阅读说明：本技术 一种含聚乙二醇的有机硅及其制备方法 (Organic silicon containing polyethylene glycol and preparation method thereof ) 是由 张刚 何雄亮 林益军 崔武林 于 2020-07-03 设计创作，主要内容包括：本发明涉及一种新的含聚乙二醇的有机硅防污抗污材料及其制备方法和应用,本发明结合具有无毒、无刺激性具有良好的水溶性且具有自组装的聚乙二醇的优势,通过将丙烯酰氯通过一步酰氯化反应得到具有双键的聚乙二醇,再通过含铂催化剂的作用下将其引入到有机硅材料中,得到一种具有抗污防污,具有良好的生物相容性,抗菌、抗蛋白粘附等特点。该材料在生物医药领域方面及船舶的抗污防污上具有广泛的应用前景。(The invention relates to a novel polyethylene glycol-containing organic silicon antifouling material and a preparation method and application thereof, wherein the preparation method combines the advantages of non-toxic, non-irritant, good water-solubility and self-assembled polyethylene glycol, and acryloyl chloride is subjected to one-step acyl chlorination reaction to obtain polyethylene glycol with double bonds, and then the polyethylene glycol is introduced into an organic silicon material under the action of a platinum-containing catalyst to obtain the organic silicon antifouling material which has the characteristics of antifouling property, good biocompatibility, antibiosis, anti-protein adhesion and the like. The material has wide application prospect in the field of biomedicine and on the aspects of fouling resistance and fouling resistance of ships.)

1. The organic silicon containing polyethylene glycol is characterized by having the following structural formula:

wherein m n is 500-1000, p is 350-1000;

r and R1 are independently selected from C1-C6 alkyl; r2 is selected from C1-C6 alkyl and aryl; r3 is selected from C1-C6 alkyl and hydroxyl.

2. The polyethylene glycol-containing silicone according to claim 1, wherein R and R1 are independently selected from methyl and ethyl; r2 is selected from C1-C6 alkyl, methylphenyl, 2-methylphenyl.

3. A method for preparing organic silicon containing polyethylene glycol is characterized by comprising the following steps: the method comprises the following steps of carrying out hydrosilylation on polyethylene glycol diallyl ether with double bonds under the action of a catalyst to introduce polyethylene glycol to a siloxane main chain, wherein the catalyst is triethylamine.

4. The method of claim 3, wherein the synthetic route is as follows:

5. the method according to claim 3, characterized by the specific steps comprising:

s1, mixing acryloyl chloride, triethylamine and polyethylene glycol in an ice bath state, stirring for 24 hours at room temperature, filtering, dialyzing, and removing a solvent to obtain double-bond-containing polyethylene glycol;

s2, mixing siloxane and polyethylene glycol containing double bonds, adding a catalyst at 60 ℃, heating to 80 ℃, reacting for 3-5h, removing the solvent, adding water, and washing to obtain the organosilicon material containing polyethylene glycol.

6. The method of any one of claims 3-5, wherein the polyethylene glycol is PEG or OEG; the molecular weight of the PEG or OEG is 500-4000.

7. The method as claimed in claim 5, wherein in the S1, the polyethylene glycol is required to be slowly added dropwise; the dropping speed is 30-40 drops/min.

8. The method of claim 5, wherein the siloxane to polyethylene glycol molar ratio is (1-8): 1; the mole ratio of the acryloyl chloride to the triethylamine to the polyethylene glycol is 5:15: 6.

9. The method according to claim 5, wherein the catalyst in S2 is a platinum catalyst; the platinum catalyst is platinum-vinyl siloxane chelate or chloroplatinic acid; the molar amount of the platinum catalyst is that the catalyst hydrogen silicone oil-double bond modified polyethylene glycol (1-10): 100; the siloxane is low hydrogen-containing silicone oil; the hydrogen content of the low hydrogen-containing silicone oil is 0.175-0.185%, and the viscosity of the low hydrogen-containing silicone oil is 50-250mm²/s。

10. The use of the silicone material containing polyethylene glycol according to claim 1 or 2 in the fields of marine antifouling and biomedical applications.

Technical Field

The invention relates to organosilicon containing polyethylene glycol and a preparation method thereof, belonging to the field of macromolecules.

Background

With the rapid development of biomedical materials in China, the requirements and the demands for medical biology are increasing (such as heart stents, artificial heart valves, blood vessels, cardiovascular insertion tubes and the like). Generally, proteins are often adsorbed on the surface of a material, but in many cases, the phenomenon that the researchers do not want to be caused in advance, such as the adsorption of nonspecific proteins on medical materials such as biosensors and the like, infection caused by artificial bones in a human body, adhesion of marine fouling on ships, increased resistance caused by the adhesion of marine fouling, increased fuel oil and damage to the coating on the surface of the ships, is undesirable.

The self-assembled PEG or OEG monomolecular layer or the hydrogel layer of the cross-linked PEG or OEG has the advantages of good protein adhesion resistance, good hydrophilicity, very low interface free energy in water, good molecular chain flexibility, high activity, good biocompatibility and the like, and is always a hotspot of research. The charge, hydrophilic and hydrophobic chemical composition, morphology and the like in the material are important factors influencing the interaction between the material and other objects. Researches find that the introduction of a substance with good biocompatibility into the material can improve the interaction of the material and the interface between organisms and improve the application value of the material in the multilayer field

The organic silicon material is a polymer with a repeated Si-O-Si bond as a main chain Si and directly connected with an organic group, and because the polysiloxane has the advantages of no toxicity, no odor, good biocompatibility, unique low surface release energy, fouling release performance and the like. Because polysiloxane is a kind of repeated Si-O-Si bonds as a main chain, silicon atoms are connected with methyl groups, and intermolecular interaction force is small, the surface of the polysiloxane is hydrophobic, so that histiocytes are not easy to adhere.

The amphiphilic silicone material containing polyethylene glycol siloxane provided by the invention has the advantages of low cost of raw materials and simple process, and has the advantages of good biocompatibility, low toxicity, no irritation and the like.

Disclosure of Invention

Aiming at the defect of stain resistance of the organosilicon material, the invention synthesizes organosilicon containing polyethylene glycol by combining the characteristics of the organosilicon material and the advantages of low polyethylene glycol, and provides a preparation method thereof.

The technical scheme of the invention is as follows:

in order to meet the requirements of the materials, the invention adopts the following technical scheme.

The organic silicon containing polyethylene glycol has the following structural formula:

wherein m n is 500-1000, and p is 350-1000.

Wherein R and R1 are independently selected from C1-C6 alkyl; r2 is selected from C1-C6 alkyl and aryl; r3 is selected from C1-C6 alkyl and hydroxyl.

Preferably, R and R1 are independently selected from methyl and ethyl; r2 is selected from C1-C6 alkyl, methylphenyl, 2-methylphenyl.

The organosilicon containing polyethylene glycol is prepared by introducing polyethylene glycol to a siloxane main chain through hydrosilylation of polyethylene glycol diallyl ether with double bonds under the action of a catalyst.

Preferably, the catalyst is triethylamine.

The synthetic route is as follows:

the specific synthesis steps comprise:

s1, mixing acryloyl chloride, triethylamine and polyethylene glycol in an ice bath state, stirring for 24 hours at room temperature, filtering, dialyzing, and removing a solvent to obtain double-bond-containing polyethylene glycol;

s2, mixing siloxane and polyethylene glycol containing double bonds, adding a catalyst at 60 ℃, heating to 80 ℃, reacting for 3-5h, removing the solvent, adding water, and washing to obtain the organosilicon material containing polyethylene glycol.

Preferably, the polyethylene glycol is PEG or OEG.

Preferably, the PEG or OEG has a molecular weight of 500-4000.

Preferably, the polyethylene glycol is pre-dissolved in the solvent.

Preferably, the solvent is tetrahydrofuran.

Preferably, the polyethylene glycol is added dropwise slowly.

Preferably, the dropping speed is 30 to 40 drops/min.

The method has the advantages of high reaction efficiency, violent heat release in the reaction process, reaction in ice bath, and slow dropwise addition of reactants.

Preferably, the molecular weight cut off in step S1 is 500-1000.

The purpose of dialysis is to remove excess unreacted polyethylene glycol and to purify the product, the different molecular weights being determined according to the molecular weight of the polyethylene glycol.

Preferably, the catalyst described in S2 above is a platinum catalyst.

Preferably, the platinum catalyst described in the above S2 is a platinum-vinylsiloxane chelate or chloroplatinic acid.

Preferably, the molar amount of the platinum catalyst used in S2 is 100 parts by weight based on the hydrogen silicone oil-double bond-modified polyethylene glycol catalyst (1-10).

Preferably, water is added for washing 2 times.

Preferably, the solvent removed in S2 is removed by a vacuum rotary evaporator.

Preferably, the silicone is a low hydrogen silicone oil.

Preferably, the hydrogen content of the low hydrogen-containing silicone oil is 0.175-0.185%, and the viscosity of the low hydrogen-containing silicone oil is 50-300mm²/s。

The low-hydrogen silicone oil contains active Si-H bonds in molecules, can react with other chemical substances containing double bonds, hydroxyl groups and other active groups under the action of a catalyst, and has good reaction activity.

Preferably, the molar ratio of the siloxane to the polyethylene glycol is (1-8): 1; the mol ratio of the acryloyl chloride to the triethylamine to the polyethylene glycol is 5:15: 6.

preferably, the solvent in S2 is one or more of ethanol, tetrahydrofuran, dichloromethane, benzene, xylene, diethyl ether, ethyl acetate, chloroform, N-dimethylformamide, and 1, 4-dioxane.

The invention also provides application of the organic silicon material containing the polyethylene glycol in the fields of marine antifouling and biomedical treatment.

The following specifically describes the silicone containing polyethylene glycol of the present invention:

polyethylene glycol (polyethylene glycol) is a water-soluble polymer material, and has good biocompatibility due to its low interfacial free energy in water, good molecular chain flexibility and high mobility. The amount of adhesion of platelets to the surface of a hydrophilic material containing a polyethylene glycol structure is small. This may be due to the fact that it has a low surface energy due to its easy wetting by aqueous media. Therefore, it is reasonable to believe that the silicone material containing polyethylene glycol of the present invention has good biocompatibility.

According to the preparation method of the organosilicon material containing polyethylene glycol, the generated HCl is consumed by the acyl chloride of acryloyl chloride and the hydroxyl in the polyethylene glycol under the alkalescent condition, so that the reaction is carried out positively. Compared with the conventional method for preparing the organosilicon material by reversible reaction of hydroxyl and carboxylic acid in the prior art, the method has high reaction efficiency.

Compared with the prior art, the invention has the following beneficial effects:

(1) the organosilicon containing the polyethylene glycol has the advantages of good biocompatibility, safety, no toxicity, small irritation, stability and difficult deterioration.

(2) The preparation method has the advantages of easily available raw materials, low price, convenient operation, simple process and mild reaction, and the prepared product has better application prospect in the fields of marine antifouling and antifouling as well as biomedical treatment and meets the requirements of industrial production.

(3) According to the preparation method of the organosilicon material containing the polyethylene glycol, the generated HCl is consumed by the acyl chloride of the acryloyl chloride and the hydroxyl in the polyethylene glycol under the alkalescent condition, so that the reaction is carried out positively, and the high-efficiency reaction efficiency is achieved.

(4) The siloxane of the invention contains relatively active Si-H bonds in molecules, can react with other chemical substances containing double bonds, hydroxyl and other active groups under the action of a catalyst, and has good reaction activity.

Drawings

FIG. 1 is the cell viability of the samples of examples 1 to 3 of the present invention at different culture times, respectively.

Detailed Description

The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.