight shown, it can be inferred that the macromolecular organic compound (B) containing double hydrophilic groups is successfully polymerized.

[0050] Step 3, 0.01 mol of the above macromolecular organic compound (B) containing double hydrophilic groups was prepared into a 0.5 mol / L solution using anisole in a three-neck flask, and 0.03 mol of sodium carbonate and 0.03 mol of γ-aminopropyl triethoxysilane (KH550) were added therein, and then the mixture was uniformly mixed and heated to 100℃, and an orange yellow solution was obtained after reacting for 24h, which was extracted with methanol solution and rotary evaporated to obtain a light yellow viscous liquid, which was a double-hydrophilic modified silane coupling agent (C).

[0051] The double-hydrophilic modified silane coupling agent (C) obtained was subjected to Fourier infrared FTIR test, and the test results are shown in Figure 4 .

[0052] As shown in Figure 4 , the bending vibration absorption peak of secondary amino-NH appeared at 1454 cm -1 ; the bending vibration absorption peak of primary amino-NH appeared at 1043 cm -1 ; and the bending vibration absorption peak of primary amino-NH appeared at 1097 cm -1ether bond-C-O-C in-plane bending vibration absorption peak and out-of-plane bending vibration absorption peak, 1724 cm -1 is the stretching vibration absorption peak of C=O, which can be inferred that the target amphiphilic modified silane coupling agent (C) is successfully synthesized.

[0053] <Embodiment 2>

[0054] An amphiphilic modified silane coupling agent

[0055] The embodiment provides an amphiphilic modified silane coupling agent and a preparation method thereof, a reaction equation is same as that of the embodiment, and the preparation method comprises the following steps:

[0056] Step 1, a three-necked flask is used to prepare 0.01 mol of polyethylene glycol monomethyl ether into a 0.33 mol / L solution by using dichloromethane, 0.01 mol of triethylamine and 0.013 mol of 2-bromoisobutyryl bromide are slowly added under the condition of an ice water bath, after uniform mixing and stirring, synthesis is carried out under the condition of maintaining the ice water bath and a nitrogen environment, after 8 hours of reaction, a white liquid is obtained, the sample is extracted 3-5 times by using a saturated sodium bicarbonate solution and deionized water, and after rotary evaporation, a macromolecular ATRP initiator (A) containing a hydrophilic group is obtained;

[0057] Step 2, 0.005 mol of the ATRP initiator (A) and anisole are added into a three-necked flask to prepare a 0.05 mol / L solution of the ATRP initiator, 0.01 mol of butyl acrylate is added, so that n:m=1:2 in the equation, after uniform mixing and stirring, the solution is frozen by using liquid nitrogen and then thawed after cooling, 0.005 mol of cuprous bromide and 0.005 mol of pentamethyldiethylenetriamine are added, after uniform mixing, the solution is heated to 130 DEG C under a nitrogen environment, after 3 hours of reaction, a dark yellow transparent liquid is obtained, the liquid is co-precipitated by using a methanol aqueous solution and is subjected to chromatography column, a yellow-brown viscous liquid is obtained, which is a macromolecular organic substance (B) containing an amphiphilic group;

[0058] Step 3, 0.01 mol of the macromolecular organic substance (B) containing the amphiphilic group is prepared into a 0.5 mol / L solution by using anisole, and 0.03 mol of sodium carbonate and 0.03 mol of γ-aminopropyl triethoxysilane (KH550) are added into the solution, after uniform mixing, the solution is heated to 100 DEG C, after 24 hours of reaction, an orange-yellow solution is obtained, the solution is extracted by using a methanol aqueous solution and is subjected to rotary evaporation, and a light yellow viscous liquid is obtained, which is an amphiphilic modified silane coupling agent (C).

[0059] <Embodiment 3>

[0060] An amphiphilic modified silane coupling agent

[0061] The embodiment provides a kind of amphiphilic modified silane coupling agent and its preparation method, reaction equation is same with embodiment, including the following steps:

[0062] Step 1, 0.01 mol of polyethylene glycol monomethyl ether is prepared into 0.33 mol / L solution using dichloromethane in three-necked flask, 0.01 mol of triethylamine and 0.013 mol of 2-bromoisobutyryl bromide are slowly added under ice-water bath condition, after mixing and stirring uniformly, synthesis is carried out under ice-water bath and nitrogen environment, after reaction for 8h, white liquid is obtained, sample is extracted 3-5 times using saturated sodium bicarbonate solution and deionized water, and after rotary evaporation, macromolecular ATRP initiator (A) containing hydrophilic group can be obtained;

[0063] Step 2, 0.01 mol of the above ATRP initiator (A) and anisole are added in three-necked flask to prepare 0.05 mol / L solution of ATRP initiator, and 0.005 mol of butyl acrylate is added, so that n:m=2:1 in equation, after mixing and stirring uniformly, after cooling after using liquid nitrogen, 0.01 mol of cuprous bromide and 0.01 mol of pentamethyldiethylenetriamine are added, after mixing uniformly, temperature is increased to 130 DEG C under nitrogen environment, after reaction for 3h, dark yellow transparent liquid is obtained, co-precipitation is carried out by methanol aqueous solution and is chromatographed, and then yellow-brown viscous liquid is obtained, that is, macromolecular organic matter (B) containing amphiphilic group;

[0064] Step 3, 0.01 mol of the above macromolecular organic matter (B) containing amphiphilic group is prepared into 0.5 mol / L solution using anisole in three-necked flask, and 0.03 mol of sodium carbonate and 0.03 mol of gamma-aminopropyl triethoxysilane (KH550) are added therein, after mixing uniformly, temperature is increased to 100 DEG C, after reaction for 24h, orange yellow solution is obtained, after extraction by methanol aqueous solution and rotary evaporation, light yellow viscous liquid is obtained, that is, amphiphilic modified silane coupling agent (C).

[0065] <Embodiment 4>

[0066] A recoatable long-acting low surface energy coating

[0067] The embodiment provides a preparation method of a recoatable long-acting low surface energy coating, including the following steps:

[0068] 74.3 parts of hydroxyl acrylic resin, 23.2 parts of isocyanate curing agent, 0.9 parts of amphiphilic modified macromolecular silane coupling agent prepared according to the method in embodiment 1, 0.5 parts of wetting agent, 0.5 parts of defoaming agent, 0.6 parts of leveling agent are weighed according to weight parts, and are mixed in a mixer to obtain a mixture.

[0069] <Embodiment 5>

[0070] A recoatable long-lasting low surface energy coating

[0071] The embodiment provides a preparation method of a recoatable long-lasting low surface energy coating, and the method comprises the following steps:

[0072] The hydroxyl acrylic resin, the isocyanate curing agent, the amphiphilic modified macromolecular silane coupling agent, the wetting agent, the defoaming agent and the leveling agent are weighed according to the weight parts, and are mixed in a mixer to obtain a mixture.

[0073] <Embodiment 6>

[0074] A recoatable long-lasting low surface energy coating

[0075] The embodiment provides a preparation method of a recoatable long-lasting low surface energy coating, and the method comprises the following steps:

[0076] The hydroxyl acrylic resin, the isocyanate curing agent, the amphiphilic modified macromolecular silane coupling agent, the wetting agent, the defoaming agent and the leveling agent are weighed according to the weight parts, and are mixed in a mixer to obtain a mixture.

[0077] <Embodiment 7>

[0078] A recoatable long-lasting low surface energy coating

[0079] The embodiment provides a preparation method of a recoatable long-lasting low surface energy coating, and the method comprises the following steps:

[0080] The hydroxyl acrylic resin, the isocyanate curing agent, the amphiphilic modified macromolecular silane coupling agent, the wetting agent, the defoaming agent and the leveling agent are weighed according to the weight parts, and are mixed in a mixer to obtain a mixture.

[0081] <Embodiment 8>

[0082] A recoatable long-lasting low surface energy coating

[0083] The embodiment provides a preparation method of a recoatable long-lasting low surface energy coating, and the method comprises the following steps:

[0084] The hydroxyl acrylic resin, the isocyanate curing agent, the amphiphilic modified macromolecular silane coupling agent, the wetting agent, the defoaming agent and the leveling agent are weighed according to the weight parts, and are mixed in a mixer to obtain a mixture.

[0085] <Comparative Example 1>

[0086] A coating

[0087] The present comparative example provides a preparation method of a coating, comprising the following steps:

[0088] 75 parts by weight of hydroxyl acrylic resin, 23.4 parts by weight of isocyanate curing agent, 0.5 parts by weight of wetting agent, 0.5 parts by weight of defoaming agent, 0.6 parts by weight of leveling agent, were weighed and mixed uniformly in a mixer.

[0089] <Comparative Example 2>

[0090] A coating

[0091] The present comparative example provides a preparation method of a coating, comprising the following steps:

[0092] 74.3 parts by weight of hydroxyl acrylic resin, 23.2 parts by weight of isocyanate curing agent, 0.9 parts by weight of amino silane coupling agent KH550, 0.5 parts by weight of wetting agent, 0.5 parts by weight of defoaming agent, 0.6 parts by weight of leveling agent, were weighed and mixed uniformly in a mixer.

[0093] <Test Example 1>

[0094] Water contact angle / intercoat adhesion test

[0095] In the present test example, the water contact angle / intercoat adhesion test was carried out on the coatings provided by Examples 4-8 and Comparative Examples 1-2.

[0096] The test method of water contact angle was according to the national standard “GB / T 30447-2013”, using a contact angle tester to test the contact angle between the coating film and water.

[0097] The test method of intercoat adhesion was according to the national standard “GB / T 5210-2006”, using a pull-off adhesion tester to test the intercoat adhesion.

[0098] The test results are shown in Table 1.

[0099] Table 1 Water contact angle / intercoat adhesion test results

[0100]

[0101] As shown in Table 1, the use of the amphiphilic modified silane coupling agent prepared by Examples 4-8 can effectively improve the hydrophobic performance of the coating, and also has good intercoat adhesion after recoating.

[0102] <Test Example 2>

[0103] Water resistance test

[0104] The test provided the coating of example 8 and comparative examples 1-2 for water resistance test, the test method according to national standard GB / T 1733-1993, using transparent adhesive tape to seal the edge of the tinplate after curing, and 2 / 3 of the position is placed under the deionized water, and the defects such as bubble, rust, peeling or discoloration are observed after 240h.

[0105] The test results are shown in table 2 and Figure 5 .

[0106] Table 2 water resistance test results

[0107]

[0108] As shown in table 2, comparative example 1 and comparative example 2 show better performance in water, and compared with comparative example 1 and comparative example 2, the water resistance of example 8 does not decrease obviously after introducing the amphiphilic group, only slight swelling occurs, and it recovers after 24h. It is proved that the introduction of amphiphilic group has no obvious effect on its water resistance.

[0109] Effects of the embodiments

[0110] According to the amphiphilic modified silane coupling agent and its preparation method involved in the above embodiment, because hydrophilic polymer containing hydroxyl group is selected to provide hydrophilic group segment, and acrylate monomer is selected to provide hydrophobic segment, a new silane coupling agent with amphiphilic macromolecular segment is prepared, so the silane coupling agent provided by the above embodiment can be effectively applied in coating, which can not only improve the interface performance between inorganic surface and organic coating, but also effectively improve the adhesion strength, anti-fouling performance and adhesion strength after recoating, while effectively guaranteeing the waterproof performance.

[0111] The above embodiments are preferred cases of the present application and do not limit the protection scope of the present application.

Claims

1. A method for preparing an amphiphilic modified silane coupling agent, characterized in that, Includes the following steps: Step 1: In the presence of an acid-binding agent and a first solvent, a hydrophilic polymer containing hydroxyl groups reacts with a haloacyl halide to obtain an ATRP initiator. Step 2: In the presence of a metal salt catalyst, ligand, and a second solvent, the ATRP initiator reacts with an acrylate monomer to obtain an active macromolecule containing an amphiphilic group. Step 3: In the presence of an alkaline reagent and a third solvent, the active macromolecule containing amphiphilic groups reacts with a silane compound containing amino groups to obtain an amphiphilic modified silane coupling agent.

2. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that: in, The hydrophilic polymer containing hydroxyl groups is selected from any one or more of polyethylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol, and polypropylene glycol monobutyl ether.

3. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that: in, In step 1, the molar ratio of the hydrophilic polymer containing hydroxyl groups, the haloacyl halide, and the acid-binding agent is 1:(0.25-3):(0.2-5).

4. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that: in, The acrylate monomers are selected from any one or more of n-butyl acrylate, tert-butyl acrylate, n-butyl methacrylate, or tert-butyl methacrylate.

5. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that: in, In step 2, the molar ratio of ATRP initiator, acrylate monomer, metal salt catalyst and ligand is 1:(0.2-5):(0.2-5):(0.6-1.8).

6. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that: in, The amino-containing silane compound is selected from any one or more of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane.

7. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that: in, In step 3, the molar ratio of the active macromolecule containing amphiphilic groups, the silane compound containing amino groups, and the base reagent is (1-2):(1-10):(1-10).

8. The method for preparing the amphiphilic modified silane coupling agent according to claim 1, characterized in that, Includes the following steps: Step 1: Dissolve the hydrophilic polymer containing hydroxyl groups in the first solvent, add the haloacyl halide and acid-binding agent under an ice-water bath, and react for 6-10 hours under an ice-water bath and inert gas protection to obtain the ATRP initiator. Step 2: Dissolve the ATRP initiator in the second solvent, add acrylate monomers, freeze and thaw, add metal salt catalyst and ligands, and react at 110-150℃ for 2-5 hours under inert gas protection. After post-treatment, an active macromolecule containing amphiphilic groups is obtained. Step 3: Mix the active macromolecule containing amphiphilic groups, the silane compound containing amino groups, the third solvent, and the alkaline reagent, heat to 90-110℃ and react for 18-36 hours, then perform post-treatment to obtain the amphiphilic modified silane coupling agent.

9. An amphiphilic modified silane coupling agent, characterized in that, The structural formula is as follows: ； In the above formula, n:m = (1-5):(1-5), 7≤n≤90.

10. The application of amphiphilic modified silane coupling agents in coatings, characterized in that, The coating includes: The composition, by weight, comprises 70-80 parts hydroxyl acrylic resin, 20-25 parts isocyanate curing agent, 0.2-1 parts amphiphilic modified silane coupling agent as described in claim 9, 0.3-0.7 parts dispersant, 0.3-0.7 parts defoamer, and 0.4-0.8 parts leveling agent.

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