CN114456707B - Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof - Google Patents
Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof Download PDFInfo
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Abstract
The invention discloses a quaternary ammonium salt antibacterial composite silicone rubber and a synthesis method thereof, and the method comprises the following steps: adding methylated branched polyethyleneimine, long-chain halogenated hydrocarbon and a solvent, and stirring at 50-120 ℃ for 1-24 hours; after the reaction is finished, removing the solvent to obtain long-chain alkyl modified methylated branched polyethyleneimine; dissolving the long-chain alkyl modified methylated branched polyethyleneimine in a compatibilization crosslinking agent, adding polydimethylsiloxane, and stirring at 50-120 ℃ for 1-24h; then adding a catalyst, and stirring for 3-5 minutes; and coating the prepared mixture on a substrate, and curing at room temperature for 1 hour to 7 days to obtain the quaternary ammonium salt antibacterial composite silicone rubber. The antibacterial silicone rubber obtained by the invention has better antibacterial capability, and compared with the traditional micromolecular antibacterial material, the antibacterial silicone rubber also has the advantages of excellent chemical stability, non-volatility, long-term activity and the like.
Description
Technical Field
The invention relates to the field of antibacterial materials, in particular to a quaternary ammonium salt antibacterial composite silicone rubber and a synthesis method thereof.
Background
Microorganisms have long been a threat to human health and social development, and millions of people and animals and plants die each year as a result of infectious diseases caused by bacterial, viral and fungal infections. Conventional antibacterial agents prepared based on natural or low molecular weight compounds have many limitations such as easy generation of resistance, easy volatility, and environmental pollution and toxicity to human body due to diffusion of killed bacteria.
The antibacterial polymer prepared based on the quaternary ammonium salt antibacterial theory has stronger antibacterial performance. Generally, quaternary ammonium salts are composed of two moieties, a hydrophilic moiety (ammonium cation) and a hydrophobic moiety (hydrophobic alkyl chain of different length). The quaternary ammonium salt deteriorates membrane fluidity and permeability by binding its hydrophobic chain to the lipid bilayer structure of the cell membrane. Ammonium cations interact with negatively charged phospholipids through electrostatic forces, hydrogen bonding, and can cause inhibition or denaturation of cell membrane proteins.
The invention provides a synthesis method of quaternary ammonium salt antibacterial composite silicone rubber. Meanwhile, the introduction of long-chain alkyl generates synergistic effect with high-density quaternary ammonium salt in the system, so that the antibacterial effect is remarkable. The polymer is prepared by methylating primary amine and tertiary amine on branched polyethyleneimine through Eschweiler-Clarke methylation reaction by using branched polyethyleneimine. And then introducing long-chain chloroacetate to react with tertiary amine to form quaternary ammonium salt branched polymer, and blending the quaternary ammonium salt branched polymer with polysiloxane to prepare the silicone rubber with excellent antibacterial performance.
Disclosure of Invention
The invention aims to provide a quaternary ammonium salt antibacterial composite silicone rubber and a synthesis method thereof.
In order to realize the purpose, the following technical scheme is provided:
a synthetic method of quaternary ammonium salt antibacterial silicone rubber comprises the following steps:
(1) Adding methylated branched polyethyleneimine, long-chain halogenated hydrocarbon and a solvent, and stirring at 50-120 ℃ for 1-24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
(2) Dissolving a certain amount of the modified methylated branched polyethyleneimine into the compatibilization crosslinking agent, adding polydimethylsiloxane, and stirring at 50-120 ℃ for 1-24h. Then adding catalyst and stirring for 3-5 minutes. And coating the prepared mixture on a substrate, and curing for 1 hour to 7 days at room temperature to obtain the silicone rubber with antibacterial property.
Preferably, the long-chain halogenated hydrocarbon is nonanol chloroacetate, decanol chloroacetate, undecanol chloroacetate, dodecanol chloroacetate, tridecanol chloroacetate, tetradecanol chloroacetate, pentadecanol chloroacetate, hexadecanol chloroacetate, heptadecanol chloroacetate, or octadecanol chloroacetate; nonanol bromoacetate, decanol bromoacetate, undecanol bromoacetate, dodecanol bromoacetate, tridecanol bromoacetate, tetradecanol bromoacetate, pentadecanol bromoacetate, hexadecanol bromoacetate, heptadecanol bromoacetate, octadecanol bromoacetate; chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorotridecane, chlorotetradecane, chloropentadecane, chlorohexadecane, chloroheptadecane, chlorooctadecane; bromo-nonane, bromo-decane, bromo-undecane, bromo-dodecane, bromo-tridecane, bromo-tetradecane, bromo-pentadecane, bromo-hexadecane, bromo-heptadecane, bromo-octadecane, but not limited thereto.
Preferably, the polydimethylsiloxane is hydroxyl-terminated polydimethylsiloxane having a viscosity of 500cts, 1000cts, 3000cts, 5000cts, 10000cts, 20000cts, but is not limited thereto.
Preferably, the crosslinking agent is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexylalkyl) ethyltriethoxysilane, but is not limited thereto.
Preferably, the catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, tetrabutyl titanate, 2-ethylhexyloxytitanic acid, but is not limited thereto.
Preferably, the solvent is toluene, xylene, N-dimethylformamide or N, N-dimethylacetamide.
Preferably, the molar ratio of the methylated branched polyethyleneimine to the long-chain halogenated hydrocarbon is 1:53-1:123.
preferably, the mass ratio of the long-chain alkyl modified methylated branched polyethyleneimine to the polydimethylsiloxane is 1:0.125-1:0.225.
the invention also provides quaternary ammonium salt antibacterial silicone rubber prepared by the method.
The invention has the beneficial effects that the branched quaternary ammonium salt is introduced into the silicon rubber system, and the epoxy group contained in the cross-linking agent in the system can react with the residual amino group on the branched quaternary ammonium salt, thereby improving the cross-linking degree of the system and solving the problem of poor mechanical property of common antibacterial polymers. Meanwhile, the high-density quaternary ammonium salt structure can ensure excellent antibacterial ability.
Drawings
FIG. 1 is a stress-strain diagram of several antimicrobial silicone rubbers;
FIG. 2 is an infrared spectrum of several antimicrobial silicone rubbers;
fig. 3 is the antimicrobial capacity of several antimicrobial silicone rubbers against e.coli (e.coli);
fig. 4 is a graph of the antimicrobial ability of several antimicrobial silicone rubbers against staphylococcus aureus (s. Aurues);
fig. 5 is a real image of the antibacterial silicone rubber prepared in the embodiment of the present invention.
Detailed description of the preferred embodiment
The principle of the invention is that long-chain halogenated hydrocarbon reacts with branched polyethyleneimine to generate quaternary ammonium salt polymer by utilizing Menschutkin reaction, and the quaternary ammonium salt polymer is mixed with polysiloxane for curing to prepare the antibacterial silicone rubber.
The methylated branched polyethyleneimine and the long-chain halogenated hydrocarbon used in the experiment are both synthesized in the laboratory.
The present invention will be further described with reference to the drawings and examples, and the objects and effects of the present invention will become more apparent.
Example 1:
methylated branched polyethyleneimine (1 g), cetylchloroacetate (3.9352g, 0.0123 mol) and toluene (5 ml) were added and stirred at 50 ℃ for 24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (2.25 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 50 ℃ for 24 hours. Then, dioctyltin dilaurate (0.06 g) was added and stirred for 5 minutes. And coating the prepared mixture on a substrate, and curing at room temperature for 7 days to obtain the silicon rubber with antibacterial property.
Example 2:
methylated branched polyethyleneimine (1 g), cetylchloroacetate (1.6865g, 0.0053mol) and xylene (5 ml) were added, and the mixture was stirred at 120 ℃ for 1 hour. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.2 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 120 ℃ for 1h. Then dioctyltin dilaurate (0.06 g) was added and stirred for 5 minutes. And coating the prepared mixture on a substrate, and curing at room temperature for 7 days to obtain the silicon rubber with antibacterial property.
Example 3:
methylated branched polyethyleneimine (1 g), cetylchloroacetate (2.8109g, 0.0088mol) and N, N-dimethylformamide (5 ml) were added and stirred at 60 ℃ for 24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.75 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 60 ℃ for 12 hours. Then, dioctyltin dilaurate (0.06 g) was added and stirred for 5 minutes. And coating the prepared mixture on a substrate, and curing at room temperature for 7 days to obtain the silicon rubber with antibacterial property.
Example 4:
methylated branched polyethyleneimine (1 g), cetylchloroacetate (2.8109g, 0.0088mol) and toluene (5 ml) were added and stirred at 60 ℃ for 24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.75 g) was dissolved in 3-glycidoxypropyltriethoxysilane (3.5 g), polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12h. Then, dioctyltin dilaurate (0.06 g) was added and stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 5:
methylated branched polyethyleneimine (1 g), cetyl chloroacetate (2.8109g, 0.0088mol), and toluene (5 ml) were added and stirred at 80 ℃ for 24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.75 g) was dissolved in 3-glycidoxypropyltriethoxysilane (3.5 g), polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12h. Tetrabutyltitanate (0.06 g) was then added and stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 6:
methylated branched polyethyleneimine (1 g), tetradecanol chloroacetate (2.5653g, 0.0088mol) and toluene (5 ml) were added and stirred at 80 ℃ for 24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.64 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12 hours. Then, dioctyltin dilaurate (0.06 g) was added and stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 7:
methylated branched polyethyleneimine (1 g), tetradecanol chloroacetate (2.5653g, 0.0088mol) and xylene (5 ml) were added and stirred at 100 ℃ for 24 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.64 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12 hours. Then, dibutyltin dilaurate (0.06 g) was added thereto, and the mixture was stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 8:
methylated branched polyethyleneimine (1 g), tetradecanol chloroacetate (3.0784g, 0.0105 mol), and toluene (5 ml) were added, and the mixture was stirred at 80 ℃ for 12 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.85 g) was dissolved in 3-glycidoxypropylmethyldiethoxysilane (4.28 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12h. Tetrabutyltitanate (0.06 g) was then added thereto, and the mixture was stirred for 5 minutes. And coating the prepared mixture on a substrate, and curing at room temperature for 7 days to obtain the silicon rubber with antibacterial property.
Example 9:
methylated branched polyethyleneimine (1 g), cetyl bromoacetate (3.2003g, 0.0088mol), and toluene (5 ml) were added and stirred at 80 ℃ for 12 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.75 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12 hours. Tetrabutyltitanate (0.06 g) was then added and stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 10:
methylated branched polyethyleneimine (1 g), cetyl bromoacetate (1.9202g, 0.0053 mol), and toluene (5 ml) were added, and stirred at 80 ℃ for 12 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.25 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12 hours. Tetrabutyltitanate (0.06 g) was then added thereto, and the mixture was stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 11:
methylated branched polyethyleneimine (1 g), chlorohexadecane (1.3708g, 0.0053mol) and toluene (5 ml) were added, and the mixture was stirred at 80 ℃ for 12 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A certain amount of the resulting modified methylated branched polyethyleneimine (1.09 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12 hours. Then, dibutyltin dilaurate (0.06 g) was added thereto, and the mixture was stirred for 5 minutes. The prepared mixture is coated on a substrate and cured for 7 days at room temperature to obtain the silicone rubber with antibacterial performance.
Example 12:
methylated branched polyethyleneimine (1 g), chlorohexadecane (2.2846g, 0.0088mol) and toluene (5 ml) were added and stirred at 80 ℃ for 12 hours. And after the reaction is finished, removing the solvent to obtain the long-chain alkyl modified methylated branched polyethyleneimine.
A quantity of the resulting modified methylated branched polyethyleneimine (1.49 g) was dissolved in 3-glycidoxypropyltrimethoxysilane (3 g), and polydimethylsiloxane (10 g) was added and stirred at 80 ℃ for 12h. Then, dibutyltin dilaurate (0.06 g) was added thereto, and the mixture was stirred for 5 minutes. And coating the prepared mixture on a substrate, and curing at room temperature for 7 days to obtain the silicon rubber with antibacterial property.
In accordance with GBThe tensile stress strain of vulcanized rubber or thermoplastic rubber was measured at room temperature using a high-low temperature twin-column tester using dumbbell type I test pieces at a tensile rate of 20mm/min, T528-1998. As shown in fig. 1, rtv is a pure silicone rubber without added quaternary ammonium salt material; RTV-30 is the sample from example 2, RTV-40 is the sample from example 3, RTV-50 is the sample from example 4, RTV-60 is the sample from example 5 and RTV-70 is the sample from example 1. Through tests, it can be seen that the elongation at break can be greatly improved by adding a certain amount of modified polyethyleneimine into the silicone rubber, but the breaking strength is reduced. The increase of the flexibility is beneficial to the application of the antibacterial silicone rubber in medical dressings and the like. FIG. 2 is an infrared spectrum of several antibacterial silicone rubbers of the present invention. RTV is pure silicon rubber without adding quaternary ammonium salt material; RTV-30 is the sample from example 2. 910cm of infrared spectrum of RTV sample -1 Characteristic peak of epoxy groups, and 910cm in the RTV-30 sample -1 No obvious characteristic peak is shown, which indicates that the epoxy group in the epoxy silane and the tertiary amine in the system have anionic polymerization reaction. This also explains the tendency of the strength of the silicone rubber in fig. 1 to decrease, increase again, and finally decrease with increasing addition of modified polyethyleneimine. The epoxy group ring-opening reaction adds a part of the breaking strength to the system.
Fig. 3 is a representation of the antibacterial ability of the antibacterial silicone rubber prepared in examples 2 and 4 against escherichia coli (e.coli), and the tests show that the antibacterial rates are 92.8% and 94.2%. Fig. 4 is a graph showing the antibacterial ability against staphylococcus aureus (s.aurues) of the antibacterial silicone rubbers manufactured in examples 2 and 4, and the tests showed that the antibacterial rates were 95.7% and 97.9%. The sample of the invention has excellent antibacterial performance.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (6)
1. A synthetic method of a quaternary ammonium salt antibacterial composite silicone rubber is characterized by comprising the following steps:
(1) Adding methylated branched polyethyleneimine, long-chain halogenated hydrocarbon and a solvent, and stirring at 50-120 ℃ for 1-24 hours; after the reaction is finished, removing the solvent to obtain long-chain alkyl modified methylated branched polyethyleneimine; the mole ratio of the methylated branched polyethyleneimine to the long-chain halogenated hydrocarbon is 1:53-1:123;
(2) Dissolving the long-chain alkyl modified methylated branched polyethyleneimine in a compatibilization crosslinking agent, wherein the compatibilization crosslinking agent is 3-glycidyl ether oxypropyltrimethoxysilane, 3-glycidyl ether oxypropyltriethoxysilane, 3-glycidyl ether oxypropylmethyldiethoxysilane or 2- (3, 4-epoxycyclohexane) ethyltriethoxysilane, adding polydimethylsiloxane, stirring for 1-24h at 50-120 ℃, and carrying out anionic polymerization reaction on an epoxy group in the compatibilization crosslinking agent and tertiary amine in a system; then adding a catalyst and stirring; coating the prepared mixture on a substrate, and curing at room temperature for 1 hour to 7 days to obtain the quaternary ammonium salt antibacterial composite silicone rubber;
the polydimethylsiloxane is hydroxyl-terminated polydimethylsiloxane, and the mass ratio of the long-chain alkyl modified methylated branched polyethyleneimine to the polydimethylsiloxane is 1:0.125-1:0.225.
2. the method for synthesizing the quaternary ammonium salt antibacterial composite silicone rubber according to claim 1, wherein the long-chain halogenated hydrocarbon is nonanol chloroacetate, decanol chloroacetate, undecanol chloroacetate, dodecanol chloroacetate, tridecanol chloroacetate, tetradecanol chloroacetate, pentadecanol chloroacetate, hexadecanol chloroacetate, heptadecanol chloroacetate, octadecanol chloroacetate, nonanol bromoacetate, decanol bromoacetate, undecanol bromoacetate, dodecanol bromoacetate, tridecanol bromoacetate, tetradecanol bromoacetate, pentadecanol bromoacetate, hexadecanol bromoacetate, heptadecanol bromoacetate, octadecanol bromoacetate, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorotridecyl, chlorotetradecyl, chlorohexadecane, chloroheptadecane, chlorooctadecane; bromononane, bromodecane, bromoundecane, bromododecane, bromotridecane, bromotetradecane, bromopentadecane, bromohexadecane, bromoheptadecane, or bromooctadecane.
3. The method for synthesizing the quaternary ammonium salt antibacterial composite silicone rubber according to claim 1, wherein the viscosity of the polydimethylsiloxane is 500cts, 1000cts, 3000cts, 5000cts, 10000cts or 20000cts.
4. The method for synthesizing the quaternary ammonium salt antibacterial composite silicone rubber according to claim 1, wherein the catalyst is dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dineodecanoate, tetrabutyl titanate or 2-ethylhexyloxytitanate.
5. The method for synthesizing the quaternary ammonium salt antibacterial composite silicone rubber according to claim 1, wherein the solvent is toluene, xylene, N-dimethylformamide or N, N-dimethylacetamide.
6. The quaternary ammonium salt antibacterial composite silicone rubber is characterized by being prepared according to the method of any one of claims 1 to 5.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146835A (en) * | 2016-07-13 | 2016-11-23 | 北京化工大学 | A kind of high molecular quaternary Antibacterial agent preparation method and application |
| CN109714968A (en) * | 2016-07-28 | 2019-05-03 | 艾克森实验室有限公司 | Antimicrobial compositions and its application method based on polymer |
| WO2019105068A1 (en) * | 2017-11-30 | 2019-06-06 | 深圳南玻应用技术有限公司 | Organosilicon antimicrobial solution, organosilicon antimicrobial agent, antimicrobial glass, preparation method therefor and use thereof |
| CN111328827A (en) * | 2020-03-11 | 2020-06-26 | 陕西科技大学 | Quaternized polysilsesquioxane nanosphere hybrid antibacterial material and preparation method thereof |
| CN112593410A (en) * | 2020-12-10 | 2021-04-02 | 辽宁恒星精细化工有限公司 | Waterborne imitation coating high-elasticity stiff and smooth finishing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911597B (en) * | 2012-10-23 | 2015-06-24 | 江苏苏博特新材料股份有限公司 | Environment-friendly coating for protecting bare concrete and preparation method thereof |
| CN103113824A (en) * | 2013-01-18 | 2013-05-22 | 中科院广州化学有限公司 | Film-forming polysiloxane emulsion and preparation method thereof |
| CN105001418B (en) * | 2014-04-16 | 2017-06-27 | 中国科学院宁波材料技术与工程研究所 | A kind of branched polyquaternium and its synthetic method |
| CN104177573B (en) * | 2014-08-13 | 2016-09-07 | 天津大学 | A kind of quaternary ammonium salt-fluorine silica acrylic acid ester block copolymer and preparation method and application are in antimicrobial coating material |
| CN104327721B (en) * | 2014-10-15 | 2016-12-07 | 大连海事大学 | Nano-antibacterial low surface energy organic silicon luminescence antifouling paint and preparation method thereof |
| CN105733268A (en) * | 2016-04-15 | 2016-07-06 | 唐山三友硅业有限责任公司 | Mouldproof antibacterial polyorganosiloxane sealing material and preparation method thereof |
| CN109320967A (en) * | 2018-09-03 | 2019-02-12 | 广州市瑞合新材料科技有限公司 | A kind of antibiotic property add-on type liquid silicon rubber and preparation method thereof |
-
2022
- 2022-02-21 CN CN202210157277.XA patent/CN114456707B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146835A (en) * | 2016-07-13 | 2016-11-23 | 北京化工大学 | A kind of high molecular quaternary Antibacterial agent preparation method and application |
| CN109714968A (en) * | 2016-07-28 | 2019-05-03 | 艾克森实验室有限公司 | Antimicrobial compositions and its application method based on polymer |
| WO2019105068A1 (en) * | 2017-11-30 | 2019-06-06 | 深圳南玻应用技术有限公司 | Organosilicon antimicrobial solution, organosilicon antimicrobial agent, antimicrobial glass, preparation method therefor and use thereof |
| CN111328827A (en) * | 2020-03-11 | 2020-06-26 | 陕西科技大学 | Quaternized polysilsesquioxane nanosphere hybrid antibacterial material and preparation method thereof |
| CN112593410A (en) * | 2020-12-10 | 2021-04-02 | 辽宁恒星精细化工有限公司 | Waterborne imitation coating high-elasticity stiff and smooth finishing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 宋增峰 ; 李俊英 ; 李天铎 ; 李树英 ; .环氧基有机硅季铵盐的合成与应用.有机硅材料.2007,第123卷(第05期),第276-278页. * |
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