Medical silicone rubber as well as preparation method and application thereof

Abstract

The invention relates to the technical field of medical silicone rubber, in particular to medical silicone rubber and a preparation method and application thereof. The medical silicone rubber specifically comprises the following components: 80-130 parts of methyl phenyl vinyl silicone rubber; 25 to 45 parts of a reinforcing agent; 1-2 parts of a vulcanizing agent; 5-10 parts of an activator; 1-2 parts of a silane coupling agent; 0.5-2 parts of an anti-aging agent; 3-6 parts of a structure control agent; 20 to 40 parts of platinum; 10 to 20 parts of quartz powder; the structure control agent comprises hydroxyl silicone oil, polyimide and polyvinylpyrrolidone; in the structure control agent, the weight ratio of the hydroxyl silicone oil to the polyimide to the polyvinylpyrrolidone is 1: (0.1-0.6): (0.2-0.7). After the medical silicone rubber provided by the invention is used for a long time, the mechanical property is reduced slightly or hardly, and the use requirements of the medical silicone rubber can be met.

Description

Technical Field

[0001] The present application relates to the technical field of medical silicone rubber, and in particular to a medical silicone rubber and a preparation method and application thereof. Background Art

[0002] Rubber is a high-molecular compound with high elasticity, which can be divided into two types: natural rubber and synthetic rubber. Natural rubber is made by extracting gum from plants such as rubber trees and rubber grass, while synthetic rubber is made by polymerization of various monomers.

[0003] At present, the mechanical properties of medical silicone rubber decrease significantly after a long service time, so it may not meet the use requirements. Therefore, it is necessary to find a new medical silicone rubber to ensure that it still has good mechanical properties after a long service time to meet the use requirements. Summary of the invention

[0004] In order to improve the above problems, the present application provides a medical silicone rubber and a preparation method and application thereof.

[0005] The medical silicone rubber provided in this application has little or no reduction in mechanical properties after a long service life, and can meet its use requirements. The medical silicone rubber provided in this application has long-term significance for the development of the medical device field.

[0006] Compared with the silicone rubber in the prior art, the medical silicone rubber provided in the present application has higher thermal stability, and can solve the problem that the mechanical properties of the silicone rubber in the prior art decrease significantly after a long service time and may not meet the use requirements.

[0007] In the first aspect, the present application provides a medical silicone rubber, which adopts the following technical solution: A medical silicone rubber, comprising the following components in parts by weight: 80-130 parts of methylphenyl vinyl silicone rubber; 25-45 parts of reinforcing agent; 1-2 parts of vulcanizing agent; 5-10 parts of activating agent; 1-2 parts of silane coupling agent; 0.5-2 parts of antioxidant; 3-6 parts of structure control agent; 20-40 parts of platinum; 10-20 parts of quartz powder; The structure control agent includes hydroxy silicone oil, polyimide and polyvinyl pyrrolidone; In the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide and the polyvinyl pyrrolidone is 1:(0.1-0.6):(0.2-0.7).

[0008] Optionally, in the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide and the polyvinyl pyrrolidone is 1:(0.3-0.4):(0.4-0.5).

[0009] In the present application, platinum is used as a catalyst to rapidly polymerize silicone rubber and improve synthesis efficiency. At the same time, platinum can also generate more crosslinking points in the silicone rubber during the vulcanization process, thereby improving the thermal stability of the silicone rubber and extending its service life.

[0010] In the present application, a structure control agent is added to the reaction system. In the rubber industry, structuring refers to the phenomenon that an insoluble gel is generated at the contact site after the elastomeric material and the highly active reinforcing agent come into contact. Adding a structure control agent can prevent or delay the structuring effect, and the active groups of the added substance react with the active hydroxyl groups on the surface of the silica to condense, thereby preventing the interaction between the silica and the silica gel.

[0011] In the present application, the three structure control agents work together to effectively improve the mechanical properties and anti-aging ability of medical silicone rubber.

[0012] Optionally, the methylphenyl vinyl silicone rubber contains 0.3-1% vinyl and C 6 H 5 0.5-2% silicone rubber.

[0013] In the present application, the above combination can make the formed medical silicone rubber material have better cross-linking properties, thereby making its mechanical properties more excellent.

[0014] Optionally, the reinforcing agent is surface-treated precipitated silica.

[0015] In the present application, in the rubber vulcanization system, unmodified silica cannot be well dispersed and filled in the polymer, and it is difficult to form coupling bonds between polymers, thereby reducing the vulcanization efficiency and reinforcement performance. The present application modifies the surface of silica so that the surface hydroxyl groups of silica can react with chemical substances, eliminate or reduce the amount of its surface active silanol groups, and increase its dispersibility in the polymer.

[0016] Optionally, the vulcanizing agent is 2,4-dichlorobenzoyl peroxide.

[0017] Optionally, the activator is selected from any one or more of active zinc oxide and active titanium dioxide.

[0018] Optionally, the silane coupling agent is selected from any one or more of bis-[3-(triethoxysilyl)propyl]-tetrasulfide, bis-[3-(triethoxysilyl)propyl]-disulfide, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxy.

[0019] Optionally, the silane coupling agent is a mixture of bis-[3-(triethoxysilyl)propyl]-tetrasulfide and bis-[3-(triethoxysilyl)propyl]-disulfide, and the weight ratio of the two is (1-2):1.

[0020] In the present application, a silane coupling agent is added to the reaction system. The addition of the silane coupling agent can not only reduce the Mooney viscosity, heat generation and rolling resistance of the rubber, improve the processing performance of the rubber, improve the wear resistance of the vulcanized rubber, but also improve its heat resistance, water resistance and weather resistance. Silane coupling agent has become an indispensable auxiliary agent for rubber filling and modification. A large number of scientific studies have found that the dispersibility of fillers in rubber matrix directly affects the performance of filled rubber, and silane coupling agent just has a dispersing effect.

[0021] Optionally, the antioxidant is selected from any one or more of antioxidant MB, antioxidant DNP and antioxidant HPG.

[0022] In a specific embodiment, a medical silicone rubber comprises the following components: 100 parts of methylphenylvinyl silicone rubber; 30 parts of reinforcing agent; 1.2 parts of vulcanizing agent; 7 parts of activating agent; 1.5 parts of silane coupling agent; 1.3 parts of antioxidant; 4.5 parts of structure control agent; 30 parts of platinum; and 16 parts of quartz powder.

[0023] In the second aspect, the present application provides a method for preparing the above-mentioned medical silicone rubber, using the following technical solution: A preparation method for medical silicone rubber, the preparation method specifically comprises the following steps: mixing methylphenylvinyl silicone rubber, a reinforcing agent, an antioxidant, a structure control agent, platinum and quartz powder and continuously stirring, controlling the reaction temperature at 25-35°C, and kneading evenly; then heating to 180-220°C within 0.5-2h, vacuuming and reacting for 2-3h, and kneading evenly; then adding an activator and a silane coupling agent, and kneading evenly; then adding a vulcanizing agent, and kneading evenly to obtain the medical silicone rubber.

[0024] In a third aspect, the present application provides the application of the above-mentioned medical silicone rubber as a medical material in the field of medical devices.

[0025] In summary, the present application includes at least one of the following beneficial technical effects: The medical silicone rubber provided in this application has little or no reduction in mechanical properties after a long service life, and can meet its use requirements. The medical silicone rubber provided in this application has long-term significance for the development of the medical device field.

[0026] Compared with the silicone rubber in the prior art, the medical silicone rubber provided in the present application has higher thermal stability, and can solve the problem that the mechanical properties of the silicone rubber in the prior art decrease significantly after a long service time and may not meet the use requirements. DETAILED DESCRIPTION

[0027] Before describing the embodiments of the present application in detail, it should be understood that the terms used herein are only used for the purpose of describing specific embodiments. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by ordinary technicians in the field to which the terms belong.

[0028] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. Further, in the description of this application, unless otherwise specified, the meaning of "plurality" is two or more.

[0029] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0030] In the present application, the terms "comprise" or "include" are open expressions, that is, including the contents specified in the present application but not excluding other contents.

[0031] The present application provides a medical silicone rubber. The medical silicone rubber specifically comprises the following components by weight: 80-130 parts of methylphenyl vinyl silicone rubber; 25-45 parts of reinforcing agent; 1-2 parts of vulcanizing agent; 5-10 parts of activating agent; 1-2 parts of silane coupling agent; 0.5-2 parts of antioxidant; 3-6 parts of structure control agent; 20-40 parts of platinum; 10-20 parts of quartz powder; The structure control agent includes hydroxy silicone oil, polyimide and polyvinyl pyrrolidone; In the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide and the polyvinyl pyrrolidone is 1:(0.1-0.6):(0.2-0.7).

[0032] In a specific embodiment, a method for preparing medical silicone rubber comprises the following steps: The methylphenyl vinyl silicone rubber, reinforcing agent, antioxidant, structure control agent, platinum and quartz powder are mixed and continuously stirred, the reaction temperature is controlled at 25-35°C, and the mixing is uniform; then the temperature is raised to 180-220°C within 0.5-2h, vacuum reaction is carried out for 2-3h, and the mixing is uniform; then an activator and a silane coupling agent are added, and the mixing is uniform; then a vulcanizing agent is added, and the mixing is uniform to obtain the medical silicone rubber.

[0033] In order to make the purpose, technical scheme and advantages of the present application clearer, the technical scheme in the embodiments of the present application will be clearly and completely described below. Based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. The embodiments described below are exemplary and are only used to explain the present application, and cannot be interpreted as limiting the present application.

[0034] If no specific techniques or conditions are specified in the examples, the techniques or conditions described in the literature in the field or the product instructions are used. If no manufacturer is specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0035] The present application is further described in detail below in conjunction with the embodiments and test results. Example Example 1

[0036] This embodiment provides a medical silicone rubber.

[0037] The preparation method of the above-mentioned medical silicone rubber specifically comprises the following steps: According to the ratio shown in Table 1, methylphenyl vinyl silicone rubber, surface-treated precipitated silica, antioxidant HPG, hydroxy silicone oil, polyimide, polyvinyl pyrrolidone, platinum and quartz powder were put into the reactor, stirred continuously, the reaction temperature was controlled at 30°C, and the mixture was mixed evenly; then the temperature was raised to 200°C within 1 hour, vacuumed and reacted for 2.5 hours, and the mixture was mixed evenly; then active zinc oxide, bis-[3-(triethoxysilyl)propyl]-tetrasulfide and bis-[3-(triethoxysilyl)propyl]-disulfide were added, and the mixture was mixed evenly; then 2,4-dichlorobenzoyl peroxide was added, and the mixture was mixed evenly to obtain medical silicone rubber.

[0038] The obtained sheet-like rubber is cut into strips and extruded on an extruder to obtain silicone rubber particles, which are then heated and processed through a mold into products required for medical devices.

[0039] Among them, methylphenyl vinyl silicone rubber contains 0.359% vinyl and C 6 H 5 0.765% silicone rubber. Example 2-11

[0040] Examples 2-11 provide a medical silicone rubber respectively. The difference between the above examples and Example 1 is that the addition of each component in the structure control agent is shown in Table 1. The remaining operation steps are consistent with Example 1.

[0041] The difference between Example 2-6 and Example 1 lies in the amount of polyimide added in the structure control agent.

[0042] The difference between Examples 7-11 and Example 4 is the amount of polyvinyl pyrrolidone added in the structure control agent. Comparative Example Comparative Examples 1-8

[0043] Comparative Examples 1-8 provide a medical silicone rubber respectively. The difference between the above examples and Example 1 is that the addition of each component in the structure control agent or the addition of platinum is specifically shown in Table 1. The remaining operation steps are consistent with Example 1.

[0044] The difference between Comparative Example 1 and Example 1 is that no platinum is added.

[0045] The difference between Comparative Example 2 and Example 1 is that no structure control agent is added.

[0046] The difference between Comparative Examples 3-5 and Example 1 is that the structure control agent only includes any one of hydroxy silicone oil, polyimide and polyvinyl pyrrolidone.

[0047] The difference between Comparative Examples 6-8 and Example 1 is that the structure control agent only includes any two of hydroxy silicone oil, polyimide, and polyvinyl pyrrolidone.

[0048] Table 1 Addition of each component in the above examples and comparative examples Performance testing

[0049] The mechanical properties and anti-aging tests of the medical silicone rubber prepared in the above examples and comparative examples were respectively tested.

[0050] (I) The mechanical strength of the medical silicone rubber prepared in the above examples and comparative examples was tested after preparation and after being kept in a high temperature and high humidity (85°C / 85%RH) environment for 30 days. The tensile strength (MPa) was tested according to the GB / T528-2009 standard, and the tear strength (KN / m) was tested according to the GB / T529-2008 standard.

[0051] The test results are shown in Table 2.

[0052] (ii) Using a double 85 wet heat aging test chamber, the medical silicone rubber prepared in the above embodiment and comparative example was subjected to an anti-aging test in accordance with standard GB T10586. The test results are shown in Table 2.

[0053] Table 2 Performance test results

[0054] It can be seen from the test results in Table 2 above that the medical silicone rubber provided in the present application has good mechanical properties and anti-aging ability. After a long service time, the medical silicone rubber provided in the present application can still meet its use requirements.

[0055] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example" or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0056] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A medical silicone rubber, characterized in that: The medical silicone rubber specifically comprises the following components in parts by weight: 80-130 parts of methylphenyl vinyl silicone rubber; 25-45 parts of reinforcing agent; 1-2 parts of vulcanizing agent; 5-10 parts of activating agent; 1-2 parts of silane coupling agent; 0.5-2 parts of antioxidant; 3-6 parts of structure control agent; 20-40 parts of platinum; 10-20 parts of quartz powder; The structure control agent includes hydroxy silicone oil, polyimide and polyvinyl pyrrolidone; In the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide and the polyvinyl pyrrolidone is 1:(0.1-0.6):(0.2-0.7).

2. The medical silicone rubber according to claim 1, characterized in that: In the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide and the polyvinyl pyrrolidone is 1:(0.3-0.4):(0.4-0.5).

3. The medical silicone rubber according to claim 1, characterized in that: The reinforcing agent is surface-treated precipitated silica.

4. The medical silicone rubber according to claim 1, characterized in that: The methylphenyl vinyl silicone rubber is a silicone rubber containing 0.3-1% vinyl and 0.5-2% C6H5.

5. The medical silicone rubber according to claim 1, characterized in that: The silane coupling agent is a mixture of bis-[3-(triethoxysilyl)propyl]-tetrasulfide and bis-[3-(triethoxysilyl)propyl]-disulfide, and the weight ratio of the two is (1-2):

1.

6. The medical silicone rubber according to claim 1, characterized in that: The antioxidant is selected from any one or more of antioxidant MB, antioxidant DNP and antioxidant HPG.

7. A method for preparing the medical silicone rubber according to any one of claims 1 to 6, characterized in that: The preparation method specifically comprises the following steps: The methylphenyl vinyl silicone rubber, reinforcing agent, antioxidant, structure control agent, platinum and quartz powder are mixed and continuously stirred, the reaction temperature is controlled at 25-35°C, and the mixing is uniform; then the temperature is raised to 180-220°C within 0.5-2h, vacuum reaction is carried out for 2-3h, and the mixing is uniform; then an activator and a silane coupling agent are added, and the mixing is uniform; then a vulcanizing agent is added, and the mixing is uniform to obtain the medical silicone rubber.

8. Use of the medical silicone rubber according to any one of claims 1 to 6 as a medical material in the field of medical devices.

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