Crosslinking type organic silicon emulsion and preparation method thereof
By cross-linking reaction of quaternary phosphonium salt-modified diene Schiff base with silicone components, the stability and antibacterial properties of the silicone emulsion are solved, and efficient antibacterial effect and stability are achieved.
Patent Information
- Application Number
- CN202510534172.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-27
- Publication Date
- 2025-08-19
AI Technical Summary
Traditional silicone emulsions have problems with poor stability and poor antibacterial effects.
The quaternary phosphonium modified diene Schiff base is used to cross-link with 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, hydrogen-containing silicone oil and other components to form the quaternary phosphonium modified diene Schiff base. The cations of the quaternary phosphonium salt are used to destroy the microbial cell membrane through electrostatic action, and the combination of the quaternary phosphonium Schiff base inhibits the enzyme activity to achieve an antibacterial effect.
It improves the antibacterial properties and stability of the silicone emulsion, inhibits the growth and reproduction of microorganisms, and maintains the long-term stability of the emulsion.
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Figure CN120504791A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of organosilicon materials, in particular to a cross-linked organosilicon emulsion and a preparation method thereof. Background Art
[0002] Due to their excellent resistance to high and low temperatures, weatherability, physiological inertness, and flame retardancy, silicone emulsions are widely used in the textile industry to improve the softness, smoothness, and wear resistance of fabrics. However, traditional silicone emulsions suffer from poor stability and inadequate antibacterial efficacy. Therefore, addressing this issue is crucial. The cations (R4P+) of quaternary phosphonium salts adsorb onto negatively charged microbial cell membranes through electrostatic interactions. The hydrophobic groups then insert into the phospholipid bilayer, causing membrane rupture and leakage of the contents. Their application in the cross-linked silicone emulsion of the present invention enhances its antibacterial efficacy. Summary of the Invention
[0003] (1) Technical problems solved
[0004] In view of the deficiencies of the prior art, the present invention provides a cross-linked organosilicon emulsion and a preparation method thereof, which has good antibacterial properties and stability.
[0005] (2) Technical solution
[0006] To achieve the above objectives, the present invention provides the following technical solution: a cross-linked silicone emulsion comprising the following components by weight: 35-55 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 8-10 parts by weight of hydrogenated silicone oil, 1-2 parts by weight of per-tert-butyl hydroperoxide initiator, 10-15 parts by weight of water, 4-6 parts by weight of quaternary phosphonium salt-modified diene Schiff base, 0.6-0.8 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.4-0.5 parts by weight of octadecyltrimethylammonium chloride.
[0007] Furthermore, the preparation method of the quaternary phosphonium salt modified diene Schiff base is:
[0008] S1. 8.1-8.3 g of 4-vinylbenzyl chloride, 13.6-14.8 g of triphenylphosphine, and 45-55 mL of acetone solvent were added to the reactor and reacted. After the reaction was completed, the reaction was cooled to room temperature and dried to obtain intermediate 1;
[0009] S2. To 50-60 mL of N,N-dimethylformamide solvent was added intermediate 1, stirred and dispersed, and then mercaptoethylamine and benzoin dimethyl ether photoinitiator were added thereto, and irradiated with ultraviolet light at 365 nm at 25-40 ° C. After completion, centrifugation, washing and drying were performed to obtain intermediate 2;
[0010] S3. Add 1,4-dialdehyde-2,5-divinylbenzene and intermediate 2 to 45-55 mL of N,N-dimethylformamide solvent, stir and react at 65-80°C for 5-6 hours, and then distill under reduced pressure, wash and dry to obtain a quaternary phosphonium salt-modified diene Schiff base.
[0011] Furthermore, the reaction temperature in S1 is 55-65°C.
[0012] Furthermore, the reaction time in S1 is 20-24 hours.
[0013] Furthermore, the mass ratio of the intermediate 1, mercaptoethylamine, and benzoin dimethyl ether photoinitiator in S2 is 7.21-7.65 g: 6.44-7.3 g: 0.012-0.015 g.
[0014] Furthermore, the irradiation time in S2 is 2-4 hours.
[0015] Furthermore, the mass ratio of 1,4-dialdehyde-2,5-divinylbenzene to intermediate 2 in S3 is 4.14-4.25 g:6.71-7.58 g.
[0016] Furthermore, the preparation method of the cross-linked silicone emulsion is: 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, hydrogenated silicone oil, water, quaternary phosphonium salt-modified diene Schiff base, isomeric tridecanol heptapolyoxyethylene ether, and octadecyltrimethylammonium chloride are stirred and mixed, and then tert-butyl hydroperoxide initiator is continuously added to carry out cross-linking, cooled, and 0.3 mol / L acetic acid is added to adjust the pH to 6-6.5 to obtain a cross-linked silicone emulsion.
[0017] Furthermore, the stirring speed is 1200-1500 r / min, and the stirring time is 20-25 min.
[0018] Furthermore, the cross-linking reaction time is 2-3 hours and the temperature is 60-65°C.
[0019] (3) Beneficial technical effects
[0020] The invention comprises the following steps: stirring and mixing 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, hydrogenated silicone oil, water, quaternary phosphonium salt modified diene Schiff base, isomeric tridecanol heptapolyoxyethylene ether, and octadecyltrimethylammonium chloride; then adding tert-butyl hydroperoxide initiator, reacting, crosslinking, cooling, and adding acetic acid to adjust pH, thereby obtaining a crosslinked organic silicone emulsion.
[0021] The quaternary phosphonium salt cation in the quaternary phosphonium salt-modified diene Schiff base is electrostatically adsorbed to the negatively charged microbial cell membrane. The hydrophobic group then inserts into the phospholipid bilayer, causing membrane rupture and leakage of contents, leading to bacterial death. The antimicrobial properties of the quaternary phosphonium salt inhibit microbial degradation, indirectly maintaining emulsion stability during long-term storage. Bacterial growth and reproduction rely on metabolic reactions catalyzed by various enzymes. The bis-Schiff base groups in the quaternary phosphonium salt-modified diene Schiff base can bind to specific enzymes within the bacteria, inhibiting their activity and ultimately killing the bacteria, resulting in a potent antimicrobial effect. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is the H NMR spectrum of intermediate 1.
[0023] Figure 2 This is the H NMR spectrum of intermediate 2. DETAILED DESCRIPTION
[0024] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.
[0025] In order to better understand the above technical solution, the above technical solution will be described in detail below with reference to the accompanying drawings and specific embodiments.
[0026] Example 1
[0027] S1. 8.1 g of 4-vinylbenzyl chloride, 13.6 g of triphenylphosphine, and 45 mL of acetone solvent were added to a reactor and reacted at 55 ° C for 20 h. After the reaction, the mixture was cooled to room temperature and dried to obtain intermediate 1;
[0028] S2. To 50 mL of N,N-dimethylformamide solvent was added 7.21 g of intermediate 1, stirred and dispersed, and then 6.44 g of mercaptoethylamine and 0.012 g of benzoin dimethyl ether photoinitiator were added thereto. The mixture was irradiated with 365 nm ultraviolet light at 25°C for 2 h, and then centrifuged, washed, and dried to obtain intermediate 2.
[0029] S3. 4.14 g of 1,4-dialdehyde-2,5-divinylbenzene and 6.71 g of intermediate 2 were added to 45 mL of N,N-dimethylformamide solvent and stirred at 65 ° C for 5 h. After the reaction, the mixture was distilled under reduced pressure, washed and dried to obtain a quaternary phosphonium salt-modified diene Schiff base;
[0030] S4. 35 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 8 parts by weight of hydrogenated silicone oil, 10 parts by weight of water, 4 parts by weight of quaternary phosphonium salt-modified diene Schiff base, 0.6 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.4 parts by weight of octadecyltrimethylammonium chloride were stirred and mixed at a stirring speed of 1200 r / min for 20 minutes, and then 1 part by weight of per-tert-butyl hydroperoxide initiator was added, and the mixture was reacted at 60°C for 2 hours for cross-linking. The mixture was cooled, and 0.3 mol / L of acetic acid was added to adjust the pH to 6 to obtain a cross-linked silicone emulsion.
[0031] Example 2
[0032] S1. 8.3 g of 4-vinylbenzyl chloride, 14.8 g of triphenylphosphine, and 55 mL of acetone solvent were added to a reactor and reacted at 65 ° C for 24 h. After the reaction, the mixture was cooled to room temperature and dried to obtain intermediate 1;
[0033] S2. 7.65 g of intermediate 1 was added to 60 mL of N,N-dimethylformamide solvent, stirred and dispersed, and then 7.3 g of mercaptoethylamine and 0.015 g of benzoin dimethyl ether photoinitiator were added thereto. The mixture was irradiated with 365 nm ultraviolet light at 40 ° C for 4 h, and then centrifuged, washed and dried to obtain intermediate 2;
[0034] S3. 4.25 g of 1,4-dialdehyde-2,5-divinylbenzene and 7.58 g of intermediate 2 were added to 55 mL of N,N-dimethylformamide solvent and stirred at 80 ° C for 6 h. After the reaction, the mixture was distilled under reduced pressure, washed and dried to obtain a quaternary phosphonium salt-modified diene Schiff base;
[0035] S4. 55 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 10 parts by weight of hydrogenated silicone oil, 15 parts by weight of water, 6 parts by weight of quaternary phosphonium salt-modified diene Schiff base, 0.8 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.5 parts by weight of octadecyltrimethylammonium chloride were stirred and mixed at a stirring speed of 1500 r / min for 25 minutes, and then 2 parts by weight of per-tert-butyl hydroperoxide initiator were added, and the mixture was reacted at 65°C for 3 hours for cross-linking. The mixture was cooled, and 0.3 mol / L of acetic acid was added to adjust the pH to 6.5 to obtain a cross-linked silicone emulsion.
[0036] Example 3
[0037] S1. 8.2 g of 4-vinylbenzyl chloride, 14.2 g of triphenylphosphine, and 50 mL of acetone solvent were added to a reactor and reacted at 60 ° C for 22 h. After the reaction, the mixture was cooled to room temperature and dried to obtain intermediate 1;
[0038] S2. To 55 mL of N,N-dimethylformamide solvent was added 7.35 g of intermediate 1, stirred and dispersed, and then 6.87 g of mercaptoethylamine and 0.013 g of benzoin dimethyl ether photoinitiator were added. The mixture was irradiated with 365 nm ultraviolet light at 30 ° C for 3 h, and then centrifuged, washed and dried to obtain intermediate 2;
[0039] S3. 4.19 g of 1,4-dialdehyde-2,5-divinylbenzene and 7.14 g of intermediate 2 were added to 50 mL of N,N-dimethylformamide solvent and stirred at 70 ° C for 5 h. After the reaction, the mixture was distilled under reduced pressure, washed and dried to obtain a quaternary phosphonium salt-modified diene Schiff base;
[0040] S4. 45 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 9 parts by weight of hydrogenated silicone oil, 14 parts by weight of water, 5 parts by weight of quaternary phosphonium salt-modified diene Schiff base, 0.7 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.45 parts by weight of octadecyltrimethylammonium chloride were stirred and mixed at a stirring speed of 1300 r / min for 24 minutes, and then 2 parts by weight of per-tert-butyl hydroperoxide initiator were added, and the mixture was reacted at 62°C for 2 hours for cross-linking. The mixture was cooled, and 0.3 mol / L of acetic acid was added to adjust the pH to 6.3 to obtain a cross-linked silicone emulsion.
[0041] Example 4
[0042] S1. 8.1 g of 4-vinylbenzyl chloride, 13.6 g of triphenylphosphine, and 45 mL of acetone solvent were added to a reactor and reacted at 55 ° C for 20 h. After the reaction, the mixture was cooled to room temperature and dried to obtain intermediate 1;
[0043] S2. To 50 mL of N,N-dimethylformamide solvent was added 7.21 g of intermediate 1, stirred and dispersed, and then 6.44 g of mercaptoethylamine and 0.012 g of benzoin dimethyl ether photoinitiator were added thereto. The mixture was irradiated with 365 nm ultraviolet light at 25°C for 2 h, and then centrifuged, washed, and dried to obtain intermediate 2.
[0044] S3. 4.19 g of 1,4-dialdehyde-2,5-divinylbenzene and 7.14 g of intermediate 2 were added to 50 mL of N,N-dimethylformamide solvent and stirred at 70 ° C for 5 h. After the reaction, the mixture was distilled under reduced pressure, washed and dried to obtain a quaternary phosphonium salt-modified diene Schiff base;
[0045] S4. 45 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 9 parts by weight of hydrogenated silicone oil, 14 parts by weight of water, 5 parts by weight of quaternary phosphonium salt-modified diene Schiff base, 0.7 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.45 parts by weight of octadecyltrimethylammonium chloride were stirred and mixed at a stirring speed of 1300 r / min for 24 minutes, and then 2 parts by weight of per-tert-butyl hydroperoxide initiator were added, and the mixture was reacted at 62°C for 2 hours for cross-linking. The mixture was cooled, and 0.3 mol / L of acetic acid was added to adjust the pH to 6.3 to obtain a cross-linked silicone emulsion.
[0046] Example 5
[0047] S1. 8.3 g of 4-vinylbenzyl chloride, 14.8 g of triphenylphosphine, and 55 mL of acetone solvent were added to a reactor and reacted at 65 ° C for 24 h. After the reaction, the mixture was cooled to room temperature and dried to obtain intermediate 1;
[0048] S2. 7.65 g of intermediate 1 was added to 60 mL of N,N-dimethylformamide solvent, stirred and dispersed, and then 7.3 g of mercaptoethylamine and 0.015 g of benzoin dimethyl ether photoinitiator were added thereto. The mixture was irradiated with 365 nm ultraviolet light at 40 ° C for 4 h, and then centrifuged, washed and dried to obtain intermediate 2;
[0049] S3. 4.19 g of 1,4-dialdehyde-2,5-divinylbenzene and 7.14 g of intermediate 2 were added to 50 mL of N,N-dimethylformamide solvent and stirred at 70 ° C for 5 h. After the reaction, the mixture was distilled under reduced pressure, washed and dried to obtain a quaternary phosphonium salt-modified diene Schiff base;
[0050] S4. 45 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 9 parts by weight of hydrogenated silicone oil, 14 parts by weight of water, 5 parts by weight of quaternary phosphonium salt-modified diene Schiff base, 0.7 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.45 parts by weight of octadecyltrimethylammonium chloride were stirred and mixed at a stirring speed of 1300 r / min for 24 minutes, and then 2 parts by weight of per-tert-butyl hydroperoxide initiator were added, and the mixture was reacted at 62°C for 2 hours for cross-linking. The mixture was cooled, and 0.3 mol / L of acetic acid was added to adjust the pH to 6.3 to obtain a cross-linked silicone emulsion.
[0051] Comparative Example 1
[0052] Compared with Example 5, this comparative example differs in that the intermediate 1 is used instead of the quaternary phosphonium salt to modify the diene Schiff base.
[0053] Comparative Example 2
[0054] Compared with Example 5, this comparative example differs in that no quaternary phosphonium salt is added to modify the diene Schiff base.
[0055] Staphylococcus aureus, Escherichia coli, and Candida albicans were used as test bacteria and the concentration was 1×10 5 A bacterial suspension with a CFU / mL was pipetted and added to a sterile Petri dish containing MH broth. A cross-linked silicone emulsion sample was then applied to the surface of the culture medium. The dish was incubated at 42°C for 15 hours in a constant temperature incubator. The diameter of the inhibition zone was then measured. The test results are shown in Table 1.
[0056] Table 1: Antimicrobial testing.
[0057]
[0058] As shown in Table 1, Examples 1-5 of the present invention have better antibacterial effects than Comparative Examples 1-2.
[0059] Stability testing
[0060] Take an appropriate amount of the emulsion and place it in a centrifuge tube. Centrifuge at 3000-5000 rpm for 15-30 minutes and observe whether there is stratification.
[0061] project Whether there is stratification Example 1 No stratification or precipitation Example 2 No stratification or precipitation Example 3 No stratification or precipitation Example 4 No stratification or precipitation Example 5 No stratification or precipitation Comparative Example 1 Slight stratification and sedimentation Comparative Example 2 Slight stratification and sedimentation
[0062] As can be seen from Table 2, Examples 1-5 of the present invention have better stability than Comparative Examples 1-2.
[0063] It should be noted that, in this document, the terms "comprises," "includes," or any other variations thereof are intended to encompass non-exclusive inclusion, such that a process, method, article, or apparatus comprising a series of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of other identical elements in the process, method, article, or apparatus comprising the element.
[0064] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.
[0065] Those skilled in the art will appreciate that the foregoing descriptions are merely specific embodiments of the present invention, and not exhaustive examples. It should be noted that numerous variations and modifications are possible for those skilled in the art, and all such variations and modifications that do not exceed the scope of the claims should be considered within the scope of protection of the present invention.
Claims
1. A cross-linked silicone emulsion, characterized in that: The invention comprises the following components by weight: 35-55 parts by weight of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 8-10 parts by weight of hydrogen-containing silicone oil, 1-2 parts by weight of per-tert-butyl hydroperoxide initiator, 10-15 parts by weight of water, 4-6 parts by weight of quaternary phosphonium salt modified diene Schiff base, 0.6-0.8 parts by weight of isomeric tridecanol heptapolyoxyethylene ether, and 0.4-0.5 parts by weight of octadecyltrimethylammonium chloride.
2. The cross-linked silicone emulsion according to claim 1, characterized in that The preparation method of the quaternary phosphonium salt modified diene Schiff base is: S1. 8.1-8.3 g of 4-vinylbenzyl chloride, 13.6-14.8 g of triphenylphosphine, and 45-55 mL of acetone solvent were added to the reactor and reacted. After the reaction was completed, the reaction was cooled to room temperature and dried to obtain intermediate 1; S2. To 50-60 mL of N,N-dimethylformamide solvent was added intermediate 1, stirred and dispersed, and then mercaptoethylamine and benzoin dimethyl ether photoinitiator were added thereto, and irradiated with ultraviolet light at 365 nm at 25-40 ° C. After completion, centrifugation, washing and drying were performed to obtain intermediate 2; S3. Add 1,4-dialdehyde-2,5-divinylbenzene and intermediate 2 to 45-55 mL of N,N-dimethylformamide solvent, stir and react at 65-80°C for 5-6 hours, and then distill under reduced pressure, wash and dry to obtain a quaternary phosphonium salt-modified diene Schiff base.
3. The cross-linked silicone emulsion according to claim 2, characterized in that The reaction temperature in S1 is 55-65°C.
4. The cross-linked silicone emulsion according to claim 2, characterized in that The reaction time in S1 is 20-24 hours.
5. The cross-linked silicone emulsion according to claim 2, characterized in that: The mass ratio of the intermediate 1, mercaptoethylamine, and benzoin dimethyl ether photoinitiator in S2 is 7.21-7.65 g: 6.44-7.3 g: 0.012-0.015 g.
6. The cross-linked silicone emulsion according to claim 2, characterized in that: The irradiation time in S2 is 2-4 hours.
7. The cross-linked silicone emulsion according to claim 2, characterized in that: The mass ratio of 1,4-dialdehyde-2,5-divinylbenzene to intermediate 2 in S3 is 4.14-4.25 g:6.71-7.58 g.
8. A method for preparing the cross-linked organosilicon emulsion according to any one of claims 1 to 7, characterized in that: The preparation method of the cross-linked silicone emulsion comprises the following steps: stirring and mixing 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, hydrogenated silicone oil, water, quaternary phosphonium salt-modified diene Schiff base, isomeric tridecanol heptapolyoxyethylene ether, and octadecyltrimethylammonium chloride; then adding tert-butyl hydroperoxide initiator to carry out cross-linking; cooling; and adding 0.3 mol / L acetic acid to adjust the pH to 6-6.5 to obtain the cross-linked silicone emulsion.
9. The method for preparing a cross-linked organosilicon emulsion according to claim 8, wherein: The stirring speed is 1200-1500 r / min, and the stirring time is 20-25 min.
10. The method for preparing a cross-linked organosilicon emulsion according to claim 8, wherein: The cross-linking reaction time is 2-3 hours, and the temperature is 60-65°C.