阅读说明：本技术 一种高分子疏水涂层及其在制备疏水瓣膜中的应用 (High-molecular hydrophobic coating and application thereof in preparation of hydrophobic valve ) 是由 王云兵 高帅 雷洋 杨立 于 2020-06-05 设计创作，主要内容包括：本发明公开了一种高分子疏水涂层及其在制备疏水瓣膜中的应用,疏水涂层由端乙烯基硅油、乙烯基硅树脂、含氢硅油、硅烷偶联剂、抑制剂、铂络合物和溶剂混合均匀后制备得到。疏水瓣膜是将疏水涂层通过浸涂、喷涂或者旋涂的方式涂覆在合成高分子心脏瓣膜上,再通过常温或者加热的方式使涂层固化所得到。经过本发明中高分子疏水涂层改性的合成高分子心脏瓣膜材料体内相容性好,在长时间的卷曲条件下不会发生变形、粘连,在使用时可以快速恢复原有形状,可以满足紧急瓣膜手术的要求。(The invention discloses a macromolecular hydrophobic coating and application thereof in preparing a hydrophobic valve. The hydrophobic valve is obtained by coating a hydrophobic coating on a synthetic polymer heart valve in a dip coating, spray coating or spin coating mode and then curing the coating in a normal temperature or heating mode. The synthetic polymer heart valve material modified by the polymer hydrophobic coating has good in-vivo compatibility, can not deform and adhere under a long-time curling condition, can quickly recover the original shape when in use, and can meet the requirements of emergency valve operation.)

1. The high-molecular hydrophobic coating is characterized by comprising the following raw materials in parts by mass: 5-40 parts of vinyl-terminated silicone oil, 1-20 parts of vinyl silicone resin, 0.1-5 parts of hydrogen-containing silicone oil, 0.5-5 parts of silane coupling agent, 0.001-0.5 part of inhibitor, 0.01-0.5 part of platinum complex and 30-93 parts of solvent; the viscosity of the vinyl-terminated silicone oil is 200-20000 mPas, the structure is shown as the formula (I),

wherein R1 is methyl, ethyl, phenyl, propyl or trifluoropropyl, and R2 is methyl, ethyl, phenyl, propyl or trifluoropropyl.

2. The polymeric hydrophobic coating according to claim 1, comprising the following raw materials in parts by mass: 30 parts of terminal vinyl dimethyl silicone oil with the viscosity of 2000mPas, 20 parts of vinyl silicone resin, 5 parts of hydrogen-containing silicone oil, 5 parts of silane coupling agent, 0.001 part of inhibitor, 0.15 part of platinum complex and 35 parts of solvent, wherein the viscosity of the terminal vinyl methyl trifluoro propyl silicone oil is 1000 mPas.

3. The polymeric hydrophobic coating of claim 1 or 2, wherein: the vinyl content in the vinyl silicone resin is 0.5 wt% -5 wt%.

4. The polymeric hydrophobic coating of claim 1 or 2, wherein: the content of active hydrogen in the hydrogen-containing silicone oil is 0.1 wt% -1.5 wt%.

5. The polymeric hydrophobic coating of claim 1 or 2, wherein: the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and gamma-methacryloxypropyltriisopropoxysilane.

6. The polymeric hydrophobic coating of claim 1 or 2, wherein: the inhibitor is at least one of tetramethyl tetravinylcyclotetrasiloxane, tetramethyl divinyl disiloxane, ethynyl cyclohexanol, butynol, tetramethyl ethylene diamine, diallyl maleate, 3-methyl-1-butyn-3 alcohol, 3-phenyl-1-butyn-3 alcohol, 3-propyl-1-butyn-3 alcohol and triphenylphosphine.

7. The polymeric hydrophobic coating of claim 1 or 2, wherein: the platinum complex is a complex of divinyltetramethyldisiloxane and chloroplatinic acid, wherein the platinum content is 500-5000 ppm.

8. The polymeric hydrophobic coating of claim 1 or 2, wherein: the solvent is at least one of heptane, n-hexane, petroleum ether and isooctane.

9. Use of the polymeric hydrophobic coating of any one of claims 1 to 8 in the preparation of a hydrophobic valve.

10. Use according to claim 9, characterized in that: the polymer hydrophobic coating is coated on the synthetic polymer heart valve in a dip-coating, spray-coating or spin-coating mode, and then the coating is solidified at the temperature of 20-80 ℃ to obtain the hydrophobic valve.

Technical Field

The invention belongs to the technical field of new medical materials, and particularly relates to a high-molecular hydrophobic coating and application thereof in preparation of a hydrophobic valve.

Background

With the increasing aging degree of the population, heart valve diseases become global huge medical problems and cause great harm to human health. According to statistics, the prevalence rate of heart valve diseases of people over 75 years old in western countries is up to 13.3%, more than 400 people exist in China for patients with heart valve diseases over 60 years old, and if the pathological damage of the heart valve of the patient reaches a certain degree, the artificial heart valve is needed to perform surgical repair.

The application of the existing heart valves except metal valves is increased year by year, and minimally invasive interventional heart valve systems which are raised in more than ten years are basically made of animal-derived pericardial tissues, so that the problem of difficult quality control is caused by the complex components and batch difference of the heart valves. In addition, the pericardial tissue biological valve needs to be stored in a glutaraldehyde solution, potential problems of the pericardial tissue biological valve are gradually obvious in the application process, and the pericardial tissue biological valve has the defects of virus infection risk, complex treatment process, high cost, easy calcification and decay and the like, and can not meet the requirements of clinical emergency valve operation.

The high polymer material has controllable synthesis, good batch stability and relatively easy quality control, and the heart valve prepared from the high polymer material can provide an alternative choice for patients. The new heart valve design can be used to solve the above problems by pre-loading the polymeric valve onto the delivery system in a dry state prior to delivery. However, the polymer valve material without surface treatment, especially the softer material, may deform and adhere under the long-term curling condition, and cannot quickly recover the original shape when in use, so that the requirement of emergency valve operation cannot be met. In addition, the untreated high molecular valve material generally has the problems of poor biocompatibility, easy generation of blood coagulation, tissue inflammation and the like.

Disclosure of Invention

The invention provides a hydrophobic coating and a preparation method of a hydrophobic valve, aiming at the problems that a preassembled type synthetic polymer heart valve without surface treatment is easy to deform, adhere and have poor biocompatibility. The prepared hydrophobic coating is coated on the synthetic polymer heart valve, and the heart valve still has good elasticity in a dry state after being cured, and has good capacity of resisting deformation and adhesion. Therefore, the valve tissue can be pre-installed on the delivery system in a dry state for a long time, can be rehydrated and unfolded after being used in a human body, plays the normal function of the valve, and solves the problem of poor biocompatibility of the synthetic polymer heart valve material.

In order to achieve the purpose, the invention adopts the technical scheme that: the polymer hydrophobic coating comprises the following raw materials in parts by mass: 5-40 parts of vinyl-terminated silicone oil, 1-20 parts of vinyl silicone resin, 0.1-5 parts of hydrogen-containing silicone oil, 0.5-5 parts of silane coupling agent, 0.001-0.5 part of inhibitor, 0.01-0.5 part of platinum complex and 30-93 parts of solvent; the viscosity of the vinyl-terminated silicone oil is 200-20000 mPas, the structure is shown as formula (I),

wherein R1 is methyl, ethyl, phenyl, propyl or trifluoropropyl, and R2 is methyl, ethyl, phenyl, propyl or trifluoropropyl.

On the basis of the technical scheme, the invention can be further improved as follows.

Further, the macromolecular hydrophobic coating comprises the following raw materials in parts by mass: 30 parts of terminal vinyl dimethyl silicone oil with the viscosity of 2000mPas, 20 parts of vinyl silicone resin, 5 parts of hydrogen-containing silicone oil, 5 parts of silane coupling agent, 0.001 part of inhibitor, 0.15 part of platinum complex and 35 parts of solvent, wherein the viscosity of the terminal vinyl methyl trifluoro propyl silicone oil is 1000 mPas.

The raw material components comprise vinyl-terminated silicone oil vinyl silicone resin, hydrogen-containing silicone oil, a silane coupling agent, an inhibitor, a platinum complex and the like. The vinyl silicone oil is used as base resin in the hydrophobic coating to participate in hydrosilylation reaction, and the vinyl silicone resin can also play a role in reinforcement in the hydrophobic coating, so that the coating has certain strength after being cured; the hydrogen-containing silicone oil is used as a cross-linking agent of the terminal vinyl silicone oil and the vinyl silicone resin in the hydrophobic coating to promote the cross-linking of the terminal vinyl silicone oil and the vinyl silicone resin, so that the coating becomes a cross-linked network structure after being cured, and the hydrogen-containing silicone oil and the silane coupling agent in the raw material act together to remarkably improve the bonding force between the hydrophobic coating and a macromolecular heart valve after being cured, so that the macromolecular hydrophobic coating can modify the heart valve more thoroughly, and the obtained hydrophobic valve has better performance; the inhibitor plays a role in inhibiting the reaction activity in the hydrophobic coating, so that the prepared hydrophobic coating is passivated, and the hydrophobic coating has better storage property at normal temperature and can be stored for a long time; the platinum complex catalyzes the hydrosilation reaction of the vinyl-terminated silicone oil, the vinyl silicone resin and the hydrogen-containing silicone oil, so that the hydrophobic coating is solidified into a cross-linked network structure.

Furthermore, the vinyl content in the vinyl silicone resin is 0.5 wt% to 5 wt%.

Furthermore, the content of active hydrogen in the hydrogen-containing silicone oil is 0.1 wt% -1.5 wt%.

In the invention, the vinyl silicone resin with 0.5-5 wt% of vinyl content and the hydrogen-containing silicone oil with 0.1-1.5 wt% of active hydrogen content are preferably selected to prepare the macromolecular hydrophobic coating, so that the curing time of the hydrophobic coating can be shortened while the reaction group has the maximum utilization rate, and the hydrophobic coating can be rapidly cured on the valve surface to form the hydrophobic valve.

Further, the silane coupling agent is at least one of gamma-methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma-methacryloxypropylmethyldimethoxysilane, gamma-methacryloxypropylmethyldiethoxysilane and gamma-methacryloxypropyltriisopropoxysilane.

Further, the inhibitor is at least one of tetramethyltetravinylcyclotetrasiloxane, tetramethyldivinyldisiloxane, ethynylcyclohexanol, butynol, tetramethylethylenediamine, diallyl maleate, 3-methyl-1-butyn-3-ol, 3-phenyl-1-butyn-3-ol, 3-propyl-1-butyn-3-ol, and triphenylphosphine.

Further, the platinum complex is a complex of divinyltetramethyldisiloxane and chloroplatinic acid, wherein the platinum content is 500-5000 ppm.

Further, the solvent is at least one of heptane, n-hexane, petroleum ether and isooctane.

The invention has the beneficial effects that: the macromolecular hydrophobic coating comprises a (methyl) acryloyloxy silane coupling agent and hydrogen-containing silicone oil, and the combination of the two can remarkably improve the bonding force of the solidified hydrophobic coating and a synthetic macromolecular heart valve material, so that the coating can be attached to the valve material for a long time. The synthetic polymer heart valve material modified by the polymer hydrophobic coating has good in-vivo compatibility, can not deform and adhere under a long-time curling condition, can quickly recover the original shape when in use, and can meet the requirements of emergency valve operation.

Drawings

Fig. 1 is a schematic view of a valve curl simulation test.

Detailed Description

The following examples are provided to illustrate specific embodiments of the present invention.