Preparation method and application of super-hydrophobic copolymer

Abstract

The invention provides a preparation method and application of a super-hydrophobic copolymer. The method for preparing the super-hydrophobic copolymer comprises the following steps: S1) mixing polydimethylsiloxane with a first silane coupling agent, and generating single-terminated polydimethylsiloxane at a first temperature; s2) mixing the single-terminated polydimethylsiloxane with a first initiator, and generating a PDMS-b-PS (Polydimethylsiloxane-b-Polystyrene) copolymer at a second temperature; and S3) mixing a second initiator, acrylic acid group-polyhedral oligomeric silsesquioxane and the PDMS-b-PS copolymer, and generating the super-hydrophobic copolymer at a third temperature.

Description

Technical Field

[0001] The invention relates to a super hydrophobic copolymer. Background Art

[0002] Since the beginning of the 21st century, superwetting surfaces represented by superhydrophobic surfaces and superamphiphobic surfaces have emerged in the fields of corrosion resistance, ice resistance, self-cleaning and oil-water separation, which has greatly promoted the development of the materials field. In recent years, the preparation technology of superwetting surfaces has become increasingly mature, and many superwetting surfaces with various excellent properties have been successfully prepared, and they have played a unique role in practical life and engineering applications.

[0003] However, the super-hydrophobic compounds in the prior art still have shortcomings. Summary of the invention

[0004] One of the present invention provides a method for preparing a super hydrophobic copolymer, which comprises the following steps:

[0005] S1) mixing polydimethylsiloxane and a first silane coupling agent at a first temperature to generate a single-terminated polydimethylsiloxane;

[0006] S2) mixing the mono-terminated polydimethylsiloxane and the first initiator to generate a PDMS-b-PS copolymer at a second temperature;

[0007] S3) mixing a second initiator, an acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer to generate the super hydrophobic copolymer at a third temperature.

[0008] In one embodiment, in step S1), the pH value is adjusted to alkaline before heating to the first temperature; preferably the pH value is adjusted to 9.5 to 10.

[0009] In one embodiment, in step S1), the pH value is adjusted with at least one of sodium hydroxide, potassium hydroxide and ammonia.

[0010] In a specific embodiment, in step S1), the first silane coupling agent is added in an amount such that the viscosity of the reaction solution is 550 to 570 mPa.s at the first temperature.

[0011] In a specific embodiment, in step S2), the mass ratio of the single-end-capped polydimethylsiloxane to the first initiator is 1:2 to 10:1.

[0012] In a specific embodiment, in step S3), the mass ratio of the acrylic-cage polysilsesquioxane to the PDMS-b-PS copolymer is 1:1 to 1:10.

[0013] In a specific embodiment, in step S3), the mass ratio of the acrylic-cage polysilsesquioxane to the PDMS-b-PS copolymer is 3:17 to 2:3.

[0014] In a specific embodiment, based on the total mass of the acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer as 100%, the amount of the acrylic-cage polysilsesquioxane is 15% to 40%, and the amount of the PDMS-b-PS copolymer is 60% to 85%.

[0015] In a specific embodiment, based on the total mass of the acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer as 100%, the amount of the second initiator is 0.1% to 2%.

[0016] In a specific embodiment, based on the total mass of the acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer as 100%, the amount of the second initiator is 0.5% to 2%.

[0017] In one embodiment, the first temperature is 70 to 80°C.

[0018] In one embodiment, the second temperature is 50 to 70°C.

[0019] In one embodiment, the third temperature is 95 to 110°C.

[0020] In one embodiment, in step S1), the reaction time at the first temperature is 0.5 to 3 hours.

[0021] In one embodiment, in step S2), the copolymerization reaction takes place at the second temperature for 18 to 32 hours.

[0022] In a specific embodiment, in step S3), the copolymerization reaction takes place at the third temperature for 5 to 10 hours.

[0023] In a specific embodiment, the first initiator is prepared by the following method:

[0024] Styrene, cyclohexane and tetrahydrofuran are uniformly mixed, and n-butyl lithium is added under the protection of an inert gas, and the mixture is stirred for reaction, and then the reaction is terminated, precipitated and separated to obtain the first initiator.

[0025] In a specific embodiment, the mass ratio of the styrene to the n-butyl lithium is 1:5 to 1:8.

[0026] In one embodiment, the reaction time is 30 to 80 min.

[0027] In one specific embodiment, aminopropyl di-terminated polydimethylsiloxane is mixed with an azo initiator and the initiator B is prepared through an esterification condensation reaction.

[0028] In one specific embodiment, the second initiator is prepared by the following method:

[0029] 1) aminopropyl di-terminated polydimethylsiloxane and the second azo initiator are uniformly mixed with dichloromethane and dimethylformamide to obtain a mixed solution;

[0030] 2) dissolving N,N'-dicyclohexylcarboximide in dichloromethane to obtain an N,N'-dicyclohexylcarboximide solution;

[0031] 3) mixing the N,N'-dicyclohexylcarboximide solution and the mixed solution, and reacting them to obtain the second initiator.

[0032] In a specific embodiment, in step 1), the mass ratio of the aminopropyl di-terminated polydimethylsiloxane to the azo initiator is 10:1.

[0033] In one embodiment, in step 1), the pH value of the mixed solution is 9.5 to 10.

[0034] In a specific embodiment, dimethylaminopyridine p-toluenesulfonate is used to adjust the pH value so that the pH value of the mixed solution is 9.5 to 10.

[0035] In a specific embodiment, in step 2), the mass content of the N,N'-dicyclohexylcarbocyanine in the N,N'-dicyclohexylcarbocyanine solution is 15% to 25%.

[0036] In one embodiment, in step 3), the reaction temperature is 40 to 50° C., and the reaction time is 6 to 12 h.

[0037] In a specific embodiment, the first silane coupling agent and the second silane coupling agent are independently at least one of KH550, KH560, KH570, A171, A151 and A172.

[0038] The second aspect of the present invention provides the use of a super hydrophobic copolymer prepared according to any one of the methods of the first aspect of the present invention in at least one of anti-corrosion, anti-icing, self-cleaning and oil-water separation.

[0039] Beneficial effects of the present invention:

[0040] The super-hydrophobic compound prepared by the present invention is coated on a glass surface by a spin coating method, and the water contact angle measured can reach 164.9±0.5° or more. The super-hydrophobic compound has strong hydrophobicity, can meet the high requirements of current super-hydrophobic materials, and has broad application prospects. DETAILED DESCRIPTION

[0041] The present invention will be further described below in conjunction with examples, but the examples of the present invention are only exemplary descriptions, and the implementation methods do not constitute limitations of the present invention under any circumstances.

[0042] Polydimethylsiloxane was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0043] Aminopropyl di-terminated polydimethylsiloxane was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0044] Example 1

[0045] Preparation of initiator A:

[0046] Cyclohexane and tetrahydrofuran were added to styrene monomer, and under the protection of inert gas, n-butyl lithium was slowly added (the mass ratio of styrene monomer to n-butyl lithium was 1:5), and the reaction was stirred for 30 minutes. Then, anhydrous ethanol was added to terminate the reaction, and anhydrous ethanol was used for precipitation. The precipitate was separated to obtain initiator A.

[0047] Preparation of initiator B:

[0048] The aminopropyl dicapped polydimethylsiloxane is mixed with an azo initiator and an initiator B is prepared through an esterification condensation reaction as follows:

[0049] 1) Add 5 g of azo initiator KH550 to 50 g of aminopropyl dicapped polydimethylsiloxane, then add 200 g of dichloromethane and 15 g of dimethylformamide (DMF), stir and mix well, adjust the pH value to 10 with dimethylaminopyridine p-toluenesulfonate (DPTS), and obtain a mixed solution;

[0050] 2) dissolving N,N'-dicyclohexylcarboximide (DCC) in dichloromethane to obtain a DCC solution with a mass fraction of 15%;

[0051] 3) Add the DCC solution into the mixed solution so that the mass fraction of DCC in the whole system is 3%, and stir the mixture at 40° C. for 12 h to obtain initiator B.

[0052] A copolymer super-hydrophobic compound, the preparation steps of which are as follows:

[0053] S1) mixing polydimethylsiloxane and silane coupling agent KH550, stirring and mixing evenly, adjusting the pH value to 9.5 with sodium hydroxide, heating to 70° C., and continuously adding silane coupling agent according to the viscosity change until the viscosity is 550 mPa.s at 70° C., to generate single-end polydimethylsiloxane;

[0054] S2) mixing the mono-terminated polydimethylsiloxane and the initiator A in a mass ratio of 5:1, stirring and mixing evenly, and heating to 60° C. for copolymerization reaction for 18 h to obtain a PDMS-b-PS copolymer;

[0055] S3) adding 0.5 g of initiator B and 15 g of acrylic-cage polysilsesquioxane to 85 g of PDMS-b-PS copolymer, heating to 110° C. under nitrogen protection, performing copolymerization for 5 h, and filtering to separate the precipitate to obtain POSS-b-PDMS-b-PS copolymer A.

[0056] Example 2

[0057] Preparation of initiator A:

[0058] Cyclohexane and tetrahydrofuran were added to styrene monomer, and under the protection of inert gas, n-butyl lithium was slowly added (the mass ratio of styrene monomer to n-butyl lithium was 1:8), and the reaction was stirred for 80 minutes. Then, anhydrous ethanol was added to terminate the reaction, and anhydrous ethanol was used for precipitation. The precipitate was separated to obtain initiator A.

[0059] Preparation of initiator B:

[0060] The aminopropyl dicapped polydimethylsiloxane is mixed with an azo initiator and an initiator B is prepared through an esterification condensation reaction as follows:

[0061] 1) Add 3 g of azo initiator KH570 to 30 g of aminopropyl dicapped polydimethylsiloxane, then add 200 g of dichloromethane and 15 g of dimethylformamide (DMF), stir and mix well, adjust the pH value to 10 with dimethylaminopyridine p-toluenesulfonate (DPTS), and obtain a mixed solution;

[0062] 2) dissolving N,N'-dicyclohexylcarboximide (DCC) in dichloromethane to obtain a DCC solution with a mass fraction of 25%;

[0063] 3) Add the DCC solution into the mixed solution so that the mass fraction of DCC in the whole system is 2.5%, and stir the reaction at 50° C. for 6 h to obtain initiator B.

[0064] A copolymer super-hydrophobic compound, the preparation steps of which are as follows:

[0065] S1) mixing polydimethylsiloxane and silane coupling agent KH560, stirring and mixing evenly, adjusting the pH value to 10.0 with potassium hydroxide, heating to 80° C., and continuously adding silane coupling agent according to the viscosity change until the viscosity is 570 mPa.s at 80° C., to generate single-end polydimethylsiloxane;

[0066] S2) mixing the mono-terminated polydimethylsiloxane and the initiator A in a mass ratio of 1:2, stirring and mixing evenly, and heating to 50° C. for copolymerization reaction for 32 hours to obtain a PDMS-b-PS copolymer;

[0067] S3) Add 2 g of initiator B and 40 g of acrylic-cage polysilsesquioxane to 60 g of PDMS-b-PS copolymer, heat to 95° C. under nitrogen protection, carry out copolymerization for 10 h, and filter to separate the precipitate to obtain POSS-b-PDMS-b-PS copolymer B.

[0068] Example 3

[0069] Preparation of initiator A:

[0070] Cyclohexane and tetrahydrofuran were added to styrene monomer, and under the protection of inert gas, n-butyl lithium was slowly added (the mass ratio of styrene monomer to n-butyl lithium was 1:6), the reaction was stirred for 60 minutes, and then anhydrous ethanol was added to terminate the reaction, and anhydrous ethanol was used for precipitation, and the precipitate was separated to obtain initiator A.

[0071] Preparation of initiator B:

[0072] The aminopropyl dicapped polydimethylsiloxane is mixed with an azo initiator and an initiator B is prepared through an esterification condensation reaction as follows:

[0073] 1) Add 5 g of azo initiator A171 to 50 g of aminopropyl dicapped polydimethylsiloxane, then add 200 g of dichloromethane and 15 g of dimethylformamide (DMF), stir and mix well, and then adjust the pH value to 9.5 with dimethylaminopyridine p-toluenesulfonate (DPTS) to obtain a mixed solution;

[0074] 2) dissolving DCC (N,N'-dicyclohexylcarboximide) in dichloromethane to obtain a DCC solution with a mass fraction of 20%;

[0075] 3) Add the DCC solution into the mixed solution so that the mass fraction of DCC in the whole system is 3%, and stir the mixture at 50° C. for 8 h to obtain initiator B.

[0076] A copolymer super-hydrophobic compound, the preparation steps of which are as follows:

[0077] S1) mixing polydimethylsiloxane and silane coupling agent A171, stirring and mixing evenly, adjusting the pH value to 10.0 with ammonia, heating to 75° C., and continuously adding silane coupling agent according to the change in viscosity until the viscosity is 560 mPa.s at 75° C., to generate single-end polydimethylsiloxane;

[0078] S2) mixing the mono-terminated polydimethylsiloxane and the initiator A in a mass ratio of 10:1, stirring and mixing evenly, and heating to 70° C. for copolymerization reaction for 25 h to obtain a PDMS-b-PS copolymer;

[0079] S3) Add 1 g of initiator B and 30 g of acrylic-cage polysilsesquioxane to 69 g of PDMS-b-PS copolymer, heat to 100° C. under nitrogen protection, carry out copolymerization for 6 h, and filter to separate the precipitate to obtain POSS-b-PDMS-b-PS copolymer C.

[0080] Performance measurement

[0081] POSS-b-PDMS-b-PS copolymer A, POSS-b-PDMS-b-PS copolymer B and POSS-b-PDMS-b-PS copolymer C were respectively coated on the glass surface by spin coating, and the water contact angle was measured by using εrma angle meter contact angle meter (Japan Kyowa Company, G-1 type), and the measurement results were as follows: the water contact angle of POSS-b-PDMS-b-PS copolymer A can reach 165.2±0.5°; the water contact angle of POSS-b-PDMS-b-PS copolymer B can reach 164.9±0.5°; the water contact angle of POSS-b-PDMS-b-PS copolymer C can reach 167.0±0.5°. The above data show that the POSS-b-PDMS-b-PS copolymer prepared by the present invention has strong hydrophobicity.

[0082] Although the present invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that various changes may be made without departing from the true spirit and scope of the present invention. In addition, the subject matter, spirit and scope of the present invention may be varied to accommodate specific situations, materials, material combinations and methods. All of these changes are included within the scope of the claims of the present invention.

Claims

1. A method for preparing a super hydrophobic copolymer, comprising the steps of: S1) mixing polydimethylsiloxane and a first silane coupling agent to generate single-end polydimethylsiloxane at a first temperature; S2) mixing the mono-terminated polydimethylsiloxane and the first initiator to generate a PDMS-b-PS copolymer at a second temperature; S3) mixing a second initiator, an acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer to generate the super hydrophobic copolymer at a third temperature.

2. The method according to claim 1, characterized in that In step S1), the pH value is adjusted to alkaline before heating to the first temperature; preferably the pH value is adjusted to 9.5 to 10; Preferably, in step S1), the pH value is adjusted with at least one of sodium hydroxide, potassium hydroxide and ammonia.

3. The method according to claim 1, characterized in that In step S1), the first silane coupling agent is added in an amount such that the viscosity of the reaction solution is 550 to 570 mPa.s at the first temperature.

4. The method according to claim 1, characterized in that In step S2), the mass ratio of the single-end polydimethylsiloxane to the first initiator is 1:2 to 10:

1.

5. The method according to claim 1, characterized in that In step S3), the mass ratio of the acrylic-cage polysilsesquioxane to the PDMS-b-PS copolymer is 1:1 to 1:10; Preferably, the mass ratio of the acrylic-cage polysilsesquioxane to the PDMS-b-PS copolymer is 3:17 to 2:3; Preferably, based on the total mass of the acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer as 100%, the amount of the acrylic-cage polysilsesquioxane is 15% to 40%, and the amount of the PDMS-b-PS copolymer is 60% to 85%; Preferably, the amount of the second initiator is 0.1% to 2%, based on the total mass of the acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer as 100%; Preferably, based on the total mass of the acrylic-cage polysilsesquioxane and the PDMS-b-PS copolymer as 100%, the amount of the second initiator is 0.5% to 2%.

6. The method according to claim 1, characterized in that The first temperature is 70 to 80° C.; and / or The second temperature is 50 to 70°C; and / or The third temperature is 95 to 110°C.

7. The method according to claim 1, characterized in that In step S1), the reaction time at the first temperature is 0.5 to 3 hours; and / or In step S2), the copolymerization reaction takes place at the second temperature for 18 to 32 hours; and / or In step S3), the copolymerization reaction takes place at the third temperature for 5 to 10 hours.

8. The method according to claim 1, characterized in that The first initiator is prepared by the following method: Mix styrene, cyclohexane and tetrahydrofuran evenly, add n-butyl lithium under the protection of inert gas, stir to react, then terminate the reaction, precipitate, separate, and obtain the first initiator; Preferably, the mass ratio of the styrene to the n-butyl lithium is 1:5 to 1:8; Preferably, the reaction time is 30 to 80 min; and / or The aminopropyl dicapped polydimethylsiloxane is mixed with an azo initiator, and an initiator B is prepared through an esterification condensation reaction; Preferably, the second initiator is prepared by the following method: 1) mixing aminopropyl di-terminated polydimethylsiloxane and the second azo initiator with dichloromethane and dimethylformamide to obtain a mixed solution; 2) dissolving N,N'-dicyclohexylcarboximide in dichloromethane to obtain an N,N'-dicyclohexylcarboximide solution; 3) mixing the N,N'-dicyclohexylcarboximide solution and the mixed solution, reacting to obtain the second initiator; Preferably, in step 1), the mass ratio of the aminopropyl dicapped polydimethylsiloxane to the azo initiator is 10:1; preferably, the pH value of the mixed solution is 9.5 to 10; preferably, the pH value is adjusted with dimethylaminopyridine p-toluenesulfonate so that the pH value of the mixed solution is 9.5 to 10; Preferably, in step 2), the mass content of the N,N'-dicyclohexylcarboximide in the N,N'-dicyclohexylcarboximide solution is 15% to 25%; Preferably, in step 3), the reaction temperature is 40 to 50° C., and the reaction time is 6 to 12 h.

9. The method according to claim 8, characterized in that The first silane coupling agent and the second silane coupling agent are independently at least one of KH550, KH560, KH570, A171, A151 and A172.

10. Use of the super hydrophobic copolymer prepared according to any one of claims 1 to 9 in at least one of anti-corrosion, anti-icing, self-cleaning and oil-water separation.