阅读说明：本技术 一种双亲性硅基功能聚合物及其制备方法和应用 (Amphiphilic silicon-based functional polymer and preparation method and application thereof ) 是由 崔家喜 郑宜君 王宏 于 2020-06-24 设计创作，主要内容包括：本发明公开了一种双亲性硅基功能聚合物及其制备方法和应用,属于高分子材料技术领域,通过将含有活泼氢的聚甲基硅氧烷与含有烯基的功能化化合物混合搅拌均匀,使用催化剂,在室温下开放环境中,制得硅基功能聚合物,此类材料一方面可以作为硅油润滑剂的添加剂,另一方面也可以作为硅树脂基底的添加剂。本发明的硅基功能聚合物,具有可调节的亲/疏水微相分离的表面、荷电中性和接受氢键的表面,具有良好的广谱抗海洋污损生物吸附,在海洋防污方面具有广阔的应用前景,其合成工艺简单易行,抗污染广谱性好,绿色环保,产率高,制备成本低,易于推广。(The invention discloses an amphiphilic silicon-based functional polymer and a preparation method and application thereof, belonging to the technical field of high molecular materials. The silicon-based functional polymer has an adjustable hydrophilic/hydrophobic microphase separation surface, a charge neutral surface and a hydrogen bond accepting surface, has good broad-spectrum marine fouling organism adsorption resistance, has a wide application prospect in the aspect of marine antifouling, and has the advantages of simple and feasible synthesis process, good pollution resistance broad-spectrum property, environmental friendliness, high yield, low preparation cost and easy popularization.)

1. An amphiphilic silicon-based functional polymer is characterized in that the structural formula is as follows:

wherein R is

R₁is H,

2. The method of claim 1, wherein the structural formula of the amphiphilic silicon-based functional polymer is:

wherein R is

R₁is H

3. The method for preparing amphiphilic silicon-based functional polymer according to claim 1 or 2, comprising the steps of:

s1, uniformly mixing polymethylsiloxane containing active hydrogen with a functional compound containing alkenyl or a polymer with terminal alkenyl functional groups to obtain a mixed solution;

s2, adding a noble metal catalyst into the mixed liquor obtained in the step S1, and stirring and reacting for 10-20h at room temperature in an open system to obtain the catalyst.

4. The method for preparing amphiphilic silicon-based functional polymer according to claim 3, wherein the molar ratio of the polymethylsiloxane containing active hydrogen in S1 to the alkenyl-containing functional compound or the terminal alkenyl-functional polymer is 1: 1-100.

5. The method according to claim 3, wherein the functionalized alkenyl-containing compound in S1 is a neutral-charged zwitterion containing alkenyl, a hydrophilic polyethylene glycol chain, a hydrophobic alkane chain with a terminal group at the other end containing chlorine, bromine, hydroxyl, carboxyl, sulfonic acid group, amino group, quaternary ammonium salt, or a polymer chain with repeating units of one or more of the foregoing compounds.

6. The method of claim 3, wherein the functionalized polymer with terminal alkenyl group in S1 is at least one of polyethylene glycol-block-polyethylene, polyethylene glycol-block-polytetrafluoroethylene, polyethylene glycol-block-polystyrene, polyethylene glycol-block-polyolefin, polyethylene glycol-block-polyvinyl chloride, polyethylene glycol-block-polycaprolactone, or polyethylene glycol-block-polymethacrylic acid-1H, 1H-perfluorooctyl ester.

7. The method of claim 3, wherein the noble metal catalyst in S2 is Pt, Pd, Rh, Ag or Ru.

8. The method for preparing amphiphilic silicon-based functional polymer according to claim 3, wherein the ratio of the catalyst to the polymethylsiloxane in S2 is 1.5-3 μ L: 1g of the total weight of the composition.

9. Use of the amphiphilic silicon-based functional polymer according to claim 1 or 2 for the preparation of a product resistant to marine biofouling.

10. The use according to claim 9, wherein the amphiphilic silicon-based functional polymer is mixed with silicone oil and applied to a surface to be protected against marine biofouling.

Technical Field

The invention belongs to the technical field of high molecular materials, and particularly relates to an amphiphilic silicon-based functional polymer, and a preparation method and application thereof.

Background

With the increasing frequency of global trade activities, the transportation industry has been developed vigorously. In terms of energy efficiency, waterway transportation is far better than aviation, road and railway transportation, the global waterway transportation industry is continuously expanded to form ships with larger volume and stronger power. The waterway transportation of China is developed vigorously, and as early as 2005, the waterway transportation amount of China reaches 21.96 million t, and the container transportation amount is 2.1992 million t according to the statistical data of the Ministry of communication of the people's republic of China, wherein 1396.15 million TEUs (20-foot containers are 1 standard box TEU) are transported by ocean, and the acceleration rate is increased by 15.6% every year. Although the energy saving efficiency of waterway transportation is better, the energy consumption is also quite large due to the rapid development of the global waterway transportation industry, and the greenhouse effect and the air pollution are aggravated.

The problem of marine biofouling is one of the major causes of high energy consumption for the water shipping industry, and costs up to $ 2000 million each year. Can cause marine fouling of more than 2000 species, and animals (more than 1300 species) such as barnacle, Concha Ostreae, calx, sea squirt, Bryozoans, mussels, and sea anemone; the plants (more than 600 kinds) such as seaweed, diatom, water cloud and enteromorpha, wherein more than 50 kinds of marine fouling organisms are common.

After marine organisms are attached to the bottom of a ship sailing in seawater, the quality and sailing resistance of the ship can be increased, the sailing speed is reduced, the fuel consumption is correspondingly increased, and the abrasion degree of mechanical equipment parts is increased. The adhesion of marine fouling organisms can cause the metal surface protective film to be damaged, so that the metal is directly exposed in seawater, the electrochemical balance of the metal surface can be changed, the metal corrosion is accelerated, and the maintenance frequency of the ship is increased. It has been reported that a ship with marine pollutants attached thereto will consume 40% more oil than a clean hull, thereby increasing the greenhouse effect and harming the environment. Meanwhile, the ship bottom fouling greatly increases the roughness of the ship shell, so that the navigation resistance of the ship is increased, and the fuel consumption is increased.

In order to reduce the adhesion of marine fouling organisms on ships, various antifouling technologies are researched, but the coating of antifouling paint is the cheapest, most effective and most convenient way to solve the problem of marine organism adhesion. The antifouling paint products used by the prior ships mainly comprise cuprous oxide antifouling paint, organic antifouling paint, inorganic self-polishing antifouling paint and low-surface-energy antifouling paint. The cuprous oxide antifouling paint generally has unstable poison leaching rate, rough surface and poor broad spectrum, and particularly accelerates the release of an antifouling agent due to poor mechanical strength and high-speed stripping action of a coating when a ship sails, so that only the pollution to the marine ecological environment is increased; the tin-free self-polishing antifouling paint has reduced or even no effect on antifouling effect if the ship speed is too low or the berthing time is too long; the low surface energy antifouling paint is basically nontoxic and has the minimum influence on marine ecology, but the static antifouling effect is not ideal enough, and the low surface energy antifouling paint can only be used for dynamic antifouling and has the problems of poor adhesion with a bottom layer anticorrosive paint, no inhibition effect on adhesion of bryophytes and algae and the like. Therefore, an antifouling paint with excellent performance should have the advantages of good antifouling effect, long effective antifouling period, economy, small influence on the environment (no heavy metal, no insecticide) and the like.

Some hydrophobic silicon-based super-lubricating materials have been developed at present, and the purpose of reducing the adsorption of marine fouling organisms is achieved by utilizing a hydrophobic surface. While these coatings can be effective in reducing the low adhesion problems of barnacles, mussels etc., the hydrophobic nature of the surface attracts other organisms such as diatoms, leading to a constant growth in the hull mucus, still causing a large degree of hydrodynamic drag.

Disclosure of Invention

The invention aims to: aiming at the problems that the prior art lacks of excellent antifouling materials aiming at pollutants and marine biofouling, the prepared antifouling paint only aims at partial pollutants, and the related application is limited, an amphiphilic silicon-based functional polymer, and a preparation method and application thereof are provided.

The technical scheme adopted by the invention is as follows:

an amphiphilic silicon-based functional polymer, the structural formula is as follows:

wherein R is

R₁Is H,

The preparation method of the amphiphilic silicon-based functional polymer comprises the following steps:

s1, uniformly mixing polymethylsiloxane containing active hydrogen with a functional compound containing alkenyl or a polymer with terminal alkenyl functional groups to obtain a mixed solution;

s2, adding a noble metal catalyst into the mixed liquor obtained in the step S1, and stirring and reacting for 10-20h at room temperature in an open system to obtain the catalyst.

Further, the structural formula is: the structural formula is as follows:

wherein R is

R₁Is H,

Furthermore, the molar ratio of the polymethylsiloxane containing active hydrogen in S1 to the functionalized compound containing alkenyl or the polymer functionalized by terminal alkenyl is 1: 1-100.

Further, the functionalized compound containing alkenyl group or the polymer functionalized by terminal alkenyl group in S1 is a polymer chain containing alkenyl group, a charge neutral zwitterion, a hydrophilic polyethylene glycol chain, a hydrophobic alkane chain of which the other terminal group contains chlorine, bromine, hydroxyl, carboxyl, sulfonic acid group, amino group, quaternary ammonium salt, or a combination of repeating units of one or more of the foregoing compounds.

Further, the polymer functionalized by the end-group alkenyl in the S1 is at least one of polyethylene glycol-block-polyethylene, polyethylene glycol-block-polytetrafluoroethylene, polyethylene glycol-block-polystyrene, polyethylene glycol-block-polyolefin, polyethylene glycol-block-polyvinyl chloride, polyethylene glycol-block-polycaprolactone or polyethylene glycol-block-polymethacrylic acid-1H, 1H-perfluorooctyl ester.

Further, the noble metal catalyst in S2 is platinum, palladium, rhodium, silver, or ruthenium.

Further, the ratio of the catalyst to the polymethylsiloxane in S2 is 1.5 to 3 μ L: 1g of a compound; preferably 3 μ L: 1g of the total weight of the composition.

The functional group of the invention can be added with polymethyl siloxane containing active hydrogen under the action of a catalyst to form a compound containing alkenyl. Provided that the reaction is carried out for 10 to 20 hours, preferably 15 hours, at room temperature in an open system.

According to the invention, the charge neutral amphipathy is realized by the following two ways, firstly, the charge neutral amphipathy is realized by modifying polydimethylsiloxane and a charge neutral compound on a hydrophobic polymethyl siloxane side chain containing active hydrogen; and secondly, modifying polydimethylsiloxane, a compound with positive charges and negative charges and a polymethylsiloxane side chain containing active hydrogen simultaneously to realize charge neutral amphipathy.

The charge neutral compounds are mainly three types, namely phosphorylcholine zwitterions (such as 2-methacryloyloxyethyl phosphorylcholine), sulfobetaine zwitterions (such as sulfobetaine methacrylate and 3- (methacrylamide) propyl-dimethyl (3-sulfonic acid) ammonium hydroxide) and carboxylic betaine zwitterions (such as 2- (2-methacryloyloxyethyl dimethylamino) acetate). The compound with positive charges is a quaternary ammonium salt compound, and the compound with negative charges is a compound containing carboxyl, sulfonic acid group and phosphoric acid group.

The second way is to modify an amphiphilic chain segment on a hydrophobic polymethylsiloxane side chain, and realize the hydrophilic-hydrophobic difference on the same chain segment, wherein the amphiphilic chain segment can be: polyethylene glycol-block-polyethylene, polyethylene glycol-block-polytetrafluoroethylene, polyethylene glycol-block-polystyrene, polyethylene glycol-block-polyacene, polyethylene glycol-block-polyvinyl chloride, polyethylene glycol-block-polycaprolactone, polyethylene glycol-block-polymethacrylic acid-1H, 1H-perfluorooctyl ester, and the like.

Therefore, the invention realizes the amphiphilic surface by modifying the hydrophilic chain segment and the hydrophobic chain segment on the hydrophobic polymethylsiloxane side chain and utilizing the microphase separation caused by different hydrophilicity and hydrophobicity of the polymer material, thereby effectively reducing the adsorption of organisms such as diatom which are only resistant to the hydrophobic surface and the adsorption of barnacles, mussels and the like which are resistant to the hydrophilic surface. The charged neutral molecules and the chlorine-containing molecules have good antibacterial performance, and can realize the antibacterial attachment and fouling of the material.

In addition, because alkynyl, hydroxyl, carboxyl and the like are introduced into the end group on the polymethyl siloxane main chain, the polymer chain is fixed on the chemical surface under the action of a chemical bond, ideal chemical fixation is realized, and compared with the fixation of common physical coating, the adhesion capability of the coating can be greatly improved, and the mechanical property of the coating is further improved. Effectively solves the problems in practical application, such as paint bubbling above fish eyes and waterlines, coating falling, poor mechanical property and the like.

Furthermore, the prepared amphiphilic polymer can be directly bound to the surface of the substrate, and the liquid polymer brush with the super-smooth function is prepared.

The amphiphilic silicon-based functional polymer is applied to preparation of marine organism fouling resistant products.

Further, the amphiphilic silicon-based functional polymer is mixed with silicone oil and coated on the surface needing to resist marine organism fouling.

Further, using a mixture of the amphiphilic silicon-based functional polymer and silicone oil, a lubricant containing a hydrophilic component can be prepared, which can be impregnated into a porous substrate to obtain a super-smooth surface.

Further, the mixture of the amphiphilic silicon-based functional polymer and the silicone oil is directly bound to the surface of the substrate, so that the liquid polymer brush with the super-smooth function can be prepared.

In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:

1. the amphiphilic silicon-based functional polymer has an adjustable amphiphilic surface, and the amphiphilic surface caused by microphase separation can effectively reduce the adsorption of marine fouling organisms; the charged neutral surface and the surface receiving hydrogen bonds can effectively avoid protein adsorption, and the charged neutral surface and the surface receiving hydrogen bonds can introduce chlorine-containing molecules and simultaneously show excellent antibacterial attachment and fouling resistance;

2. the amphiphilic silicon-based functional polymer has an adjustable surface structure, can effectively reduce the adsorption of marine fouling organisms, and has a wide application prospect in the aspect of marine organism fouling resistance;

3. the preparation method of the amphiphilic silicon-based functional polymer has the advantages of simple and feasible process, environmental protection, high yield, low preparation cost and easy popularization.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a nuclear magnetic diagram of an amphiphilic silicon-based functional polymer prepared in example 1;

FIG. 2 is an optical microscope image of the amphiphilic silicon-based functional polymer in a porous state;

FIG. 3 is a diagram of an embodiment of the amphiphilic silicon-based functional polymer of the present invention;

FIG. 4 is a porous super-slip diagram of an amphiphilic silicon-based functional polymer of the present invention;

FIG. 5 is a drawing showing the protein adsorption resistance of the amphiphilic silicon-based functional polymer surface coating material according to the present invention;

FIG. 6 is an antibacterial pattern of the amphiphilic silicon-based functional polymer surface coating material of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.

Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.

It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The features and properties of the present invention are described in further detail below with reference to examples.