Preparation method of wear-resistant disulfide-free medical liquid silicone rubber with high mechanical property

By using ultra-low-wave split-bodied silicon oil and nanopod β-phosphate triglycerium, prepare the abrasion-resistant medical liquid silicone rubber-free medical liquid silicon rubber, which solves the lack of abrasion resistance and mechanical properties of medical liquid silicon rubber in existing medical liquid. A combination of low volatile scores and excellent performance.

CN119371826APending Publication Date: 2025-01-28HUBEI XINGRUI SILICON MATERIAL CO LTD
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Patent Information

Application Number
CN202411352617.X
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2024-09-26
Publication Date
2025-01-28

AI Technical Summary

Technical Problem

Existing medical liquid silicone rubbers have shortcomings in wear resistance and mechanical properties, and secondary vulcanization is required to reduce volatile components, but this will affect performance.

Method used

Silicon oil with ultra-low hair scores as the basic polymer, and add nano-grade β-phosphate triglycerium as additives, through specific preparation processes, including pinching, dehydration and vulcanization steps to prepare the abrasion-free medical liquid Silicon rubber.

Benefits of technology

It significantly improves the abrasion resistance and mechanical properties of medical liquid silicon rubber, avoids the adverse effects of secondary vulcanization on performance, and meets the requirements of the medical liquid silicone rubber volatilization of less than 0.35%.

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Abstract

The invention relates to the technical field of disulfide-free medical liquid silicone rubber, in particular to wear-resistant disulfide-free medical liquid silicone rubber with high mechanical property. The preparation method of the composite material comprises the following steps: step 1, adding vinyl-terminated silicone oil, beta-tricalcium phosphate, white carbon black, silazane and deionized water into a kneading machine, mixing, vacuumizing, cooling and grinding to obtain base rubber; 2, taking 100 parts of the base rubber obtained in the step 2, adding vinyl silicone oil and a platinum catalyst, and mixing at normal temperature to obtain a component A; 3, taking 100 parts of the base rubber obtained in the step 2, adding a cross-linking agent and an inhibitor, and mixing at normal temperature to obtain a component B; 4, the component A and the component B are mixed according to a certain proportion and then vulcanized, the disulfide-free medical liquid silicone rubber is obtained, and the finally prepared disulfide-free medical liquid silicone rubber has good wear resistance, high mechanical property and high-temperature stability.
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Description

Technical Field

[0001] The invention provides a wear-resistant disulfide-free medical liquid silicone rubber with high mechanical properties, belonging to the technical field of organic silicon. Background Art

[0002] Liquid silicone rubber is divided into condensation type liquid silicone rubber and addition type liquid silicone rubber according to the cross-linking mechanism. Condensation type liquid silicone rubber will release organic small molecules such as alcohol, acid, ketone, amide or ketoxime according to different base polymers during the vulcanization process, so its application is subject to certain restrictions. Addition liquid silicone rubber is mainly cross-linked through the mechanism of silicon hydrogen addition, and no by-products are produced during the vulcanization process. It has the characteristics of high temperature resistance, good thermal conductivity, low linear shrinkage, and good biocompatibility. It is widely used in aerospace, automobile and shipbuilding, photovoltaic power, and medical fields. It has become one of the basic materials for improving the comprehensive performance of products in many manufacturing fields. For example, medical silicone rubber has the characteristics of disinfection resistance, anti-aging, breathability, hydrophobicity, non-carcinogenicity, good anti-coagulation and excellent biocompatibility in the medical field. As a high-performance biomaterial, medical silicone rubber is suitable for making products of various shapes and can meet the application requirements of various medical devices and their components. It is mainly used in Class II medical devices such as medical catheters, respiratory masks, and laryngeal masks for anesthesia, and Class III medical devices such as instant puncture artificial blood vessels and implantable artificial prostheses. It can also be used in medical materials such as silicone gel wound dressings and silicone gel scar removal sprays.

[0003] In order to realize the localization of high-performance medical liquid silicone rubber, technicians in this field have conducted a series of beneficial attempts. The main method is to add different additives to conventional liquid silicone rubber to prepare medical liquid silicone rubber with strong antibacterial properties and excellent mechanical properties. However, the conventional preparation method has a cumbersome process route, high preparation cost, and usually requires disulfide, which limits its application. In order to solve the above problems, Chinese patent application CN113045901A discloses a method for preparing a secondary vulcanization-free addition type liquid silicone rubber, which uses low-volatile vinyl silicone oil as a raw material to prepare a secondary vulcanization-free addition liquid silicone rubber with good mechanical properties and a hardness of 50A. However, the liquid silicone rubber prepared by this method does not have wear resistance, and the volatile matter of the prepared silicone rubber is still relatively high, which makes it difficult to meet the requirement that the volatile matter of medical liquid silicone rubber is less than 0.35%, and there is only one product with a hardness of 50A. At present, the preparation of medical silicone rubber usually uses 200 o C or so secondary vulcanization to reduce the volatile matter of medical silicone rubber requires more energy and equipment investment, and will also have an adverse effect on its mechanical properties. Summary of the invention

[0004] The main purpose of the present invention is to provide a method for preparing a wear-resistant, secondary vulcanization-free medical liquid silicone rubber, which uses ultra-low volatile silicone oil as a base polymer and special β-tricalcium phosphate as an additive, and can solve the problem that the medical silicone rubber in the prior art has poor wear resistance and poor mechanical properties, and requires secondary vulcanization to reduce the volatile matter, which affects its performance.

[0005] In the first aspect, an embodiment of the present application provides a method for preparing a base rubber of a wear-resistant, secondary vulcanization-free medical liquid silicone rubber, wherein the raw materials include 40-90 parts of vinyl-terminated silicone oil, 10-30 parts of β-tricalcium phosphate, 20-50 parts of white carbon black, 2-8 parts of silazane and 1-3.5 parts of deionized water.

[0006] In some embodiments, the base rubber is specifically prepared by the following process: first, vinyl-terminated silicone oil, β-tricalcium phosphate, white carbon black, silazane and deionized water are added into a kneader, dehydrated and kneaded for 200-360 min at a temperature of 120-180°C and a vacuum degree of 0.05-0.09 MPa, cooled, discharged, vacuum degassed for 2-10 min, and cooled and ground to obtain the base rubber.

[0007] In some embodiments, the vinyl-terminated silicone oil in the base glue is a single silicone oil or a mixed silicone oil with a vinyl content of 0.05-0.5%, a viscosity of 5000-100000 mPa•s at 25°C, and a volatile matter of less than 1%.

[0008] In some embodiments, the nano β-tricalcium phosphate described in the base gel is high-purity medical-grade nano β-tricalcium phosphate with a particle size of 200-500 nm.

[0009] In some embodiments, the white carbon black in the base rubber is fumed white carbon black, and the specific surface area of ​​the fumed white carbon black is 150-400 m 2 / g.

[0010] In some embodiments, the silazane described in the base glue is a hydrophobic treatment agent for fumed silica, including one or more of organic silazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane, trimethyltriphenylcyclotrisilazane and tetramethyldivinylsilazane.

[0011] On the other hand, the embodiment of the present application also provides a method for preparing the above-mentioned wear-resistant, secondary vulcanization-free medical liquid silicone rubber, comprising component A and component B, wherein component A comprises the following raw materials in parts by mass: 85-100 parts of base rubber, 5-10 parts of vinyl silicone oil; 0.5-2 parts of platinum catalyst; the component B comprises the following raw materials in parts by mass: 70-100 parts of base rubber, 15-30 parts of cross-linking agent, and 0.5-2 parts of inhibitor; the mass ratio of component A to component B is 1:1, comprising the following steps: (1) Preparation of component A: Add vinyl silicone oil and platinum catalyst to the base rubber, stir and vacuum mix to obtain component A; (2) Preparation of component B: Add crosslinking agent and inhibitor to the base rubber, stir and vacuum mix to obtain component B; (3) Mixing: Mix component A and component B in a mass ratio of 1:1 and stir at 100-200 o After vulcanization, disulfide-free medical liquid silicone rubber is obtained.

[0012] In some embodiments, the vinyl silicone oil in component A is polyvinyl silicone oil, with a vinyl content of 1-10%, a viscosity of 1000-10000 mPa•s at 25° C., and a volatile matter of less than 1%.

[0013] In some embodiments, the platinum catalyst is one of tetramethyldisiloxane chloroplatinate complex, tetramethyldivinylsiloxane chloroplatinate complex and tetramethyltetravinylcyclotetrasiloxane chloroplatinate complex, and the concentration of the catalyst is 1000-5000 ppm.

[0014] In some embodiments, the crosslinking agent is a mixture of one or more of side hydrogen-containing silicone oil, terminal hydrogen-containing silicone oil or side hydrogen-containing phenyl silicone oil; the viscosity of the crosslinking agent is 30 mPa•s to 300 mPa•s, and the hydrogen content of the crosslinking agent is 0.1 to 1.6 wt%.

[0015] In some embodiments, the inhibitor is an alkynol inhibitor, including one or more of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and 3,5-dimethyl-1-hexyn-3-ol. The beneficial effects brought by the technical solution provided by the present application include: 1. The organic silicon foam material provided by the present application improves the wear resistance by adding nano-scale β-tricalcium phosphate. At the same time, clinical studies on β-tricalcium phosphate show that it will not affect the hematopoietic function of the bone marrow, and there is no toxic side effect, rejection reaction or allergic phenomenon, and will not cause cancer. It is an ideal bone replacement material, which can meet medical needs when used in medical silicone rubber; at the same time, the active hydrogen on its surface can participate in the cross-linking reaction, effectively improving the strength of liquid silicone rubber, and has very excellent mechanical properties. 2. The present application uses ultra-low volatile raw materials to prepare the base rubber, and prolongs the kneading time to further reduce the volatile matter of the base rubber, so that medical liquid silicone rubber with excellent performance can be obtained without secondary vulcanization. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. Figure 1 This is a scanning electron microscopic image of β-tricalcium phosphate of this application. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the present application will be clearly and completely described below in combination with specific implementations. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by the technical personnel in the field of spectrum ketone without making creative work are within the scope of protection of the present application.

[0018] Unless otherwise stated, all starting materials used in the examples were either commercially available or prepared by known methods.

[0019] Glue base preparation example 1: By weight, 50 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 60000 mPa•s and a vinyl content of 0.08% with a volatile matter less than 1%, 30 parts of fumed white carbon black, 4 parts of β-tricalcium phosphate, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then the temperature is raised to 150-160°C and vacuumed for 3-5 hours, then the temperature is lowered to 100-110°C, 10 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 20000 mPa•s and a vinyl content of 0.1% are added, the mixture is stirred evenly, vacuum degassed for 2-10 minutes, cooled and ground to obtain base rubber 1.

[0020] Glue base preparation example 2: In parts by weight, 40 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 60000 mPa•s and a vinyl content of 0.08% with a volatile matter less than 1%, 35 parts of fumed white carbon black, 6 parts of β-tricalcium phosphate, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then the temperature is raised to 150-160°C and vacuumed for 3-5 hours, then the temperature is lowered to 100-110°C, 13 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 10000 mPa•s and a vinyl content of 0.12% are added, the mixture is stirred evenly, vacuum degassed for 2-10 min, cooled and ground to obtain base rubber 2.

[0021] Glue base preparation example 3: In parts by weight, 35 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 100000 mPa•s and a vinyl content of 0.06% with a volatile matter less than 1%, 45 parts of fumed white carbon black, 8 parts of β-tricalcium phosphate, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then the temperature is raised to 150-160°C and vacuumed for 3-5 hours, then the temperature is lowered to 100-110°C, 6 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 10000 mPa•s and a vinyl content of 0.12% are added, the mixture is stirred evenly, vacuum degassed for 2-10 min, cooled and ground to obtain base rubber 3.

[0022] Glue base preparation example 4: The difference from Example 3 of preparing the base glue is that the raw material replaces the nano-β-tricalcium phosphate with calcium phosphate, and the preparation steps include: By weight, 35 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 100000 mPa•s and a vinyl content of 0.06% with a volatile matter less than 1%, 45 parts of fumed white carbon black, 8 parts of calcium phosphate, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then heated to 150-160°C and evacuated for 3-5 hours, then cooled to 100-110°C, 6 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 10000 mPa•s and a vinyl content of 0.12% are added, stirred evenly, vacuum degassed for 2-10 min, cooled and ground to obtain base glue 4.

[0023] Medical liquid silicone rubber preparation example 1: Preparation of component A: by weight, 85 parts of base rubber 1, 10 parts of vinyl silicone oil with a viscosity of 5000 mPa•s and a vinyl content of 2% (volatile matter less than 0.5%), 4.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%), and 0.5 parts of Custer platinum catalyst are mixed evenly, and vacuum degassing is performed to obtain component A; Preparation of component B: by weight, 80 parts of base rubber 1, 15 parts of vinyl silicone oil with a viscosity of 50 mPa•s and a vinyl content of 0.5% (volatile matter less than 1%), 4.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.3% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol are mixed evenly, and vacuum degassing is performed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170°C for 10 min to prepare a 2 mm thick specimen.

[0024] Medical liquid silicone rubber preparation example 2: Preparation of component A: by weight, 80 parts of base rubber 2, 13 parts of vinyl silicone oil with a viscosity of 3000 mPa•s and a vinyl content of 2.3% (volatile matter less than 0.5%), 6.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%), and 0.5 parts of Custer platinum catalyst are mixed evenly, and vacuum degassing is performed to obtain component A; Preparation of component B: by weight, 83 parts of base rubber 2, 12 parts of vinyl silicone oil with a viscosity of 30 mPa•s and a vinyl content of 0.95% (volatile matter less than 1%), 4.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.2% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol are mixed evenly, and vacuum degassing is performed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170 °C for 10 min to prepare a 2 mm thick specimen.

[0025] Medical liquid silicone rubber preparation example 3: Preparation of component A: by weight, 82 parts of base rubber 3, 15 parts of vinyl silicone oil with a viscosity of 10000 mPa•s and a vinyl content of 8.8% (volatile matter less than 0.5%), 2.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%) and 0.5 parts of Custer platinum catalyst are mixed evenly, and vacuum degassing is performed to obtain component A; Preparation of component B: by weight, 80 parts of base rubber 3, 10 parts of vinyl silicone oil with a viscosity of 60 mPa•s and a vinyl content of 1.25% (volatile matter less than 1%), 9.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.8% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol are mixed evenly, and vacuum degassing is performed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170°C for 10 min to prepare a 2 mm thick specimen.

[0026] Medical liquid silicone rubber preparation example 4: Preparation of component A: by weight, 82 parts of base rubber 4, 15 parts of vinyl silicone oil with a viscosity of 10000 mPa•s and a vinyl content of 8.8% (volatile matter less than 0.5%), 2.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%) and 0.5 parts of Custer platinum catalyst are mixed evenly, and vacuum degassing is performed to obtain component A; Preparation of component B: by weight, 80 parts of base rubber 4, 10 parts of vinyl silicone oil with a viscosity of 60 mPa•s and a vinyl content of 1.25% (volatile matter less than 1%), 9.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.8% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol are mixed evenly, and vacuum degassing is performed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170°C for 10 min to prepare a 2 mm thick specimen.

[0027] Comparative Example Base 1 The difference from the base glue preparation example 1 is that the raw materials do not include nano β-tricalcium phosphate, and the preparation steps include: In parts by weight, 50 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 60000 mPa•s and a vinyl content of 0.08% with a volatile matter less than 1%, 30 parts of fumed white carbon black, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then the temperature is raised to 150-160°C and vacuumed for 3-5 hours, then the temperature is lowered to 100-110°C, 10 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 20000 mPa•s and a vinyl content of 0.1% are added, the mixture is stirred evenly, vacuum degassed for 2-10 minutes, and the base rubber is obtained by cooling and grinding, i.e., the base rubber 1 of the comparative example is obtained.

[0028] Comparative Example Base 2 The difference from Example 2 for preparing the base glue is that the raw materials do not include nano-β-tricalcium phosphate, and the preparation steps include: In parts by weight, 40 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 60000 mPa•s and a vinyl content of 0.08% with a volatile matter less than 1%, 35 parts of fumed white carbon black, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then the temperature is raised to 150-160°C and vacuumed for 3-5 hours, then the temperature is lowered to 100-110°C, 13 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 10000 mPa•s and a vinyl content of 0.12% are added, and after stirring evenly, vacuum degassing is carried out for 2-10 minutes, and the base rubber is obtained by cooling and grinding, that is, the base rubber 2 of the comparative example is obtained.

[0029] Comparative Example Glue 3: In parts by weight, 35 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 100000 mPa•s and a vinyl content of 0.06% with a volatile matter less than 1%, 45 parts of gas phase white carbon black, 4 parts of silazane and 2 parts of deionized water are fully mixed in a kneader for 1-2 hours, then the temperature is raised to 150-160°C and vacuumed for 3-5 hours, then the temperature is lowered to 100-110°C, 6 parts of vinyl siloxane (volatile matter less than 1%) with a viscosity of 10000 mPa•s and a vinyl content of 0.12% are added, and after stirring evenly, vacuum degassing is carried out for 2-10 minutes, and the base rubber is obtained by cooling and grinding, that is, the base rubber 3 of comparative example is obtained.

[0030] Comparative Example 1 of Preparation of Medical Liquid Silicone Rubber: Preparation of component A: by weight, 85 parts of comparative base rubber 1, 10 parts of vinyl silicone oil with a viscosity of 5000 mPa•s and a vinyl content of 2% (volatile matter less than 0.5%), 4.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%), and 0.5 parts of Custer platinum catalyst were mixed evenly, and vacuum degassed to obtain component A; Preparation of component B: by weight, 80 parts of the base rubber 1 of the comparative example, 15 parts of vinyl silicone oil with a viscosity of 50 mPa•s and a vinyl content of 0.5% (volatile matter less than 1%), 4.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.3% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol were mixed evenly, and vacuum degassed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170°C for 10 min to prepare a 2 mm thick specimen.

[0031] Medical liquid silicone rubber preparation comparative example 2: Preparation of component A: by weight, 80 parts of comparative base rubber 2, 13 parts of vinyl silicone oil with a viscosity of 3000 mPa•s and a vinyl content of 2.3% (volatile matter less than 0.5%), 6.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%), and 0.5 parts of Custer platinum catalyst were mixed evenly, and vacuum degassed to obtain component A; Preparation of component B: by weight, 83 parts of comparative base rubber 2, 12 parts of vinyl silicone oil with a viscosity of 30 mPa•s and a vinyl content of 0.95% (volatile matter less than 1%), 4.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.2% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol were mixed evenly, and vacuum degassed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170 °C for 10 min to prepare a 2 mm thick specimen.

[0032] Comparative Example 3 of Preparation of Medical Liquid Silicone Rubber: Preparation of component A: In parts by weight, 82 parts of comparative base rubber 3, 15 parts of vinyl silicone oil with a viscosity of 10000 mPa•s and a vinyl content of 8.8% (volatile matter less than 0.5%), 2.5 parts of vinyl silicone oil with a viscosity of 1000 mPa•s and a vinyl content of 0.45% (volatile matter less than 0.5%) and 0.5 parts of Custer platinum catalyst are mixed evenly, and vacuum degassing is performed to obtain component A.

[0033] Preparation of component B: by weight, the base rubber 3 of comparative example, 10 parts of vinyl silicone oil with a viscosity of 60 mPa•s and a vinyl content of 1.25% (volatile matter less than 1%), 9.5 parts of vinyl silicone oil with a viscosity of 100 mPa•s and a vinyl content of 0.8% (volatile matter less than 1%), and 0.5 parts of 1-ethynylcyclohexanol were mixed evenly, and vacuum degassed to obtain component B; The AB components were uniformly mixed at a mass ratio of 1:1 at room temperature, and then vulcanized at 170°C for 10 min to prepare a 2 mm thick specimen.

[0034] Performance testing experiment Detection Methods The medical liquid silicone rubber prepared in Examples 1-3 and Comparative Examples 1-3 of the medical liquid silicone rubber preparation were used as test samples.

[0035] According to CBT 25262-2010 “Guide for Abrasion Testing of Vulcanized Rubber or Thermoplastic Rubber”, the obtained medical liquid silicone rubber sample was subjected to abrasion test, and the test results are shown in Table 1.

[0036] The tensile strength of the medical liquid silicone rubber sample was tested according to GBT528-2009 “Determination of tensile stress properties of vulcanized rubber or thermoplastic rubber”. The test results are shown in Table 1.

[0037] The tear strength of the medical liquid silicone rubber sample was tested according to GBT528-2008 “Determination of tear strength of vulcanized rubber or thermoplastic rubber (trouser-shaped, right-angled and crescent-shaped tests)”. The test results are shown in Table 1.

[0038] Table 1 Performance test results

[0039] As can be seen from Table 1, the second-rate-free medical liquid silicone rubber provided by the present application has excellent comprehensive performance, especially high wear resistance and mechanical properties. In combination with Examples 1-3 and Comparative Examples 1-3, by comparing whether β-tricalcium phosphate is added, it can be seen that the use of medical-grade nano β-tricalcium phosphate as an additive greatly improves the wear resistance of medical liquid silicone rubber, and at the same time, the mechanical properties of medical liquid silicone rubber are also improved. In combination with Example 3 and Example 4, it can be seen that compared with ordinary calcium phosphate, medical-grade nano β-tricalcium phosphate can better improve its performance.

Claims

1. A wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber, characterized in that: The invention comprises component A and component B; the component A comprises the following raw materials in parts by weight: 85-100 parts of base rubber, 5-10 parts of vinyl silicone oil, and 0.5-2 parts of platinum catalyst; the component B comprises the following raw materials in parts by weight: 70-100 parts of base rubber, 15-30 parts of cross-linking agent, and 0.5-2 parts of inhibitor.

2. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 1, characterized in that: The preparation method of the base glue is as follows: vinyl siloxane, fumed white carbon black, β-tricalcium phosphate, silazane and water are mixed, heated to 150-160° C., reacted under vacuum, then cooled to 100-110° C., vinyl siloxane is added, stirred for reaction, and vacuum degassing is performed to obtain the base glue.

3. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 2, characterized in that: The vinyl content of vinyl siloxane is 0.05-0.5%, the viscosity is 5000-100000 mPa•s at 25°C, and the volatile matter is less than 1%.

4. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 2, characterized in that: The particle size of the nano β-tricalcium phosphate is 200-500 nm.

5. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 2, characterized in that: The specific surface area of ​​the fumed silica is 150-400 m 2 / g, the silazane includes one or more of hexamethyldisilazane, hexamethylcyclotrisilazane, trimethyltriphenylcyclotrisilazane and tetramethyldivinylsilazane organosilazane.

6. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 1, characterized in that: The vinyl silicone oil in the component A is polyvinyl silicone oil, with a vinyl content of 1-10%, a viscosity of 1000-10000 mPa•s at 25° C., and a volatile matter of less than 1%.

7. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 1, characterized in that: The platinum catalyst in the A component is one of chloroplatinic acid tetramethyldisiloxane complex, chloroplatinic acid tetramethyldivinylsiloxane complex and chloroplatinic acid tetramethyltetravinylcyclotetrasiloxane complex, and the concentration of the catalyst is 1000-5000ppm.

8. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 1, characterized in that: The crosslinking agent in the B component is hydrogen-containing silicone oil containing at least two Si-H bonds, with a hydrogen content of 0.1-2% and a volatile matter of less than 1%.

9. The wear-resistant, high mechanical performance disulfide-free medical liquid silicone rubber according to claim 1, characterized in that: The inhibitor in the B component is an acetylenic alcohol inhibitor, including one or more of 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol and 3,5-dimethyl-1-hexyn-3-ol.

10. The method for preparing the wear-resistant, high mechanical property disulfide-free medical liquid silicone rubber according to any one of claims 1 to 9, characterized in that: (1) Preparation of component A: Add vinyl silicone oil and platinum catalyst to the base rubber, stir and vacuum mix to obtain component A; (2) Preparation of component B: Add crosslinking agent and inhibitor to the base rubber, stir and vacuum mix to obtain component B; (3) Mixing: Component A and component B are uniformly mixed in a mass ratio of 1:1, and vulcanized at 100-200°C to obtain disulfide-free medical liquid silicone rubber.

Citation Information

Patent Citations

  • Preparation method of secondary vulcanization-free addition type liquid silicone rubber

    CN113045901A