Antibacterial liquid silicone rubber and preparation method thereof
By introducing triazole derivatives into silicone rubber and cross-linking agent to form cross-linked polymers, the problem of bacterial invasion during storage and placement of silicone rubber catheters is solved, and its antibacterial and mechanical properties are improved. Ensures higher biosecurity.
Patent Information
- Application Number
- CN202411383455.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2025-01-03
AI Technical Summary
During storage and placement, existing silicone rubber catheters are easily a way for bacteria to enter the patient's body, and their antibacterial properties are insufficient, making it difficult to effectively prevent bacterial growth and spread.
By introducing triazole derivatives into the silicone rubber and crosslinking with silane coupling agent to form a crosslinked polymer, and combining specific component ratios and process flows, liquid silicone rubber with antibacterial properties is prepared.
It improves the mechanical properties and antibacterial ability of silicone rubber, significantly enhances the inhibitory effect on bacteria, and ensures higher biosafety.
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Abstract
Description
Technical Field
[0001] The invention relates to silicone rubber, in particular to the technical field of silicone rubber with antibacterial effect. Background Art
[0002] Catheters made of silicone rubber are soft, safe and have good biocompatibility, and are widely used in the medical field. However, the storage and placement of catheters also provide conditions for bacteria to enter the patient's body.
[0003] Based on the good antibacterial properties of triazole pyridine compounds, they can affect the structure and function of cell membranes, causing them to stagnate or even die. The present invention provides a method for preparing liquid silicone rubber with antibacterial properties, wherein the vinyl groups on triazole derivatives are cross-linked with silane coupling agents to obtain cross-linked polymers. Summary of the invention
[0004] In order to solve the problems in the prior art, the purpose of the present invention is to provide a method for preparing antibacterial liquid silicone rubber.
[0005] To achieve the above object, the technical solution adopted by the present invention is: An antibacterial liquid silicone rubber is composed of component A and component B in a mass ratio of 1:1, wherein component A is composed of the following raw materials in parts by mass: 93.6-97.4 parts of base rubber, 1.5-1.6 parts of polyvinyl polysiloxane, 0.5-3.8 parts of triazole derivatives, and 0.9-1.6 parts of platinum catalyst.
[0006] Component B is composed of the following raw materials by mass: Component B comprises the following raw materials in parts by weight: 89.4 to 92 parts of base rubber, 2.8 to 3.6 parts of side hydrogen-containing silicone oil, 3.6 to 6.2 parts of double-end hydrogen-containing silicone oil, and 0.8 to 1.6 parts of inhibitor.
[0007] In component A and component B, the base rubber is prepared by the following method: 47 to 48 parts of double-terminal vinyl polysiloxane and 4 to 5 parts of silane coupling agent are mixed, and then 28 to 33 parts of fumed silica and 1.8 to 2 parts of deionized water are added, the material temperature is controlled at 40-50°C, fully kneaded for 1-2 hours, and then heated to 120 to 160°C and vacuum kneaded for 3-4 hours, and then cooled to 90 to 110°C, 13 to 18.2 parts of double-terminal vinyl polysiloxane are added for dilution, and vacuum kneading is continued for 1 to 2 hours, and stirred evenly to obtain the base rubber.
[0008] In component A and component B, the double-terminal vinyl polysiloxane structure of the base glue is ViMe 2 Si0(Me 2 Si0)SiMe 2Vi, wherein the viscosity is 60000-100000 mPa.s at 25°C; In some preferred cases, the dual-terminal vinyl polysiloxane is a dual-terminal vinyl polysiloxane having a viscosity of 60,000 mPa·s at 25° C. and a vinyl content of 0.08% wt, or a dual-terminal vinyl polysiloxane having a viscosity of 100,000 mPa·s and a vinyl content of 0.07% wt.
[0009] In component A and component B, the fumed silica of the base rubber is not treated with a silane coupling agent for hydrophobicity, and has a specific surface area of 350 to 410 m 2 / g.
[0010] In component A and component B, the silane coupling agent of the base glue is hexamethyldisilazane.
[0011] In component A and component B, the polyvinyl silicone oil has a viscosity of 330 to 9000 mPa·s at 25° C. and a vinyl content of 1.22 to 8.98%wt.
[0012] In component A and component B, the structure of the triazole derivative is as follows: Where R 1 , R 2 Selected from (CH 2 ) 3 , (CH 2 ) 4 , (CH 2 ) 5 , 1-indanyl or 9-fluorenyl, and is a terminal olefin, that is, the terminal position is an olefin structure.
[0013] In some embodiments, the triazole derivative has the structural formula: Where R 1 , R 2 The structure is -CH 2 CH 2 =CH 2 .
[0014] In component A and component B, the platinum catalyst is tetramethyl divinyl disiloxane chloroplatinic acid complex, wherein the mass content of platinum is 200-300 ppm.
[0015] In component A and component B, the side hydrogen-containing silicone oil has a viscosity of 60-80 mPa·s at 25° C. and a hydrogen content of 0.5-0.8 wt %, preferably a hydrogen content of 0.75 wt %.
[0016] In component A and component B, the double-ended hydrogen-containing silicone oil has a viscosity of 12 to 20 mPa·s at 25° C. and a hydrogen content of 0.12 to 0.18 wt %.
[0017] In component A and component B, the inhibitor is 1-ethynylcyclohexanol, which is prepared into a 10 wt % solution, and the solvent is a methyl-terminated polysiloxane with a viscosity of 45-50 mPa.s at 25°C.
[0018] According to the technical solution of the present invention, the preparation method of component A includes: mixing and dispersing 93.6 to 97 parts of base rubber, 1.5 to 1.6 parts of polyvinyl polysiloxane, 0.5 to 3.8 parts of triazole derivatives and 0.9 to 1.6 parts of platinum catalyst evenly, and then vacuum degassing to obtain component A.
[0019] According to the technical solution of the present invention, the preparation method of the B component includes: mixing and dispersing 89.4 to 92 parts of base rubber, 2.8 to 3.6 parts of side hydrogen-containing silicone oil, 3.6 to 6.2 parts of double-end hydrogen-containing silicone oil and 0.8 to 1.6 parts of inhibitor evenly, and then vacuum degassing to obtain the B component.
[0020] According to the technical solution of the present invention, the vulcanization scheme is to mix and disperse the AB components of equal mass evenly, the vulcanization temperature is 110-120°C, the vulcanization pressure is 7-12Mpa, and the vulcanization time is 5-10min to obtain the silicone rubber.
[0021] Compared with the prior art, the present invention has the following beneficial effects: The vinyl group of triazole derivatives is introduced into the silicone rubber system, and the hydrogenated silicone oil in the system can react with the vinyl group, thereby increasing the degree of cross-linking of the system and improving the poor mechanical properties of ordinary antibacterial silicone rubber. At the same time, the high-density triazole derivatives can ensure excellent antibacterial ability. DETAILED DESCRIPTION
[0022] The technical solution of the present invention will be further described in detail below in conjunction with specific implementation examples.
[0023] An antibacterial liquid silicone rubber is vulcanized by vulcanizing component A and component B in a mass ratio of 1:1. Unless otherwise specified, the raw materials and reagents in the following examples are all commercially available products or prepared by known methods.
[0024] Preparation of Liquid Silicone Rubber Base In a kneader, 48 parts by weight of a double-terminal vinyl polysiloxane having a viscosity of 100,000 mPa·s and a vinyl content of 0.08% wt, and 28 parts by weight of a BET specific surface area of 350 m 2 / g of fumed silica, 4 parts of hexamethyldisilazane, and 1.8 parts of deionized water are added in batches, the material temperature is controlled below 50°C, fully kneaded for 2h, then heated to 150-160°C and kneaded in vacuum for 4h, then cooled to 110°C, 18.2 parts of double-terminal vinyl polysiloxane with a content of 100000mPa·s and 0.07%wt of alkenyl are added, and vacuum kneading is continued for 1-2h. Stir evenly to obtain liquid silicone rubber base glue I.
[0025] Preparation of Liquid Silicone Rubber Base II In a kneader, 47 parts by weight of a double-terminal vinyl polysiloxane having a viscosity of 60000 mPa·s and a vinyl content of 0.08% wt, and 33 parts by weight of a BET specific surface area of 350 m 2 / g of fumed silica, 5 parts of hexamethyldisilazane and 2 parts of deionized water are added in batches, the material temperature is controlled below 50°C, fully kneaded for 2h, then heated to 150-160°C and kneaded in vacuum for 4h, then cooled to 110°C, 13 parts of double-terminal vinyl polysiloxane with a content of 60000mPa·s and 0.08%wt of alkenyl are added, and vacuum kneading is continued for 1-2h. Stir evenly to obtain liquid silicone rubber base II.
[0026] Example Preparation of Liquid Silicone Rubber Example 1 Preparation and vulcanization of component AB: 97 parts of the above-mentioned base rubber I, 1.6 parts of polyvinyl polysiloxane with a viscosity of 80 mPa·s and an olefin content of 8.98%wt, 0.9 parts of Custer-type platinum catalyst, and 0.5 parts of triazole derivatives were stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0027] 92 parts of the above-mentioned base rubber 1, 3.6 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 80mPa·s and containing SiH on the side chain, 3.6 parts of hydrogen-containing silicone oil with a hydrogen content of 0.18%wt and a viscosity of 20mPa·s and containing SiH at both ends, 0.8 parts of a 10wt% 1-ethynylcyclohexanol solution, and a solvent of methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0028] The structural formula of the triazole derivative is The structure of R is -CH 2 CH 2 =CH 2 .
[0029] Component A and component B in equal weight proportions were mixed evenly, and then vulcanized at 110°C for 10 minutes to obtain a 2 mm thick test piece.
[0030] Example 2 Preparation and vulcanization of component AB: 97 parts of the above-mentioned base rubber II, 1.6 parts of polyvinyl polysiloxane with a viscosity of 330 mPa·s and an olefin content of 8.98%wt, 0.9 parts of Custer-type platinum catalyst, and 0.5 parts of triazole derivatives were stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0031] 89.4 parts of the above-mentioned base rubber II, 3.2 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 20mPa·s and containing SiH on the side chain, 5.8 parts of hydrogen-containing silicone oil with a hydrogen content of 0.12%wt and a viscosity of 12mPa·s and containing SiH at both ends, 1.6 parts of 10wt% 1-ethynylcyclohexanol solution, and the solvent is methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0032] The structural formula of the triazole derivative is The structure of R is -CH 2 CH 2 =CH 2 .
[0033] Component A and component B were mixed evenly in equal weight proportions, and then vulcanized at 110°C for 10 min to obtain a 2 mm thick test piece.
[0034] Example 3 Preparation and vulcanization of component AB: 95.6 parts of the above-mentioned base rubber II, 1.6 parts of polyvinyl polysiloxane with a viscosity of 9000 mPa·s and a vinyl content of 1.22%wt, 1.6 parts of Custer-type platinum catalyst, and 1.2 parts of triazole derivatives were stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0035] 89.4 parts of the above-mentioned base rubber II, 2.8 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 80mPa·s and containing SiH on the side chain, 6.2 parts of hydrogen-containing silicone oil with a hydrogen content of 0.12%wt and a viscosity of 12mPa·s and containing SiH at both ends, 1.6 parts of 10wt% 1-ethynylcyclohexanol solution, and the solvent is methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0036] The structural formula of the triazole derivative is The structure of R is -CH 2 CH 2 CH 2 =CH 2 .
[0037] Component A and component B were mixed evenly in equal weight proportions, and then vulcanized at 110°C for 10 min to obtain a 2 mm thick test piece.
[0038] Example 4 Preparation and vulcanization of component AB: 93.6 parts of the above-mentioned base rubber II, 1.6 parts of polyvinyl polysiloxane with a viscosity of 330 mPa·s and an olefin content of 8.98%wt, 1 part of a Custer-type platinum catalyst, and 3.8 parts of a triazole derivative were stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0039] 89.4 parts of the above-mentioned base rubber II, 3.2 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 80mPa·s and containing SiH on the side chain, 5.8 parts of hydrogen-containing silicone oil with a hydrogen content of 0.12%wt and a viscosity of 12mPa·s and containing SiH at both ends, 1.6 parts of 10wt% 1-ethynylcyclohexanol solution, and the solvent is methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0040] The structural formula of the triazole derivative is The structure of R is -CH 2 CH 2 =CH 2 .
[0041] Component A and component B were mixed evenly in equal weight proportions, and then vulcanized at 110°C for 10 min to obtain a 2 mm thick test piece.
[0042] Example 5 Preparation and vulcanization of component AB: 95.2 parts of the above-mentioned base rubber I, 1.6 parts of polyvinyl polysiloxane with a viscosity of 330 mPa·s and an olefin content of 8.98%wt, 0.9 parts of Custer-type platinum catalyst, and 2.3 parts of triazole derivatives were stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0043] 92 parts of the above-mentioned base rubber I, 3.6 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 80mPa·s and containing SiH in the side chain, 3.6 parts of hydrogen-containing silicone oil with a hydrogen content of 0.18%wt and a viscosity of 12mPa·s and containing SiH at both ends, 0.8 parts of 10wt% 1-ethynylcyclohexanol solution, and the solvent is methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0044] The structural formula of the triazole derivative is The structure of R is -CH 2 CH 2 CH 2 CH 2 =CH 2 .
[0045] Component A and component B were mixed evenly in equal weight proportions, and then vulcanized at 110°C for 10 min to obtain a 2 mm thick test piece.
[0046] Example 6 The method and steps are the same as those in Example 1, except that the structural formula of the triazole derivative is The structure of R is 1-indanyl.
[0047] Example 7 The method and steps are the same as those in Example 1, except that the structural formula of the triazole derivative is The structure of R is 9-fluorenyl.
[0048] Comparative Example 1 Preparation and vulcanization of component AB: 93.6 parts of the above-mentioned base rubber II, 1.6 parts of polyvinyl polysiloxane with a viscosity of 330 mPa·s and an olefin content of 8.98%wt, 1 part of a Custer-type platinum catalyst, and 3.8 parts of triazole pyridine were stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0049] The structural formula of triazolopyridine is: .
[0050] 89.4 parts of the above-mentioned base rubber II, 3.2 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 80mPa·s and containing SiH on the side chain, 5.8 parts of hydrogen-containing silicone oil with a hydrogen content of 0.12%wt and a viscosity of 12mPa·s and containing SiH at both ends, 1.6 parts of 10wt% 1-ethynylcyclohexanol solution, and the solvent is methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0051] Component A and component B were mixed evenly in equal weight proportions, and then vulcanized at 110°C for 10 min to obtain a 2 mm thick test piece.
[0052] Comparative Example 2 Preparation and vulcanization of component AB: 97.4 parts of the above-mentioned base rubber II, 1.6 parts of polyvinyl polysiloxane with a viscosity of 330 mPa·s and an olefin content of 8.98%wt, and 1 part of a Custer-type platinum catalyst are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component A.
[0053] 89.4 parts of the above-mentioned base rubber II, 3.2 parts of hydrogen-containing silicone oil with a hydrogen content of 0.75%wt and a viscosity of 80mPa·s and containing SiH in the side chain, 5.8 parts of hydrogen-containing silicone oil with a hydrogen content of 0.12%wt and a viscosity of 12mPa·s and containing SiH at both ends, 1.6 parts of 10wt% 1-ethynylcyclohexanol solution, and the solvent is methyl-terminated polysiloxane with a viscosity of 45-50mPa.s, are stirred and dispersed in a planetary mixer for 60 minutes, mixed evenly, and then vacuumed and degassed to obtain the antibacterial liquid silicone rubber component B.
[0054] Component A and component B were mixed evenly in equal weight proportions, and then vulcanized at 110°C for 10 min to obtain a 2 mm thick test piece.
[0055] At room temperature, an AI-7000S1 tensile testing machine (High Speed Rail Testing Instruments (Dongguan) Co., Ltd.) was used to measure the hardness of the antibacterial liquid silicone rubber after vulcanization in accordance with GB-T531.1-2008, the tear strength of the antibacterial liquid silicone rubber after vulcanization was measured in accordance with GB-T 529-2008, and the tensile strength and elongation at break of the antibacterial liquid silicone rubber after vulcanization were measured in accordance with GB-T 528-2009.
[0056] According to GB4789.2-2010, the antibacterial properties of silicone rubber composite materials were tested by film sticking method. Candida albicans CNCM1180-79 was selected as the test bacteria.
[0057] The antibacterial property of silicone rubber composite materials was tested by calculating the antibacterial rate. The antibacterial rate calculation formula is: R (%, CFU / mL) = (Cb-Ca) / Cb × 100%. In the formula, R is the antibacterial rate, Ca is the colony count of the silicone rubber composite sample, and Cb is the colony count of the blank control group.
[0058] The product performances of Examples 1-5 of the present invention and Comparative Examples 1-2 are compared, and the results are shown in Table 1 below: Table 1
[0059] As shown in Table 1, the antibacterial silicone rubber can greatly improve the antibacterial property of the antibacterial silicone rubber composite material by adding the triazole derivative. Moreover, by comparing the examples and comparative examples, it is found that the lack of the triazole derivative or the replacement with other substances with a triazole structure will lead to a significant decrease in the antibacterial property of the antibacterial silicone rubber.
[0060] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. An antibacterial liquid silicone rubber, characterized in that: The invention comprises the following raw materials in parts by weight: Component A comprises the following raw materials by weight: 93.6-97.4 parts of base rubber, 1.5-1.6 parts of polyvinyl polysiloxane, 0.5-3.8 parts of triazole derivatives, and 0.9-1.6 parts of platinum catalyst; Component B comprises the following raw materials in parts by mass: 89.4-92 parts of base rubber, 2.8-3.6 parts of side hydrogen-containing silicone oil, 3.6-6.2 parts of double-end hydrogen-containing silicone oil, and 0.8-1.6 parts of inhibitor.
2. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The base rubber is prepared by the following method: 47-48 parts of double-terminal vinyl polysiloxane and 4-5 parts of silane coupling agent are mixed, and then 28-33 parts of fumed silica and 1.8-2 parts of deionized water are added, the material temperature is controlled at 40-50°C, fully kneaded for 1-2 hours, then heated to 120-160°C and vacuum kneaded for 3-4 hours, then cooled to 90-110°C, 13-18.2 parts of double-terminal vinyl polysiloxane are added for dilution, vacuum kneading is continued for 1-2 hours, and stirred evenly to obtain the base rubber.
3. The antibacterial liquid silicone rubber according to claim 2, characterized in that: The double-terminal vinyl polysiloxane has a structural formula of ViMe2Si0(Me2Si0)SiMe2Vi, wherein the viscosity is 60000-100000 mpa.s at 25°C; The silane coupling agent is hexamethyldisilazane, and the specific surface area of fumed silica is 350-410 m 2 / g.
4. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The polyvinyl polysiloxane has a viscosity of 330 to 9000 mPa·s at 25° C. and a vinyl content of 1.22 to 8.98%wt.
5. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The structure of the triazole derivative is shown below: Wherein R1 and R2 are selected from (CH2)3, (CH2)4, (CH2)5, 1-indanyl or 9-fluorenyl, and are terminal olefins.
6. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The platinum catalyst is a chloroplatinic acid tetramethyl divinyl disiloxane complex, wherein the mass content of platinum is 200-300 ppm.
7. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The side hydrogen-containing silicone oil has a viscosity of 60-80 mPa·s at 25° C. and a hydrogen content of 0.5-0.8%wt.
8. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The double-ended hydrogen-containing silicone oil has a viscosity of 12 to 20 mPa·s at 25° C. and a hydrogen content of 0.12 to 0.18%wt.
9. The antibacterial liquid silicone rubber according to claim 1, characterized in that: The inhibitor is 1-ethynylcyclohexanol, which is prepared into a solution of 8-10%wt, and the solvent is a methyl-terminated polysiloxane with a viscosity of 45-50 mPa.s at 25°C.
10. The method for preparing the antibacterial liquid silicone rubber according to any one of claims 1 to 9, characterized in that: Component A and component B are mixed and stirred in a weight ratio of 1:1 to evenly degas, and vulcanized at 110-120° C. for 5-10 minutes to obtain the antibacterial liquid silicone rubber.