CN111303637A - Preparation method of medical organic silicon rubber composition - Google Patents
Preparation method of medical organic silicon rubber composition Download PDFInfo
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- CN111303637A CN111303637A CN202010282495.7A CN202010282495A CN111303637A CN 111303637 A CN111303637 A CN 111303637A CN 202010282495 A CN202010282495 A CN 202010282495A CN 111303637 A CN111303637 A CN 111303637A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a preparation method of a medical organic silicon rubber composition, which is prepared by uniformly mixing (i) organopolysiloxane containing two or more unsaturated groups, (ii) polyhydrosiloxane, (iii) medical antibacterial filler, (iv) platinum catalyst and (V) inhibitor and heating and curing at 130-200 ℃. The medical organic silicon rubber composition provided by the preparation method provided by the invention adopts the medical antibacterial filler as the reinforcing filler, the medical antibacterial filler can simultaneously improve the mechanical property and the antibacterial property of the medical organic silicon rubber composition, and the medical organic silicon rubber composition can be used for preparing medical hoses and catheters and has a huge application prospect in other fields.
Description
Technical Field
The invention relates to the field of silicone rubber, in particular to a medical organic silicone rubber composition and a preparation method thereof.
Background
Silicone rubber is physiologically inert and reacts little when contacting biological tissues, and is therefore widely used in the medical industry, such as medical hoses, catheters, and the like. As a material for medical catheters, soft polyvinyl chloride is generally used in addition to silicone rubber, and silicone rubber is superior in biocompatibility and flexibility to polyvinyl chloride materials, but its mechanical properties, particularly tensile strength and tear strength, are insufficient. In addition, as a medical material, the silicone rubber surface may have a large number of bacteria on it, which may even cause infection.
CN104448443A discloses a corrosion-resistant medical rubber and a preparation method thereof, wherein styrene-butadiene rubber, fluorosilicone rubber and ethylene propylene diene monomer are adopted, but a vulcanizing agent is not used in the preparation method, and the obtained material has poor mechanical properties.
CN10444828A discloses an antibacterial drug-loaded microsphere silicone rubber composite material, in the method, a silicone rubber matrix and PLGA drug-loaded microspheres are uniformly mixed, and the prepared composite material has good antibacterial property but poor mechanical property.
Disclosure of Invention
Therefore, the invention aims to provide a medical organic silicon rubber composition and a preparation method thereof.
The invention also provides a medical antibacterial filler and a preparation method thereof.
The medical antibacterial filler is obtained by reacting quaternary ammonium organosilane with white carbon black, wherein the white carbon black is precipitated white carbon black or gas-phase white carbon black or a mixture of the precipitated white carbon black and the gas-phase white carbon black, and the gas-phase white carbon black is preferred. According to the test by a BET method, the specific surface area of the white carbon black is 50-500 m2Per g, preferably from 200 to 400 m2/g。
The white carbon black can be white carbon black powder or white carbon black water slurry obtained by high-speed grinding of white carbon black and deionized water; the quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium bromide, 3- (trimethoxysilyl) propyl didecylmethyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyltetradecyl ammonium bromide and 3- (triethoxysilyl) propyl dimethyloctadecyl ammonium chloride. The quaternary organosilanes described may be either self-made in the laboratory or commercially available, and are typically applied from a solvent solution (e.g., a lower alcohol); the auxiliary solvent is lower alcohol, preferably one or more of methanol and ethanol.
The preparation method of the medical antibacterial filler comprises the following steps: adding white carbon black into a reaction kettle, adding deionized water, stirring uniformly, controlling the reaction temperature at 60-90 ℃, adding a catalyst to adjust the pH value of the solution, adding quaternary amine organosilane into the solution, reacting for 0.1-10 hours, performing suction filtration, and drying to obtain the medical antibacterial filler.
Wherein, the mass content of the white carbon black in the mixed solution of the white carbon black and the deionized water is 1-25%, preferably 5-20%, and more preferably 10-20%.
The mass amount of the quaternary amine organosilane is 1-50%, preferably 5-30%, more preferably 10-25% of the mass amount of the white carbon black.
The catalyst is an acidic catalyst, preferably one or more of hydrochloric acid, dilute sulfuric acid, benzoic acid and acetic acid.
The pH of the reaction solution is between 1 and 6, preferably between 2 and 5, more preferably between 2.5 and 4.5.
The reaction temperature is 60 to 90 ℃, preferably 70 to 90 ℃.
The reaction time is 0.1 to 10 hours, preferably 0.5 to 5 hours, more preferably 2 to 5 hours.
The medical antibacterial filler can be used as an additive of plastics, resin and rubber, can be applied to the fields of foods, cosmetics, fiber products, household electrical appliances, building material products, office supplies, toys and medical products, and can be used for preparing products such as plastic boxes, pipelines, clothes, medical hoses, masks, films, gloves, baby feeding bottles and the like.
The invention provides a medical organic silicon rubber composition, which is prepared by mixing, heating and curing raw materials, wherein the raw materials comprise the following components in parts by weight:
(i) 100-300 parts of organopolysiloxane containing two or more unsaturated groups
(ii) 0.2-20 parts of polyhydrosiloxane
(iii) 10-80 parts of medical antibacterial filler
(iv) 0.002-1 part of platinum catalyst
(V) 0.01-1 part of inhibitor
The medical antibacterial filler is obtained by reacting quaternary ammonium organosilane with white carbon black, wherein the white carbon black is precipitated white carbon black or gas-phase white carbon black or a mixture of the precipitated white carbon black and the gas-phase white carbon black, and the gas-phase white carbon black is preferred. According to the test by a BET method, the specific surface area of the white carbon black is 50-500 m2Per g, preferably from 200 to 400 m2/g。
The white carbon black can be white carbon black powder or white carbon black water slurry obtained by high-speed grinding of white carbon black and deionized water; the quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium bromide, 3- (trimethoxysilyl) propyl didecylmethyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyltetradecyl ammonium bromide and 3- (triethoxysilyl) propyl dimethyloctadecyl ammonium chloride. The quaternary organosilanes described may be either self-made in the laboratory or commercially available, and are typically applied from a solvent solution (e.g., a lower alcohol); the auxiliary solvent is lower alcohol, preferably one or more of methanol and ethanol.
The preparation method of the medical antibacterial filler comprises the following steps: adding white carbon black into a reaction kettle, adding deionized water, stirring uniformly, controlling the reaction temperature at 60-90 ℃, adding a catalyst to adjust the pH value of the solution, adding quaternary amine organosilane into the solution, reacting for 0.1-10 hours, performing suction filtration, and drying to obtain the medical antibacterial filler.
Wherein, the mass content of the white carbon black in the mixed solution of the white carbon black and the deionized water is 1-25%, preferably 5-20%, and more preferably 10-20%.
The mass amount of the quaternary amine organosilane is 1-50%, preferably 5-30%, more preferably 10-25% of the mass amount of the white carbon black.
The catalyst is an acidic catalyst, preferably one or more of hydrochloric acid, dilute sulfuric acid, benzoic acid and acetic acid.
The pH of the reaction solution is between 1 and 6, preferably between 2 and 5, more preferably between 2.5 and 4.5.
The reaction temperature is 60 to 90 ℃, preferably 70 to 90 ℃.
The reaction time is 0.1 to 10 hours, preferably 0.5 to 5 hours, more preferably 2 to 5 hours.
Component (i) is a linear, cyclic or branched organopolysiloxane composed of structural units of the formula RaR1 bSiO(4-a-b)/2，
In the formula, R is substituted or unsubstituted alkyl of C1-C18; r1Substituted or unsubstituted alkylene or alkynyl of C2-C10 in Si-C bond;
a is an integer of 0-3, b is an integer of 0-2, and a + b is less than or equal to 3.
Specifically, R may be the same or different, the hydrocarbon group includes aliphatic hydrocarbon groups which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl or decyl, and aromatic hydrocarbon groups; the aromatic hydrocarbon group may be a phenyl group or a benzyl group; preferred hydrocarbon groups are C1-C6 aliphatic hydrocarbon groups or phenyl groups, preferably methyl or phenyl groups.
R1Preferably vinyl, propenyl, methallyl, ethynyl, butadienyl, hexadienyl, vinylphenyl or styryl, more preferably vinyl.
The organopolysiloxane of component (i) may be an olefin-based polysiloxane of relatively low molecular weight, or may be a highly polymerized polydimethylsiloxane having at least two silicon-bonded vinyl groups along the chain or at the chain ends; the structure of the oligomeric or highly polymeric siloxanes can be linear, cyclic or branched, and also dendritic or network-like structures. The linear or cyclic polysiloxane is mainly represented by the formula R3SiO1/2、R2R1SiO1/2、R1RSiO2/2Or R2SiO2/2The structural unit of (1); wherein R is1And R is as defined above.
Component (i) is most preferably an organopolysiloxane having a linear polysiloxane viscosity of from 1 mPas to 100000 mPas (at a temperature of 25 ℃) and a molar mass of 102～106g/mol。
In one embodiment of the present invention, the organopolysiloxane of component (i) is α, ε -vinyldimethylpolysiloxane, having the following structural formula:
wherein n is greater than 0 and n represents the degree of polymerization.
Component (ii) is a polyhydrosiloxane consisting of structural units of the formula:
RcHdSiO(4-c-d)/2
in the formula, R is a substituted or unsubstituted saturated alkyl of C1-C18; c is an integer of 0-3, d is an integer of 0-2, and c + d is less than or equal to 3; an average of at least 2 silicon-bonded hydrogen atoms per molecule; the polyhydrogensiloxane preferably contains 0.1 to 1.6 weight percent silicon-bonded hydrogen atoms.
Specifically, R may be the same or different, the hydrocarbon group includes aliphatic hydrocarbon groups which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl or decyl, and aromatic hydrocarbon groups; the aromatic hydrocarbon group may be a phenyl group or a benzyl group; preferred hydrocarbon groups are C1-C6 aliphatic hydrocarbon groups or phenyl groups, preferably methyl or phenyl groups.
The polyhydrosiloxane of component (ii) may be a relatively low molecular weight SiH functional oligosiloxane, such as tetramethyldisiloxane; highly polymerized polydimethylsiloxanes having SiH groups along or at the chain ends are also possible, although any different mixture of siloxanes which are known to meet the performance criteria after curing can be used. The quantity of the polyhydrosiloxane of component (ii) used must be such that the molar ratio of SiH groups to all the aliphatic unsaturation of the silicone rubber component is between 0.9 and 10.
Component (ii) is most preferably a polyhydrosiloxane having a linear polysiloxane viscosity of from 1 to 10000 mPas (at a temperature of 25 ℃) and a molar mass of 102～106g/mol。
In one embodiment of the present invention, the component (ii), the polyhydrosiloxane, has the formula:
wherein c and d represent polymerization degrees, c is more than or equal to 0, and d is more than 0.
The platinum catalyst described under component (iv) is preferably a platinum compound compatible in polyorganosiloxanes and component (iv) is selected from the group consisting of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex, bis (alkynyl) (1, 5-cyclooctadiene) platinum complex, bis (alkynyl) (bicyclo [2.2.1] hepta-2, 5-diene) platinum complex, bis (alkynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex or bis (alkynyl) (1, 6-dimethyl-1, 5-cyclooctadiene) platinum complex.
Component (iv) the amount of platinum catalyst used depends on factors such as the rate of crosslinking and economics and the use of each component, and is typically between 2 and 5000 ppm of platinum catalyst per 100 parts by weight of curable organopolysiloxane.
The alkyne-containing inhibitor described in component (v) is used for controlled adjustment of the processing time, the initiation temperature and the crosslinking speed of the silicone rubber of the invention. Commonly used inhibitors are acetylenic inhibitors, preferably component (v) is selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol.
The invention also provides a preparation method of the medical organic silicon rubber composition, which is prepared by mixing, heating and curing the raw materials in parts by weight:
(i) 100-300 parts of organopolysiloxane containing two or more unsaturated groups
(ii) 0.2-20 parts of polyhydrosiloxane
(iii) 10-80 parts of medical antibacterial filler
(iv) 0.002-1 part of platinum catalyst
(V) 0.01-1 part of inhibitor
The process of heating and curing at 130-200 ℃ after uniformly mixing the raw materials comprises the following steps: uniformly mixing the components (i) and (iii) to obtain a basic rubber material; taking 40-60% of the basic rubber material in percentage by mass, adding the component (iv), and uniformly stirring to obtain a component (A) for later use; adding the components (ii) and (v) into the rest base rubber material, and uniformly stirring to obtain a component (B) for later use; the component (A) and the component (B) are uniformly mixed and heated and cured at the temperature of 100-200 ℃ to obtain the high-performance polyurethane adhesive.
The above-mentioned technological steps of mixing, stirring and heating-curing in the course of heating-curing are all adopted by existent technology in the field.
The medical antibacterial filler is obtained by reacting quaternary ammonium organosilane with white carbon black, wherein the white carbon black is precipitated white carbon black or gas-phase white carbon black or a mixture of the precipitated white carbon black and the gas-phase white carbon black, and the gas-phase white carbon black is preferred. According to the test by a BET method, the specific surface area of the white carbon black is 50-500 m2Per g, preferably from 200 to 400 m2/g。
The white carbon black can be white carbon black powder or white carbon black water slurry obtained by high-speed grinding of white carbon black and deionized water; the quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium bromide, 3- (trimethoxysilyl) propyl didecylmethyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyltetradecyl ammonium bromide and 3- (triethoxysilyl) propyl dimethyloctadecyl ammonium chloride. The quaternary organosilanes described may be either self-made in the laboratory or commercially available, and are typically applied from a solvent solution (e.g., a lower alcohol); the auxiliary solvent is lower alcohol, preferably one or more of methanol and ethanol.
The preparation method of the medical antibacterial filler comprises the following steps: adding white carbon black into a reaction kettle, adding deionized water, stirring uniformly, controlling the reaction temperature at 60-90 ℃, adding a catalyst to adjust the pH value of the solution, adding quaternary amine organosilane into the solution, reacting for 0.1-10 hours, performing suction filtration, and drying to obtain the medical antibacterial filler.
Wherein, the mass content of the white carbon black in the mixed solution of the white carbon black and the deionized water is 1-25%, preferably 5-20%, and more preferably 10-20%.
The mass amount of the quaternary amine organosilane is 1-50%, preferably 5-30%, more preferably 10-25% of the mass amount of the white carbon black.
The catalyst is an acidic catalyst, preferably one or more of hydrochloric acid, dilute sulfuric acid, benzoic acid and acetic acid.
The pH of the reaction solution is between 1 and 6, preferably between 2 and 5, more preferably between 2.5 and 4.5.
The reaction temperature is 60 to 90 ℃, preferably 70 to 90 ℃.
The reaction time is 0.1 to 10 hours, preferably 0.5 to 5 hours, more preferably 2 to 5 hours.
Component (i) is a linear, cyclic or branched organopolysiloxane composed of structural units of the formula RaR1 bSiO(4-a-b)/2，
In the formula, R is substituted or unsubstituted alkyl of C1-C18; r1Substituted or unsubstituted alkylene or alkynyl of C2-C10 in Si-C bond;
a is an integer of 0-3, b is an integer of 0-2, and a + b is less than or equal to 3.
Specifically, R may be the same or different, the hydrocarbon group includes aliphatic hydrocarbon groups which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl or decyl, and aromatic hydrocarbon groups; the aromatic hydrocarbon group may be a phenyl group or a benzyl group; preferred hydrocarbon groups are C1-C6 aliphatic hydrocarbon groups or phenyl groups, preferably methyl or phenyl groups.
R1Preferably vinyl, propenyl, methallyl, ethynyl, butadienyl, hexadienyl, vinylphenyl or styryl, more preferably vinyl.
The organopolysiloxane of component (i) may be an olefin-based polysiloxane of relatively low molecular weight, or may be a highly polymerized polydimethylsiloxane having at least two silicon-bonded vinyl groups along the chain or at the chain ends; the structure of the oligomeric or highly polymeric siloxanes can be linear, cyclic or branched, and also dendritic or network-like structures. The linear or cyclic polysiloxane is mainly represented by the formula R3SiO1/2、R2R1SiO1/2、R1RSiO2/2Or R2SiO2/2Structural sheet ofMeta-formation; wherein R is1And R is as defined above.
Component (i) is most preferably an organopolysiloxane having a linear polysiloxane viscosity of from 1 mPas to 100000 mPas (at a temperature of 25 ℃) and a molar mass of 102～106g/mol。
In one embodiment of the present invention, the organopolysiloxane of component (i) is α, ε -vinyldimethylpolysiloxane, having the following structural formula:
wherein n is greater than 0 and n represents the degree of polymerization.
Component (ii) is a polyhydrosiloxane consisting of structural units of the formula:
RcHdSiO(4-c-d)/2
in the formula, R is a substituted or unsubstituted saturated alkyl of C1-C18; c is an integer of 0-3, d is an integer of 0-2, and c + d is less than or equal to 3; an average of at least 2 silicon-bonded hydrogen atoms per molecule; the polyhydrogensiloxane preferably contains 0.1 to 1.6 weight percent silicon-bonded hydrogen atoms.
Specifically, R may be the same or different, the hydrocarbon group includes aliphatic hydrocarbon groups which may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl or decyl, and aromatic hydrocarbon groups; the aromatic hydrocarbon group may be a phenyl group or a benzyl group; the preferable alkyl is C1-C6 aliphatic alkyl or phenyl, preferably methyl or phenyl.
The polyhydrosiloxane of component (ii) may be a relatively low molecular weight SiH functional oligosiloxane, such as tetramethyldisiloxane; highly polymerized polydimethylsiloxanes having SiH groups along or at the chain ends are also possible, although any different mixture of siloxanes which are known to meet the performance criteria after curing can be used. The quantity of the polyhydrosiloxane of component (ii) used must be such that the molar ratio of SiH groups to all the aliphatic unsaturation of the silicone rubber component is between 0.9 and 10.
Component (ii) is most preferably a polyhydrosiloxane having a linear polysiloxane viscosity of from 1 to 10000 mPas (at a temperature of 25 ℃) and a molar mass of 102～106g/mol。
In one embodiment of the present invention, the component (ii), the polyhydrosiloxane, has the formula:
wherein c and d represent polymerization degrees, c is more than or equal to 0, and d is more than 0.
The platinum catalyst described under component (iv) is preferably a platinum compound compatible in polyorganosiloxanes and component (iv) is selected from the group consisting of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex, bis (alkynyl) (1, 5-cyclooctadiene) platinum complex, bis (alkynyl) (bicyclo [2.2.1] hepta-2, 5-diene) platinum complex, bis (alkynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex or bis (alkynyl) (1, 6-dimethyl-1, 5-cyclooctadiene) platinum complex.
The amount of platinum catalyst used depends on the rate of crosslinking and economics and the use of the components, and is typically between 2 and 5000 ppm per 100 parts by weight of the curable organopolysiloxane.
The alkyne-containing inhibitor described in component (v) is used for controlled adjustment of the processing time, the initiation temperature and the crosslinking speed of the silicone rubber of the invention. Commonly used inhibitors are acetylenic inhibitors, preferably component (v) is selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol.
By adopting the existing mould in the prior art and common processing means such as extrusion, molding and the like, the medical organic silicon rubber composition can be processed into common shapes such as a tubular shape, a sheet shape, a strip shape, a cylindrical shape and the like, can be used for preparing a transfusion tube and a catheter, can also be used for preparing rubber nipples, pacifiers, milk spoons and other baby products, and can also be used for preparing products such as gloves, goggles, masks and the like.
According to the medical organic silicon rubber composition provided by the invention, the white carbon black modified by quaternary ammonium organosilane is used as a reinforcing filler, and the modified white carbon black can be well mixed with the rest components, so that a silicon rubber product with excellent mechanical property is obtained.
According to the invention, the white carbon black modified by quaternary ammonium organosilane is used as the medical antibacterial filler, the surface hydroxyl of the white carbon black is reduced by the white carbon black modified by the quaternary ammonium organosilane, and the dispersibility of the medical antibacterial filler in a silicon rubber matrix is improved, so that the mechanical property of the silicon rubber is improved. The medical antibacterial filler simultaneously retains the antibacterial property of quaternary ammonium organosilane, so that the silicone rubber has good antibacterial performance, the antibacterial rate of the prepared silicone rubber to bacteria exceeds 95 percent, the bacteria comprise staphylococcus aureus, escherichia coli and candida albicans, and the medical antibacterial filler can be used for preparing medical hoses, masks and glove products.
The raw materials used in the invention can be obtained commercially, and the raw materials have the characteristics of wide and simple sources, low cost and simple and convenient preparation method. The medical antibacterial filler provided by the invention can be widely applied to the field of organic silicon, and the obtained medical organic silicon rubber composition has good mechanical property and antibacterial property, so that the medical organic silicon rubber composition has a good application prospect, and particularly has a good application prospect in the field of medical treatment.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
Synthesis example 1
65 parts by weight of fumed silica (specific surface area 250 m)2Product of Cambot corporation, USA), adding 650 parts by weight of deionized water, stirring uniformly, heating to 75 ℃ with an oil bath pot, adjusting the pH value of the solution to 3.5 with dilute sulfuric acid, adding 3- (trimethoxy-silyl) propyl dimethyl octadecyl ammonium chloride with 10 mass percent of white carbon black, reacting for 2.5 hours, filtering, and drying to obtain the medical antibacterial filler.
Synthesis example 2
70 parts by weight of fumed silica (specific surface area 250 m)2Product of Cambot corporation, USA), adding 700 parts by weight of deionized water into a reaction kettle, stirring uniformly, heating to 80 ℃ by an oil bath pot, adjusting the pH value of the solution to 3.5 by dilute sulfuric acid, adding 3- (triethoxy-silyl) propyl dimethyl octadecyl ammonium chloride with the white carbon black mass content of 12%, reacting for 3 hours, filtering, and drying to obtain the medical antibacterial filler.
Synthesis example 3
70 parts by weight of fumed silica (specific surface area 250 m)2Product of Cambot corporation, USA), adding 700 parts by weight of deionized water into a reaction kettle, stirring uniformly, heating to 80 ℃ by an oil bath pot, adjusting the pH value of the solution to 4 by dilute sulfuric acid, adding 3- (trimethoxy-silyl) propyl dimethyl octadecyl ammonium chloride with 10 mass percent of white carbon black, reacting for 3.5 hours, filtering, and drying to obtain the medical antibacterial filler.
Example 1
Adding 210 parts by weight of α, epsilon-vinyl dimethyl polydimethylsiloxane (viscosity is 10000mPa & s, 25 ℃) into a vacuum kneader, adding 60 parts by weight of the medical antibacterial filler obtained in synthesis example 1 into the vacuum kneader in 8 times, uniformly mixing, heating to 150 ℃, heating and kneading for 2 hours, removing low molecules in vacuum for 2 hours, cooling, grinding by a three-roll machine, and filtering to obtain the silicone rubber base rubber.
The silicone rubber base rubber is averagely divided into two parts, 0.01 part by weight of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added into one part of silicone rubber base, and the components are uniformly stirred, degassed and filtered to obtain the component (A).
Adding 3.0 parts by weight of polymethylhydrosiloxane (with the viscosity of 60mPa & s, the temperature of 25 ℃, H% = 0.99%) and 0.04 part by weight of 1-ethynyl-1-cyclohexanol reaction inhibitor into the other part of silicone rubber base material, uniformly mixing at room temperature, removing bubbles, and filtering to obtain the component (B).
Uniformly mixing the component (A) and the component (B) according to the mass ratio of 1:1, injecting the mixture into a mold, and curing the mixture for 5min at 150 ℃ to obtain the medical organic silicon rubber material.
Example 2
230 parts by weight of α, epsilon-vinyl dimethyl polydimethylsiloxane (viscosity 10000mPa & s, 25 ℃) is added into a vacuum kneader, 60 parts by weight of the medical antibacterial filler obtained in synthesis example 2 is added into the vacuum kneader for 8 times and mixed evenly, the temperature is raised to 150 ℃, the mixture is heated and kneaded for 2 hours, the low molecules are removed in vacuum for 2 hours, the mixture is cooled and ground by a three-roll machine, and the silicone rubber base rubber is obtained after filtration.
The silicone rubber base rubber is averagely divided into two parts, 0.01 part by weight of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added into one part of silicone rubber base, and the components are uniformly stirred, degassed and filtered to obtain the component (A).
Adding 3.0 parts by weight of polymethylhydrosiloxane (with the viscosity of 60mPa & s, the temperature of 25 ℃, H% = 0.99%) and 0.04 part by weight of 1-ethynyl-1-cyclohexanol reaction inhibitor into the other part of silicone rubber base material, uniformly mixing at room temperature, removing bubbles, and filtering to obtain the component (B).
Uniformly mixing the component (A) and the component (B) according to the mass ratio of 1:1, injecting the mixture into a mold, and curing the mixture for 5min at 150 ℃ to obtain the medical organic silicon rubber material.
Example 3
Adding 200 parts by weight of α, epsilon-vinyl dimethyl polydimethylsiloxane (viscosity is 10000mPa & s, 25 ℃) into a vacuum kneader, adding 60 parts by weight of the medical antibacterial filler obtained in the synthesis example 3 into the vacuum kneader in 8 times, uniformly mixing, heating to 150 ℃, heating and kneading for 2 hours, removing low molecules in vacuum for 2 hours, cooling, grinding by a three-roll machine, and filtering to obtain the silicone rubber base rubber.
The silicone rubber base rubber is averagely divided into two parts, 0.01 part by weight of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added into one part of silicone rubber base, and the components are uniformly stirred, degassed and filtered to obtain the component (A).
Adding 3.0 parts by weight of polymethylhydrosiloxane (with the viscosity of 60mPa & s, the temperature of 25 ℃, H% = 0.99%) and 0.04 part by weight of 1-ethynyl-1-cyclohexanol reaction inhibitor into the other part of silicone rubber base material, uniformly mixing at room temperature, removing bubbles, and filtering to obtain the component (B).
Uniformly mixing the component (A) and the component (B) according to the mass ratio of 1:1, injecting the mixture into a mold, and curing the mixture for 5min at 150 ℃ to obtain the medical organic silicon rubber material.
Example 4
200 parts by weight of α, epsilon-vinyl dimethyl polydimethylsiloxane (viscosity: 10000 mPa.s, 25 ℃) is added into a vacuum kneader, 65 parts by weight of the medical antibacterial filler obtained in synthesis example 1 is added in 8 times and mixed evenly, the temperature is raised to 150 ℃, the mixture is heated and kneaded for 2 hours, the low molecules are removed in vacuum for 2 hours, the mixture is cooled and ground by a three-roll machine, and the silicone rubber base rubber is obtained after filtration.
The silicone rubber base rubber is averagely divided into two parts, 0.01 part by weight of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added into one part of silicone rubber base, and the components are uniformly stirred, degassed and filtered to obtain the component (A).
Adding 3.0 parts by weight of polymethylhydrosiloxane (with the viscosity of 60mPa & s, the temperature of 25 ℃, H% = 0.99%) and 0.04 part by weight of 1-ethynyl-1-cyclohexanol reaction inhibitor into the other part of silicone rubber base material, uniformly mixing at room temperature, removing bubbles, and filtering to obtain the component (B).
Uniformly mixing the component (A) and the component (B) according to the mass ratio of 1:1, injecting the mixture into a mold, and curing the mixture for 5min at 150 ℃ to obtain the medical organic silicon rubber material.
Comparative example 1
200 parts by weight of α, ε -vinyldimethylpolysiloxane (viscosity: 10000 mPas, 25 ℃) was added into a vacuum kneader, and 60 parts by weight of fumed silica (specific surface area: 250 m) was added thereto in 8 portions2Hexamethyldisilazane surface modification, product of cabot corporation, usa) and mixing uniformly, heating to 150 ℃, heating and kneading for 2 hours, removing low molecules for 2 hours in vacuum, cooling, grinding by a three-roll machine, and filtering to obtain the silicone rubber base rubber material.
The silicone rubber base rubber is averagely divided into two parts, 0.01 part by weight of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added into one part of silicone rubber base, and the components are uniformly stirred, degassed and filtered to obtain the component (A).
Adding 3.0 parts by weight of polymethylhydrosiloxane (with the viscosity of 60mPa & s, the temperature of 25 ℃, H% = 0.99%) and 0.04 part by weight of 1-ethynyl-1-cyclohexanol reaction inhibitor into the other part of silicone rubber base material, uniformly mixing at room temperature, removing bubbles, and filtering to obtain the component (B).
Uniformly mixing the component (A) and the component (B) according to the mass ratio of 1:1, injecting the mixture into a mold, and curing the mixture for 5min at 150 ℃ to obtain the silicone rubber material.
Comparative example 2
Adding α parts by weight of epsilon-vinyl dimethyl polydimethylsiloxane (viscosity is 10000mPa & s, 25 ℃) 210 parts by weight of α parts by weight into a vacuum kneader, uniformly mixing the materials by 8 times, adding 3- (trimethoxy-silyl) propyl dimethyl octadecyl ammonium chloride with the mass of 10% of the white carbon black, heating to 150 ℃, kneading for 2 hours, removing low molecules in vacuum for 2 hours, cooling, grinding by a three-roll machine, and filtering to obtain the silicone rubber base rubber material.
The silicone rubber base rubber is averagely divided into two parts, 0.01 part by weight of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex is added into one part of silicone rubber base, and the components are uniformly stirred, degassed and filtered to obtain the component (A).
Adding 3.0 parts by weight of polymethylhydrosiloxane (with the viscosity of 60mPa & s, the temperature of 25 ℃, H% = 0.99%) and 0.04 part by weight of 1-ethynyl-1-cyclohexanol reaction inhibitor into the other part of silicone rubber base material, uniformly mixing at room temperature, removing bubbles, and filtering to obtain the component (B).
Uniformly mixing the component (A) and the component (B) according to the mass ratio of 1:1, injecting the mixture into a mold, and curing the mixture for 5min at 150 ℃ to obtain the silicone rubber material.
The tensile strength, elongation and tear strength of the samples of the medical silicone rubber materials in examples 1-4 and comparative examples 1-2 were measured according to GB/T528-2009 and GB/T529-2008, respectively. The antibacterial performance of the materials obtained in examples 1-4 and comparative example 2 was determined according to the antibacterial performance of ISO 22196-2011 plastic and other nonporous surfaces. Part 5 of the biological evaluation of medical devices according to the standard GB/T16886.5-2003: in vitro cytotoxicity assays were performed. Examples 1-4 the medical silicone rubber material was grade 0 cytotoxic.
TABLE 1 test results of physical and mechanical properties and antibacterial properties
As can be seen from the above test results, the medical silicone rubber compositions of examples 1-4 of the present invention have better mechanical properties and antibacterial properties than the comparative silicone rubber composition.
Although the invention has been described in detail above with reference to specific embodiments and general illustrations, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (6)
1. The preparation method of the medical organic silicon rubber composition is characterized by comprising the following raw materials in parts by weight:
(i) 100-300 parts of organopolysiloxane containing two or more unsaturated groups
(ii) 0.2-20 parts of polyhydrosiloxane
(iii) 10-80 parts of medical antibacterial filler
(iv) 0.002-1 part of platinum catalyst
(V) 0.01-1 part of inhibitor
The preparation process comprises the following steps: uniformly mixing the components (i) and (iii) to obtain a basic rubber material; taking 40-60% of the basic rubber material in percentage by mass, adding the component (iv), and uniformly stirring to obtain a component (A) for later use; adding the components (ii) and (v) into the rest base rubber material, and uniformly stirring to obtain a component (B) for later use; uniformly mixing the component (A) and the component (B), and heating and curing at 100-200 ℃ to obtain the composite material;
the medical antibacterial filler is obtained by reacting quaternary amine organosilane with white carbon black, and the preparation method of the medical antibacterial filler comprises the following steps: adding white carbon black into a reaction kettle, adding deionized water, uniformly stirring, controlling the reaction temperature at 60-90 ℃, adding a catalyst to adjust the pH value of the solution, adding quaternary ammonium organosilane into the solution, reacting for 0.1-10 hours, performing suction filtration, and drying to obtain the medical antibacterial filler;
the quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium bromide, 3- (trimethoxysilyl) propyl didecylmethyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyltetradecyl ammonium bromide and 3- (triethoxysilyl) propyl dimethyloctadecyl ammonium chloride;
wherein the mass content of the white carbon black in the mixed solution of the white carbon black and deionized water is 1-25%;
the mass consumption of the quaternary amine organosilane is 1-50% of the mass consumption of the white carbon black;
the catalyst is one or more of hydrochloric acid, dilute sulfuric acid, benzoic acid and acetic acid;
the pH value of the reaction solution is between 1 and 6;
the reaction temperature is 60-90 ℃;
the reaction time is 0.1-10 h.
2. The method according to claim 1, wherein the reaction mixture,
component (i) has the structural formula shown below:
wherein n is greater than 0 and represents the degree of polymerization;
component (ii) has the formula shown below:
wherein c and d are more than 0, and c and d represent polymerization degrees.
3. The method of claim 2, wherein:
component (iv) is selected from the group consisting of 1, 3-divinyl-1, 1,3, 3-tetramethyldisiloxane platinum complex, bis (alkynyl) (1, 5-cyclooctadiene) platinum complex, bis (alkynyl) (bicyclo [2.2.1] hepta-2, 5-diene) platinum complex, bis (alkynyl) (1, 5-dimethyl-1, 5-cyclooctadiene) platinum complex or bis (alkynyl) (1, 6-dimethyl-1, 5-cyclooctadiene) platinum complex;
component (v) is selected from 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol.
4. The method of claim 3, wherein:
the white carbon black is precipitated white carbon black or gas-phase white carbon black or a mixture of the precipitated white carbon black and the gas-phase white carbon black, and the specific surface area of the white carbon black is 50-500 m by a BET method2/g；
The quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyloctadecyl ammonium chloride, 3- (trimethoxysilyl) propyl didecylmethyl ammonium chloride, 3- (trimethoxy-silyl) propyl dimethyltetradecyl ammonium chloride and 3- (triethoxysilyl) propyl dimethyloctadecyl ammonium chloride.
5. The method of claim 3, wherein:
the white carbon black is fumed silica;
the quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyl octadecyl ammonium chloride and 3- (triethoxysilyl) propyl dimethyl octadecyl ammonium chloride;
the mass consumption of the quaternary amine organosilane is 5-30% of the mass consumption of the white carbon black;
the catalyst is one or more of hydrochloric acid, dilute sulfuric acid, benzoic acid and acetic acid;
the pH value of the reaction solution is between 2 and 5;
the reaction temperature is 70-90 ℃;
the reaction time is 0.5-10 h.
6. The method of claim 3, wherein:
the white carbon black is fumed silica;
the quaternary amine organosilane is one or more of 3- (trimethoxy-silyl) propyl dimethyl octadecyl ammonium chloride and 3- (triethoxysilyl) propyl dimethyl octadecyl ammonium chloride;
the mass consumption of the quaternary amine organosilane is 10-25% of the mass consumption of the white carbon black;
the catalyst is dilute sulfuric acid;
the pH value of the reaction solution is between 2.5 and 4.5;
the reaction temperature is 70-90 ℃;
the reaction time is 2-10 h.
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| CN113952517A (en) * | 2021-11-01 | 2022-01-21 | 新安天玉有机硅有限公司 | Silicone rubber for medical catheter balloon and preparation method thereof |
| CN118064076A (en) * | 2024-04-24 | 2024-05-24 | 山东沃赛新材料科技有限公司 | Flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive and preparation method thereof |
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| CN113952517A (en) * | 2021-11-01 | 2022-01-21 | 新安天玉有机硅有限公司 | Silicone rubber for medical catheter balloon and preparation method thereof |
| CN118064076A (en) * | 2024-04-24 | 2024-05-24 | 山东沃赛新材料科技有限公司 | Flame-retardant temperature-resistant antibacterial mildew-proof beautifying trimming adhesive and preparation method thereof |
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