CN111269660A - Self-adhesive antibacterial silicone rubber and preparation method thereof - Google Patents
Self-adhesive antibacterial silicone rubber and preparation method thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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Abstract
The invention belongs to the technical field of rubber materials, and particularly relates to self-adhesive antibacterial silicone rubber and a preparation method thereof, wherein the self-adhesive antibacterial silicone rubber patch comprises the following components in parts by weight: 100 parts of antibacterial silicone rubber, 20-60 parts of reinforcing agent, 3-8 parts of structure control agent, 1-3 parts of vulcanizing agent, 1-3 parts of flame retardant and 1-3 parts of antioxidant. The components of the invention have better synergistic effect and good compatibility with silicon rubber, and the prepared silicon rubber patch has the advantages of broad-spectrum high antibacterial property, good biocompatibility, low toxicity, good weather resistance, excellent mechanical property, good self-adhesion and storage stability, and in addition, the preparation method is simple, the raw materials are easy to obtain, the energy is saved, the environment is protected, the reproducibility is good, and the production efficiency is high.
Description
Technical Field
The invention belongs to the technical field of rubber materials, and particularly relates to self-adhesive antibacterial silicone rubber and a preparation method thereof.
Background
Silicone rubber materials are widely used in the assembly and production of electronic components, equipment components, and the like. In many cases, the silicone rubber is required to have good adhesion to components and parts to achieve an ideal effect. In the assembly and production methods in the prior art, an adhesive is usually coated on a component or an assembly in advance, or a layer of pressure-sensitive adhesive is attached to the surface of a silicon rubber material to achieve better adhesion between the components or the assembly, but the method has the defects of complicated processing procedures and higher requirements on the adhesive, and the adhesive is usually required to have good comprehensive properties such as antibacterial property, weather resistance and the like. However, the polymers applied in these fields are exposed to the outside for a long time, and the surfaces of the polymers are extremely easy to grow and propagate various harmful microorganisms, which can cause biofouling and biological corrosion of materials over time, and can seriously even threaten the health of human beings. The antibacterial function modification of the polymer surface can prevent the breeding of harmful microorganisms. Recent researches show that the breeding of pathogenic bacteria on the surface of a polymer material can be well prevented by introducing an antibacterial agent or a group into the polymer in a chemical bonding mode, and meanwhile, the environmental hazard caused by the release of the traditional antibacterial agent can be avoided. Therefore, the research and preparation of the silicon rubber material with broad-spectrum antibacterial property and excellent self-adhesion and comprehensive performance has very important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses self-adhesive antibacterial silicone rubber and a preparation method thereof, the prepared silicone rubber patch has the advantages of broad-spectrum high antibacterial property, good biocompatibility, low toxicity, good weather resistance, excellent mechanical property, good self-adhesion and storage stability, and in addition, the preparation method is simple, the raw materials are easy to obtain, the energy is saved, the environment is protected, the reproducibility is good, and the production efficiency is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
the self-adhesive antibacterial silicone rubber comprises the following components in parts by weight: 100 parts of antibacterial silicone rubber, 20-60 parts of reinforcing agent, 3-8 parts of structure control agent, 1-3 parts of vulcanizing agent, 1-3 parts of flame retardant and 1-3 parts of antioxidant;
the antibacterial silicone rubber consists of 80-90 parts of antibacterial base material and 10-20 parts of methyl hydrogen polysiloxane;
the reinforcing agent is prepared by hexamethyldisilazane surface treatment with the specific surface area of 150-300m2Fumed silica per gram;
the structure control agent has a hydroxyl content of 5-12% and a viscosity of 10-30mm at 25 deg.C2A hydroxyl silicone oil/s;
the vulcanizing agent is one of dicumyl peroxide (DCP), 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane (2, 5-hexane) and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) -3-hexyne (2, 5-hexyne);
the flame retardant is triphenyl phosphate and decabromodiphenyl ether in a weight ratio of 3: 1;
the antioxidant is pentaerythritol tetrakis [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ] and thiodipropionate diester in a weight ratio of 3: 1.
Further, the antibacterial base material consists of 70 parts of guanidino-containing antibacterial polymer, 60 parts of α, omega-divinyl polydimethylsiloxane and 0.5-1 part of boric acid.
Further, the guanidine group-containing antibacterial polymer has the following structural formula:
wherein n is 100.
Further, the guanidine group-containing antibacterial polymer is prepared by the following method:
(1) under the nitrogen atmosphere, 1 part of guanidine is dissolved in 5 parts of deionized water, 1mol/L of NaOH solution and 2-2.2 parts of methacrylic acid chloride are simultaneously dripped into guanidine aqueous solution at the temperature of 0-10 ℃, the dripping speed of NaOH is controlled, the pH of the system is maintained at 9-12, after dripping is finished, the system is stirred and reacts for 8-12 hours at the temperature of 10-25 ℃, after the reaction is finished, chloroform is used for extracting mixed solution, extract liquor is respectively washed with 5% acetic acid aqueous solution and saturated sodium bicarbonate for three times, after washing is finished, the solvent is removed by reduced pressure distillation to obtain a product I, and the reaction equation is as follows:
(2) dissolving 1 part of dodecamethylhydrohexasiloxane in 50 parts of tetrahydrofuran, and mixing 1.2-1.4 parts of product I, 1 wt% of polymerization inhibitor and 10 parts of product I-4Dissolving catalyst in 10 portions of tetrahydrofuran, adding into a constant pressure dropping funnel, controlling the dropping speed, stirring, 60-120 deg.CAfter reacting for 3-5h, distilling under reduced pressure to remove the solvent, adding 30 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3h, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent to obtain a product II, namely the antimicrobial polymer containing guanidino, wherein the reaction equation is as follows:
wherein n is 100.
Further, the polymerization inhibitor is 2, 6-di-tert-butyl-p-methylphenol, hydroquinone or p-hydroxyanisole.
Further, the catalyst is chloroplatinic acid, carbene alkane, platinum dioxide or aluminum trichloride.
Further, the preparation method of the self-adhesive antibacterial silicone rubber specifically comprises the following steps:
(1) preparing antibacterial silicone rubber, namely adding 70 parts by weight of antibacterial polymer containing guanidino, 60 parts by weight of α, omega-divinyl polydimethylsiloxane and 0.5-1 part by weight of boric acid into a kneading machine at 60-80 ℃ under the protection of nitrogen, stirring, keeping the temperature for 2 hours to obtain an antibacterial base material, then adding methyl hydrogen polysiloxane according to parts by weight, heating to 80-100 ℃, and stirring at the constant temperature for 2.5 hours to obtain the antibacterial silicone rubber;
(2) preparation of self-adhesive antibacterial silicone rubber patch master batch: adding antibacterial silicone rubber, a reinforcing agent, a flame retardant and an antioxidant into an internal mixer according to parts by weight, adjusting the temperature of the internal mixer to be 100-; adding a structure control agent, continuously banburying for 2h, controlling the glue temperature at 120-;
(3) preparing a self-adhesive antibacterial silicone rubber patch: mixing a vulcanizing agent and the master batch in the step (2) on an open mill uniformly, performing thin-pass and sheet discharge, vulcanizing by using a flat vulcanizing machine, cooling, trimming, inspecting and packaging to obtain a self-adhesive antibacterial silicone rubber patch;
further, the mixing temperature in the step (3) is 80-100 ℃, and the mixing time is 10-30 min; the vulcanization temperature is 150-180 ℃, the time is 10-30min, and the pressure is 10-15 MPa.
The invention has the following beneficial effects:
(1) the components contained in the silicon rubber and the structure regulator in the self-adhesive antibacterial silicon rubber patch disclosed by the invention all contain Si-O bonds with higher bond energy on the molecular chain structure, hydroxyl on the structure control agent ensures that the chains can be mutually staggered during vulcanization, boric acid contained in the base material and a vulcanizing agent supplement each other, the crosslinking degree and the uniformity of density are greatly improved, and the product performance is better controlled, so that the crosslinked silicon rubber patch can have excellent comprehensive performance, can be well adhered to various components or assemblies such as metal, glass, plastic and the like, can keep durable adhesion, and is flexible in texture.
(2) The self-adhesive antibacterial silicone rubber patch prepared by the invention introduces guanidino into a siloxane molecular chain, is similar to the structure of natural antibacterial peptide, has broad-spectrum efficient antibacterial property and excellent biocompatibility, is free from environmental pollution, has better designability and regulation and control performance, and has more durable antibacterial property because a macromolecular antibacterial agent is not easy to leach and leach compared with a micromolecular antibacterial agent.
(3) According to the invention, the white carbon black subjected to surface treatment by hexamethyldisilazane is used as a reinforcing agent, so that the compatibility and the dispersibility of the white carbon black in a system are facilitated, the white carbon black is not easy to agglomerate in an internal mixing process, and the silicon rubber patch has better mechanical properties such as tensile strength, elongation at break and the like after crosslinking
(4) The components of the invention have better synergistic effect and good compatibility with silicon rubber, and the prepared silicon rubber patch has the advantages of broad-spectrum high antibacterial property, good biocompatibility, low toxicity, good weather resistance, excellent mechanical property, good self-adhesion and storage stability, and in addition, the preparation method is simple, the raw materials are easy to obtain, the energy is saved, the environment is protected, the reproducibility is good, and the production efficiency is high.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Example 1
The self-adhesive antibacterial silicone rubber comprises the following components in parts by weight:
100 parts of antibacterial silicone rubber consisting of 90 parts of antibacterial base material and 10 parts of methylhydrogenpolysiloxane, and the specific surface area of the antibacterial silicone rubber subjected to surface treatment by hexamethyldisilazane is 150m235 parts of fumed silica per gram, 8 percent of hydroxyl content and 10mm of viscosity at 25 DEG C25 parts of hydroxyl silicone oil per second, 1 part of dicumyl peroxide, 3 parts of flame retardant consisting of triphenyl phosphate and decabromodiphenyl oxide in a weight ratio of 3:1, and 1 part of antioxidant consisting of tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and thiodipropionic acid diester in a weight ratio of 3: 1;
the antibacterial base material consists of 70 parts of an antibacterial polymer containing guanidine, 60 parts of α, omega-divinyl polydimethylsiloxane and 0.5 part of boric acid.
The antimicrobial polymer containing guanidine groups is prepared by the following method:
(1) dissolving 1 part of guanidine in 5 parts of deionized water under the atmosphere of nitrogen, simultaneously dropwise adding 1mol/L NaOH solution and 2.1 parts of methacryloyl chloride into a guanidine aqueous solution at the temperature of 0-10 ℃, controlling the dropwise adding speed of NaOH, maintaining the pH of a system at 9-12, stirring and reacting at the temperature of 10 ℃ for 12 hours after dropwise adding, extracting a mixed solution by using trichloromethane after the reaction is finished, washing the extract liquid by using 5% acetic acid aqueous solution and saturated sodium bicarbonate water for three times respectively, and removing the solvent by reduced pressure distillation after washing to obtain a product I;
(2) dissolving 1 part of dodecamethylhydrohexasiloxane in 50 parts of tetrahydrofuran, and mixing 1.2 parts of product I, 1 wt% of polymerization inhibitor hydroquinone and 10 wt% of product I-4Dissolving chloroplatinic acid serving as a catalyst in 10 parts of tetrahydrofuran, adding the solution into a constant-pressure dropping funnel, controlling the dropping speed, stirring, reacting at 60 ℃ for 5 hours, distilling under reduced pressure to remove the solvent, adding 30 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3 hours, separating a water phase, taking an organic layer, and distilling under reduced pressure to remove the solvent to obtain a product II, namely the antimicrobial polymer containing the guanidyl.
Examples 2 to 5, comparative examples 1 to 5 differ from example 1 as shown in Table 1,
TABLE 1
The preparation method of the self-adhesive antibacterial silicone rubber described in embodiments 1 to 5 specifically includes the following steps:
(1) preparing antibacterial silicone rubber, namely adding 70 parts by weight of antibacterial polymer containing guanidino, 60 parts by weight of α, omega-divinyl polydimethylsiloxane and 0.5-1 part by weight of boric acid into a kneading machine at 60-80 ℃ under the protection of nitrogen, stirring, keeping the temperature for 2 hours to obtain an antibacterial base material, then adding methyl hydrogen polysiloxane according to parts by weight, heating to 80-100 ℃, and stirring at the constant temperature for 2.5 hours to obtain the antibacterial silicone rubber;
(2) preparation of self-adhesive antibacterial silicone rubber patch master batch: adding antibacterial silicone rubber, a reinforcing agent, a flame retardant and an antioxidant into an internal mixer according to parts by weight, adjusting the temperature of the internal mixer to be 100-; adding a structure control agent, continuously banburying for 2h, controlling the glue temperature at 120-;
(3) preparing a self-adhesive antibacterial silicone rubber patch: uniformly mixing a vulcanizing agent and the master batch in the step (2) on an open mill at the temperature of 80-100 ℃ for 10-30min, thinly passing, taking out, vulcanizing by using a flat vulcanizing machine at the vulcanization temperature of 150-180 ℃ for 10-30min under the pressure of 10-15MPa, cooling, trimming, inspecting and packaging to obtain the self-adhesive antibacterial silicone rubber patch;
performance testing
Self-adhesion test:
the examples 1 to 5 and the comparative examples 1 to 5 were subjected to a self-adhesion test: taking a stainless steel, glass, polyethylene and polytetrafluoroethylene model block with a smooth surface and a size of about 200mm multiplied by 20mm multiplied by 5mm, respectively placing the test samples of examples 1-5 and comparative examples 1-5 with a diameter of 25mm and a thickness of 4mm on the test surface of each model block, marking the positions, standing each model block on a laboratory bench, keeping the included angle between the test surface and the test bench surface at 90 degrees, standing for 96h, wherein the test samples of examples 1-5 do not fall off or have obvious slippage, and the test samples of comparative examples 2 and 4 all fall off; when the standing time reaches 240h, the test samples of the examples 1 to 5 do not slip, while the test sample of the comparative example 5 slips and falls off, when the standing time reaches 720h, the test samples of the examples 1 to 5 still do not slip, while the test sample of the comparative example 1 clearly slips, and the comparative example 3 slips.
(II) antimicrobial Property test
TABLE 2
(III) mechanical Property test
TABLE 3
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. The self-adhesive antibacterial silicone rubber is characterized in that the self-adhesive antibacterial silicone rubber patch comprises the following components in parts by weight: 100 parts of antibacterial silicone rubber, 20-60 parts of reinforcing agent, 3-8 parts of structure control agent, 1-3 parts of vulcanizing agent, 1-3 parts of flame retardant and 1-3 parts of antioxidant;
the antibacterial silicone rubber consists of 80-90 parts of antibacterial base material and 10-20 parts of methyl hydrogen polysiloxane;
the reinforcing agent is prepared by hexamethyldisilazane surface treatment with the specific surface area of 150-300m2Fumed silica per gram;
the structure control agent has a hydroxyl content of 5-12% and a viscosity of 10-30mm at 25 deg.C2A hydroxyl silicone oil/s;
the vulcanizing agent is one of dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) hexane and 2, 5-dimethyl-2, 5-bis (tert-butyl peroxide) -3-hexyne;
the flame retardant is triphenyl phosphate and decabromodiphenyl ether in a weight ratio of 3: 1;
the antioxidant is pentaerythritol tetrakis [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionate ] and thiodipropionate diester in a weight ratio of 3: 1.
2. The self-adhesive antibacterial silicone rubber according to claim 1, wherein the antibacterial base material comprises 70 parts of a guanidino-containing antibacterial polymer, 60 parts of α, omega-divinylpolydimethylsiloxane, and 0.5-1 part of boric acid.
3. The self-adhesive antibacterial silicone rubber according to claim 2, wherein the guanidine group-containing antibacterial polymer has the following structural formula:
wherein n is 100.
4. The self-adhesive antibacterial silicone rubber according to claim 2, wherein the antimicrobial polymer containing guanidine groups is prepared by the following method:
(1) dissolving 1 part of guanidine in 5 parts of deionized water under the atmosphere of nitrogen, simultaneously dropwise adding 1mol/L NaOH solution and 2-2.2 parts of methacryloyl chloride into guanidine aqueous solution at the temperature of 0-10 ℃, controlling the dropwise adding speed of NaOH, maintaining the pH of the system at 9-12, stirring and reacting at the temperature of 10-25 ℃ for 8-12h after dropwise adding is finished, extracting mixed solution by trichloromethane after reaction is finished, washing extract liquor by 5% acetic acid aqueous solution and saturated sodium bicarbonate water for three times respectively, and removing the solvent by reduced pressure distillation after washing is finished to obtain a product I;
(2) dissolving 1 part of dodecamethylhydrohexasiloxane in 50 parts of tetrahydrofuran, and mixing 1.2-1.4 parts of product I, 1 wt% of polymerization inhibitor and 10 parts of product I-4Portions of catalyst, solutionAdding 10 parts of tetrahydrofuran into a constant-pressure dropping funnel, controlling the dropping speed, stirring, reacting at 60-120 ℃ for 3-5h, distilling under reduced pressure to remove the solvent, adding 30 parts of toluene, excessive sodium bicarbonate and 10 parts of deionized water, stirring at 60 ℃ for 3h, separating a water phase, taking an organic layer, distilling under reduced pressure to remove the solvent, and obtaining a product II, namely the antimicrobial polymer containing guanidino.
5. The self-adhesive antibacterial silicone rubber according to claim 4, wherein the polymerization inhibitor is 2, 6-di-tert-butyl-p-methylphenol, hydroquinone or p-hydroxyanisole.
6. The self-adhesive antibacterial silicone rubber according to claim 4, wherein the catalyst is chloroplatinic acid, carbene alkane, platinum dioxide or aluminum trichloride.
7. The preparation method of the self-adhesive antibacterial silicone rubber patch according to claim 1, characterized by comprising the following steps:
(1) preparing antibacterial silicone rubber, namely adding 70 parts by weight of antibacterial polymer containing guanidino, 60 parts by weight of α, omega-divinyl polydimethylsiloxane and 0.5-1 part by weight of boric acid into a kneading machine at 60-80 ℃ under the protection of nitrogen, stirring, keeping the temperature for 2 hours to obtain an antibacterial base material, then adding methyl hydrogen polysiloxane according to parts by weight, heating to 80-100 ℃, and stirring at the constant temperature for 2.5 hours to obtain the antibacterial silicone rubber;
(2) preparation of self-adhesive antibacterial silicone rubber patch master batch: adding antibacterial silicone rubber, a reinforcing agent, a flame retardant and an antioxidant into an internal mixer according to parts by weight, adjusting the temperature of the internal mixer to be 100-; adding a structure control agent, continuously banburying for 2h, controlling the glue temperature at 120-;
(3) preparing a self-adhesive antibacterial silicone rubber patch: and (3) uniformly mixing a vulcanizing agent and the master batch in the step (2) on an open mill, thinly passing, discharging, vulcanizing by using a flat vulcanizing machine, cooling, trimming, inspecting and packaging to obtain the self-adhesive antibacterial silicone rubber patch.
8. The preparation method of the self-adhesive antibacterial silicone rubber according to claim 7, wherein the mixing temperature in the step (3) is 80 ℃ to 100 ℃, and the mixing time is 10 min to 30 min; the vulcanization temperature is 150-180 ℃, the time is 10-30min, and the pressure is 10-15 MPa.
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| CN111269660B (en) | 2022-04-19 |
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