A medical silicone rubber, its preparation method and application
Through specific proportions and improved preparation methods, the problem of degradation of mechanical properties of medical silicone rubber is solved, and higher thermal stability and extended service life are achieved, meeting the application needs in the medical device field.
Patent Information
- Application Number
- CN202510052537.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2025-05-27
- Estimated Expiration
- 2045-01-14
AI Technical Summary
After a long service time, the mechanical properties of existing medical silicone rubber have decreased a lot and cannot meet the needs of use.
Components with specific ratios are adopted, including methylphenyl vinyl silicone rubber, reinforcement, vulcanizing agent, activator, silane coupling agent, anti-aging agent, structural control agent, platinum and quartz powder, and the thermal stability and mechanical properties of silicone rubber are improved through improved preparation methods.
It significantly improves the mechanical properties of medical silicone rubber after long-term service, extends its service life, and enhances its application value in the field of medical devices.
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Abstract
Description
Technical Field
[0001] This application relates to the technical field of medical silicone rubber, and in particular to a medical silicone rubber, a preparation method thereof, and an application thereof. Background Art
[0002] Rubber is a high-molecular compound with high elasticity, which can be divided into natural rubber and synthetic rubber. Natural rubber is processed from the gum extracted from plants such as rubber trees and rubber grass; while synthetic rubber is obtained by polymerizing various monomers.
[0003] At present, after a long service time, the mechanical properties of medical silicone rubber decrease significantly, so it may not be able to meet the usage 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 usage requirements. Summary of the Invention
[0004] In order to improve the above problems, this application provides a medical silicone rubber, a preparation method thereof, and an application thereof.
[0005] The medical silicone rubber provided by this application has less or almost no decrease in mechanical properties after a long service time, and can meet its usage requirements. The medical silicone rubber provided by 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 by this 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 be able to meet the usage requirements.
[0007] In the first aspect, this application provides a medical silicone rubber, adopting the following technical solution:
[0008] A medical silicone rubber, by weight, specifically includes the following components:
[0009] 80 - 130 parts of methylphenylvinyl silicone rubber; 25 - 45 parts of reinforcing agent; 1 - 2 parts of vulcanizing agent; 5 - 10 parts of activator; 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;
[0010] The structure control agent includes hydroxy silicone oil, polyimide, and polyvinylpyrrolidone;
[0011] In the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide, and the polyvinylpyrrolidone is 1:(0.1 - 0.6):(0.2 - 0.7).
[0012] Optionally, in the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide, and the polyvinylpyrrolidone is 1:(0.3 - 0.4):(0.4 - 0.5).
[0013] In this application, platinum is used as a catalyst, which can enable the rapid polymerization of silicone rubber and improve the synthesis efficiency. At the same time, platinum can also generate more cross-linking points during the vulcanization process of silicone rubber, improve the thermal stability of silicone rubber, and extend its service life.
[0014] In this 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 formed at the contact site after an elastomeric material contacts a highly active reinforcing agent. Adding a structure control agent can prevent or delay the structuring effect, and the active groups of the added substance undergo a condensation reaction with the active hydroxyl groups on the surface of the silica, thereby preventing the interaction between the silica and the silica gel.
[0015] In this application, through the combined action of three structure control agents, the mechanical properties and anti-aging ability of medical silicone rubber can be effectively improved.
[0016] Optionally, the methylphenylvinyl silicone rubber contains 0.3 - 1% vinyl and 0.5 - 2% C 6 H 5 0.5 - 2% silicone rubber.
[0017] In this application, the above combination can make the formed medical silicone rubber material have better crosslinkability, thereby making its mechanical properties more excellent.
[0018] Optionally, the reinforcing agent is surface-treated precipitated silica.
[0019] In this 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 the polymer and the filler, thereby reducing the vulcanization efficiency and reinforcing performance. In this application, by modifying the surface of the silica, the surface hydroxyl groups of the silica can react with chemical substances to eliminate or reduce the amount of surface active silanol groups and increase its dispersibility in the polymer.
[0020] Optionally, the vulcanizing agent is 2,4-dichlorobenzoyl peroxide.
[0021] Optionally, the activator is selected from any one or more of active zinc oxide and active titanium dioxide.
[0022] 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-mercaptopropyltriethoxysilane.
[0023] 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 in the mixture is (1-2):1.
[0024] In the present application, adding a silane coupling agent to the reaction system can not only reduce the Mooney viscosity, heat generation and rolling resistance of the rubber compound, improve the processing performance of the rubber compound, and enhance the abrasion resistance of the vulcanized rubber, but also improve its heat resistance, water resistance, weather resistance, etc. The silane coupling agent has become an indispensable additive for rubber filling and modification. A large number of scientific studies have found that the dispersibility of fillers in the rubber matrix directly affects the performance of filled rubber, and the silane coupling agent exactly has a dispersion-promoting effect.
[0025] Optionally, the anti-aging agent is selected from any one or more of anti-aging agent MB, anti-aging agent DNP, and anti-aging agent HPG.
[0026] In a specific embodiment, a medical silicone rubber specifically comprises the following components: 100 parts of methylphenylvinyl silicone rubber; 30 parts of reinforcing agent; 1.2 parts of vulcanizing agent; 7 parts of activator; 1.5 parts of silane coupling agent; 1.3 parts of anti-aging agent; 4.5 parts of structure control agent; 30 parts of platinum; 16 parts of quartz powder.
[0027] In a second aspect, the present application provides a preparation method of the above-mentioned medical silicone rubber, adopting the following technical solution:
[0028] A preparation method of a medical silicone rubber, the preparation method specifically comprises the following steps: mixing methylphenylvinyl silicone rubber, reinforcing agent, anti-aging agent, structure control agent, platinum and quartz powder and continuously stirring, controlling the reaction temperature at 25-35°C, and kneading evenly; then raising the temperature to 180-220°C within 0.5-2 h, carrying out a vacuum reaction for 2-3 h, 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.
[0029] In a third aspect, the present application provides an application of the above-mentioned medical silicone rubber as a medical material in the field of medical devices.
[0030] In summary, the present application includes at least one of the following beneficial technical effects:
[0031] After a long service time, the mechanical properties of the medical silicone rubber provided by the present application are reduced less or hardly decreased, and it can meet its usage requirements. The medical silicone rubber provided by the present application has long-term significance for the development of the field of medical devices.
[0032] Compared with the silicone rubber in the prior art, the medical silicone rubber provided by the present application has higher thermal stability, and can solve the problem that after a long service time of the silicone rubber in the prior art, the mechanical properties decrease significantly and may not meet the use requirements. Detailed Embodiments
[0033] Before describing the embodiments of the present application in detail, it should be understood that the terms used herein are for the purpose of describing specific embodiments only. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this term belongs.
[0034] It should be noted that the terms "first" and "second" are used for descriptive purposes only and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, features defined with "first" and "second" may explicitly or implicitly include one or more of such features. Further, in the description of the present application, unless otherwise stated, the meaning of "a plurality" is two or more.
[0035] In the present application, the endpoints and any values disclosed in the ranges are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.
[0036] In the present application, the term "comprising" or "including" is an open expression, that is, it includes the content specified in the present application, but does not exclude other aspects.
[0037] The present application provides a medical silicone rubber. By weight, the medical silicone rubber specifically comprises the following components:
[0038] 80 - 130 parts of methylphenylvinyl silicone rubber; 25 - 45 parts of reinforcing agent; 1 - 2 parts of vulcanizing agent; 5 - 10 parts of activator; 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;
[0039] The structure control agent includes hydroxy silicone oil, polyimide and polyvinylpyrrolidone;
[0040] In the structure control agent, the weight ratio of the hydroxy silicone oil, the polyimide and the polyvinylpyrrolidone is 1:(0.1 - 0.6):(0.2 - 0.7).
[0041] In a specific embodiment, a preparation method of a medical silicone rubber specifically comprises the following steps:
[0042] Mix methylphenylvinyl silicone rubber, reinforcing agent, anti-aging agent, structure control agent, platinum and quartz powder and continuously stir, control the reaction temperature at 25 - 35 °C, and knead evenly; then raise the temperature to 180 - 220 °C within 0.5 - 2 h, evacuate and react for 2 - 3 h, and knead evenly; then add an activator and a silane coupling agent, and knead evenly; then add a vulcanizing agent, and knead evenly to obtain the medical silicone rubber.
[0043] To make the objectives, technical solutions and advantages of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative efforts fall within the scope of protection of this application. The embodiments described below are exemplary and are only used to explain this application and should not be construed as a limitation of this application.
[0044] For those not specifying specific techniques or conditions in the embodiments, follow the techniques or conditions described in the literature in this field or follow the product specifications. For reagents or instruments not indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.
[0045] The following further elaborates on this application in conjunction with embodiments and test results.
[0046] Embodiment
[0047] Embodiment 1
[0048] This embodiment provides a medical silicone rubber.
[0049] The preparation method of the above-mentioned medical silicone rubber specifically includes the following steps:
[0050] According to the ratio shown in Table 1, put methylphenylvinyl silicone rubber, surface-treated precipitated silica, anti-aging agent HPG, hydroxy silicone oil, polyimide, polyvinylpyrrolidone, platinum and quartz powder into the reactor, continuously stir, control the reaction temperature at 30 °C, and knead evenly; then raise the temperature to 200 °C within 1 h, evacuate and react for 2.5 h, and knead evenly; then add activated zinc oxide, bis-[3-(triethoxysilyl)propyl]-tetrasulfide and bis-[3-(triethoxysilyl)propyl]-disulfide, and knead evenly; then add 2,4-dichlorobenzoyl peroxide, and knead evenly to obtain the medical silicone rubber.
[0051] Cut the obtained sheet rubber into strips and extrude them on an extruder to obtain silicone rubber pellets, and heat the silicone rubber pellets and process them through a mold into the products required for medical devices.
[0052] Among them, the methylphenylvinyl silicone rubber contains 0.359% vinyl and contains C6 H 5 0.765% silicone rubber.
[0053] Examples 2 - 11
[0054] Examples 2 - 11 respectively provide a medical silicone rubber. The differences between the above examples and Example 1 are as follows: the addition of each component in the structure control agent, as shown in Table 1 specifically. The remaining operation steps are all consistent with Example 1.
[0055] Among them, the differences between Examples 2 - 6 and Example 1 are: the addition amount of polyimide in the structure control agent.
[0056] Among them, the differences between Examples 7 - 11 and Example 4 are: the addition amount of polyvinylpyrrolidone in the structure control agent.
[0057] Comparative Examples
[0058] Comparative Examples 1 - 8
[0059] Comparative Examples 1 - 8 respectively provide a medical silicone rubber. The differences between the above examples and Example 1 are: the addition of each component in the structure control agent or the addition of platinum, as shown in Table 1 specifically. The remaining operation steps are all consistent with Example 1.
[0060] Among them, the difference between Comparative Example 1 and Example 1 is: no platinum is added.
[0061] Among them, the difference between Comparative Example 2 and Example 1 is: no structure control agent is added.
[0062] Among them, the differences between Comparative Examples 3 - 5 and Example 1 are: the structure control agent only includes any one of hydroxy silicone oil, polyimide, and polyvinylpyrrolidone.
[0063] Among them, the differences between Comparative Examples 6 - 8 and Example 1 are: the structure control agent only includes any two of hydroxy silicone oil, polyimide, and polyvinylpyrrolidone.
[0064] Table 1 The addition of each component in the above examples and comparative examples
[0065]
[0066] Performance detection test
[0067] The mechanical properties and anti - aging tests of the medical silicone rubbers prepared in the above examples and comparative examples are detected respectively.
[0068] (1) The mechanical strength of the medical silicone rubbers prepared in the above-mentioned 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. Among them, the tensile strength (MPa) was tested according to the standard of GB / T 528-2009, and the tear strength (KN / m) was tested according to the standard of GB / T 529-2008.
[0069] The test results are shown in Table 2.
[0070] (2) A double 85 damp heat aging test chamber was used to conduct anti-aging tests on the medical silicone rubbers prepared in the above-mentioned examples and comparative examples respectively according to the standard of GB / T 10586.
[0071] The test results are shown in Table 2.
[0072] Table 2 Performance test results
[0073]
[0074] It can be seen from the test results in Table 2 above that the medical silicone rubber provided by this application has good mechanical properties and anti-aging ability. After a long service time, the medical silicone rubber provided by this application can still meet its usage requirements.
[0075] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example" or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of this 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 can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.
[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, rather than to limit them; although this application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of each embodiment of this application.
Claims
1. A medical silicone rubber, characterized in that: 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:(0.3-0.4):(0.4-0.5).
2. The medical silicone rubber according to claim 1, characterized in that: The reinforcing agent is surface-treated precipitated silica.
3. 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.
4. 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.
5. 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.
6. A method for preparing the medical silicone rubber according to any one of claims 1 to 5, 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.
7. Use of the medical silicone rubber according to any one of claims 1 to 5 as a medical material in the field of medical devices.
Citation Information
Patent Citations
Medical organosilicone material for pancreas and intestine anastomosis instrument and preparation method thereof
CN104474592A