Preparation method and application of super-hydrophobic copolymer

Abstract

The invention provides a preparation method and application of a super-hydrophobic copolymer. The method comprises the following steps: 1) generating a POSS-PMMA (polyhedral oligomeric silsesquioxane-polymethyl methacrylate) copolymer from epoxy group-containing polyhedral oligomeric silsesquioxane, polymethyl methacrylate and a first initiator at a first temperature; and 2) generating the super-hydrophobic copolymer from the POSS-PMMA copolymer under the action of a second initiator at a second temperature.

Description

Technical Field

[0001] The invention provides 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] 1) generating a POSS-PMMA copolymer by reacting a cage-type polysilsesquioxane containing an epoxy group, polymethyl methacrylate and a first initiator at a first temperature;

[0006] 2) generating the super hydrophobic copolymer by reacting the POSS-PMMA copolymer with a second initiator at a second temperature.

[0007] In a specific embodiment, in step 1), the mass ratio of the cage-type polysilsesquioxane to polymethyl methacrylate is 1:1 to 4:1.

[0008] In one specific embodiment, in step 1), cage-type polysilsesquioxane and polymethyl methacrylate are mixed with tetrahydrofuran to obtain a reaction system, and based on the mass of the reaction system being 100%, the amount of the first initiator is 0.3% to 0.5%.

[0009] In a specific embodiment, the epoxy-containing cage-type polysilsesquioxane is a cage-type polysilsesquioxane-triepoxy group.

[0010] In a specific embodiment, the first initiator is azobisisobutyronitrile.

[0011] In one embodiment, in step 1), the copolymerization reaction time is 3 to 6 hours; and / or

[0012] In one specific embodiment, in step 2), the copolymerization reaction time is 5 to 10 hours.

[0013] In a specific embodiment, in step 2), the mass ratio of the second initiator to the POSS-PMMA copolymer is 1:2 to 1:2.5.

[0014] In one specific embodiment, the second initiator is hydroxyl mono-terminated polydimethylsiloxane, which can be purchased from conventional commercial companies, such as Shanghai Dingfen Chemical Technology Co., Ltd., or can be self-made.

[0015] In a specific embodiment, the hydroxyl mono-terminated polydimethylsiloxane is prepared by the following method: polydimethylsiloxane and a silane coupling agent are mixed, stirred and mixed evenly, the pH value is adjusted to alkaline to obtain a reaction solution, and heated to a third temperature to generate hydroxyl mono-terminated polydimethylsiloxane.

[0016] In one embodiment, the pH is adjusted using at least one of sodium hydroxide, potassium hydroxide and ammonia.

[0017] In one embodiment, the pH is adjusted to between 10 and 11.

[0018] In one embodiment, the amount of the silane coupling agent added is such that the viscosity of the reaction solution is 550 to 570 mPa.s at the third temperature.

[0019] In a specific embodiment, the silane coupling agent is at least one of KH550, KH560, KH570, A171, A151 and A172.

[0020] In a specific embodiment, the first temperature is 55 to 65°C.

[0021] In one embodiment, the second temperature is 75 to 85°C.

[0022] In one embodiment, the third temperature is 35 to 80°C.

[0023] The second aspect of the present invention provides the use of a super hydrophobic copolymer prepared by 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. Beneficial effects of the present invention:

[0024] 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 161.7±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

[0025] 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.

[0026] Example 1

[0027] Polydimethylsiloxane was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0028] Azobisisobutyronitrile was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0029] A super hydrophobic compound, the preparation steps are as follows:

[0030] S1) drying the polydimethylsiloxane under a nitrogen environment, mixing the polydimethylsiloxane and the silane coupling agent A171, stirring evenly, adjusting the pH value to 10 with sodium hydroxide, heating to 60° C. under nitrogen protection, and continuously adding the silane coupling agent A171 according to the viscosity change until the viscosity is 560 mPa.s at 60° C., thereby generating a hydroxyl-terminated polydimethylsiloxane;

[0031] S2) mixing cage-type polysilsesquioxane-triepoxy and polymethyl methacrylate (PMMA) in a mass ratio of 2:1, and adding azobisisobutyronitrile and solvent tetrahydrofuran to obtain a reaction system, heating the reaction system to 55° C. under nitrogen protection to carry out copolymerization reaction for 6 hours, and then filtering to separate the precipitate to obtain a POSS-PMMA copolymer;

[0032] Wherein, taking the total mass of the reaction system as 100%, the sum of the mass of the cage-type polysilsesquioxane-triepoxy and polymethyl methacrylate accounts for 5%, and the sum of the mass of azobisisobutyronitrile accounts for 0.4%;

[0033] S3) The initiator hydroxyl mono-terminated polydimethylsiloxane is dissolved in benzene to prepare an initiator solution with a mass concentration of 20% (the total mass of the initiator solution is taken as 100%), and then the initiator and the POSS-PMMA copolymer are added to the initiator solution in a mass ratio of 1:2, and the temperature is raised to 75°C under nitrogen protection, and the reaction is carried out for 10 hours, and then the precipitate is separated by filtration to obtain the target product A, i.e., POSS-PMMA-b-PDMS super hydrophobic compound A.

[0034] Example 2

[0035] Polydimethylsiloxane was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0036] Azobisisobutyronitrile was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0037] S1) drying the polydimethylsiloxane under a nitrogen environment, mixing the polydimethylsiloxane and the silane coupling agent A171, stirring evenly, adjusting the pH value to 11 with sodium hydroxide, heating to 35° C. under nitrogen protection, and continuously adding the silane coupling agent A151 according to the viscosity change until the viscosity is 550 mPa.s at 30° C., thereby generating a hydroxyl-terminated polydimethylsiloxane;

[0038] S2) mixing cage-type polysilsesquioxane-triepoxy and PMMA in a mass ratio of 1:1, and adding azobisisobutyronitrile and solvent tetrahydrofuran to obtain a reaction system, heating the reaction system to 65° C. under nitrogen protection to carry out copolymerization reaction for 3 hours, and then filtering to separate the precipitate to obtain a POSS-PMMA copolymer;

[0039] Wherein, taking the total mass of the reaction system as 100%, the sum of the mass of the cage-type polysilsesquioxane-triepoxy and polymethyl methacrylate accounts for 2%, and the sum of the mass of azobisisobutyronitrile accounts for 0.3%;

[0040] S3) The initiator hydroxyl mono-terminated polydimethylsiloxane is dissolved in benzene to prepare an initiator solution with a mass concentration of 20% (the total mass of the initiator solution is taken as 100%), and then the initiator and the POSS-PMMA copolymer are added to the initiator solution at a mass ratio of 1:2.5, and the temperature is raised to 85°C under nitrogen protection, and the reaction is carried out for 5 hours, and then the precipitate is separated by filtration to obtain the target product B, i.e., POSS-PMMA-b-PDMS super hydrophobic compound B.

[0041] Example 3

[0042] Polydimethylsiloxane was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0043] Azobisisobutyronitrile was purchased from Shanghai Dingfen Chemical Technology Co., Ltd.

[0044] S1) After drying the polydimethylsiloxane under a nitrogen environment, the polydimethylsiloxane and the silane coupling agent A171 are mixed, stirred evenly, the pH value is adjusted to 10.5 with potassium hydroxide, heated to 80° C. under nitrogen protection, and the silane coupling agent A172 is continuously added according to the viscosity change until the viscosity is 570 mPa.s at 80° C., thereby generating a hydroxyl-terminated polydimethylsiloxane;

[0045] S2) mixing cage-type polysilsesquioxane-triepoxy and PMMA in a mass ratio of 4:1, and adding azobisisobutyronitrile and solvent tetrahydrofuran to obtain a reaction system, heating the reaction system to 60° C. under nitrogen protection to carry out copolymerization reaction for 5 hours, and then filtering to separate the precipitate to obtain a POSS-PMMA copolymer;

[0046] Wherein, taking the total mass of the reaction system as 100%, the sum of the mass of the cage-type polysilsesquioxane-triepoxy and polymethyl methacrylate accounts for 10%, and the sum of the mass of azobisisobutyronitrile accounts for 0.5%;

[0047] S3) The initiator hydroxyl mono-terminated polydimethylsiloxane is dissolved in benzene to prepare an initiator solution with a mass concentration of 20% (the total mass of the initiator solution is taken as 100%), and then the initiator and the POSS-PMMA copolymer are added to the initiator solution at a mass ratio of 1:2.5, and the temperature is raised to 80°C under nitrogen protection, and the reaction is carried out for 8 hours, and then the precipitate is separated by filtration to obtain the target product C, i.e., POSS-PMMA-b-PDMS super hydrophobic compound C.

[0048] Performance measurement

[0049] The target product A, the target product B and the target product C were dissolved in tetrahydrofuran (the total amount of tetrahydrofuran and the target product was calculated as 100%) at a concentration of 2 wt %, and then coated on the glass surface by spin coating, leveled, dried, and the water contact angle was measured using an εrma angle meter contact angle measuring instrument (Japan Kyowa Company, G-1 type). The measurement results are: the water contact angle of the target product A can reach 162.4±0.5°; the water contact angle of the target product B can reach 161.7±0.5°; the water contact angle of the target product C can reach 164.1±0.5°. The above data show that the target product prepared by the present invention has strong hydrophobicity.

[0050] 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: 1) generating a POSS-PMMA copolymer by reacting a cage-type polysilsesquioxane containing an epoxy group, polymethyl methacrylate and a first initiator at a first temperature; 2) generating the super hydrophobic copolymer by reacting the POSS-PMMA copolymer with a second initiator at a second temperature.

2. The method according to claim 1, characterized in that In step 1), the mass ratio of the cage-type polysilsesquioxane to polymethyl methacrylate is 1:1 to 4:

1.

3. The method according to claim 1, characterized in that: In step 1), cage-type polysilsesquioxane and polymethyl methacrylate are mixed with tetrahydrofuran to obtain a reaction system, and the amount of the first initiator used is 0.3% to 0.5% based on the mass of the reaction system as 100%; Preferably, the epoxy-containing cage-type polysilsesquioxane is a cage-type polysilsesquioxane-triepoxy group; Preferably, the first initiator is azobisisobutyronitrile.

4. The method according to claim 1, characterized in that: In step 1), the copolymerization reaction time is 3 to 6 hours; and / or In step 2), the copolymerization reaction time is 5 to 10 hours.

5. The method according to claim 1, characterized in that In step 2), the mass ratio of the second initiator to the POSS-PMMA copolymer is 1:2 to 1:2.

5.

6. The method according to claim 1, characterized in that The second initiator is hydroxyl mono-terminated polydimethylsiloxane.

7. The method according to claim 6, characterized in that The hydroxyl mono-terminated polydimethylsiloxane is prepared by the following method: The polydimethylsiloxane and the silane coupling agent are mixed and stirred to be uniform, and then the pH value is adjusted to alkaline to obtain a reaction solution, and the reaction solution is heated to a third temperature to generate a hydroxyl mono-terminated polydimethylsiloxane; Preferably, the pH is adjusted with at least one of sodium hydroxide, potassium hydroxide and ammonia; Preferably, the pH is adjusted to 10 to 11. Preferably, the silane coupling agent is added in an amount such that the viscosity of the reaction solution is 550 to 570 mPa.s at the third temperature.

8. The method according to claim 7, characterized in that The silane coupling agent is at least one of KH550, KH560, KH570, A171, A151 and A172.

9. The method according to claim 7, characterized in that: The first temperature is 55 to 65°C; and / or The second temperature is 75 to 85°C; and / or The third temperature is 35 to 80°C.

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.