CN114376944B - Hydrophilic organosilicon elastomer compound and preparation method thereof - Google Patents
Hydrophilic organosilicon elastomer compound and preparation method thereof Download PDFInfo
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- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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Abstract
The invention belongs to the technical field of cosmetics, and particularly relates to a hydrophilic organic silicon elastomer compound with excellent stability and a preparation method thereof. The hydrophilic organosilicon elastomer compound is prepared from polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer, deionized water, an emulsifier and butanediol grafted modified silica powder through initiating polymerization reaction. According to the invention, the polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer, silica and butanediol are connected in a chemical bonding mode, and the prepared aqueous organosilicon elastomer compound has excellent dispersion performance and stability, so that the application range of the product in the cosmetic industry is greatly expanded.
Description
Technical Field
The invention belongs to the technical field of cosmetics, and particularly relates to a hydrophilic organic silicon elastomer compound with excellent stability and a preparation method thereof.
Background
The polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer is organosilicon elastomer powder with the particle size distribution of 3-15 microns, and is widely applied to products such as beauty, skin care, sun protection, infant care and the like due to the advantages of no toxicity, no sensitization, no stimulation, safety, reliability and the like. Polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymers are relatively soft and less slippery, and the powdery or coated feel of the polymers is generally improved by the addition of silica powder.
However, polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymers are mostly used in oil phase systems due to their good hydrophobic properties, and the polymers have poor hydrophilic properties and cannot be used in aqueous phase systems, and the range of applications is greatly limited. The key point for expanding the application range of the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is to effectively improve the dispersibility of the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer in an aqueous phase system. For this purpose, polyols, in particular butanediol, are generally added to improve the dispersibility of the polymers in aqueous systems.
Chinese patent (application number: 201310398447.4) provides a water-based BB cream with comfortable coating, which is prepared by mixing, emulsifying and homogenizing polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer, silica, butanediol, cyclopentadimethylsiloxane, ethylhexyl methoxycinnamate, polymethylsilsesquioxane and deionized water together with other auxiliary agents in proportion. However, according to the technical scheme, raw material components are emulsified and homogenized in a physical mixing mode to obtain BB cream, the hydrophilic component butanediol is in a free state, and the interface bonding performance between silica and the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is poor, so that the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is poor in dispersibility in a water phase system, and the layering and precipitation phenomena of emulsion are easy to generate, so that the shelf life is influenced.
Disclosure of Invention
Aiming at the problems existing in the background technology, the invention provides a hydrophilic organic silicon elastomer compound with excellent stability and a preparation method thereof, and aims to improve the dispersion stability of a silica-containing polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer formula in an aqueous phase system and widen the application range of the silica-containing polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer formula.
In order to solve the technical problems, the technical scheme of the invention is characterized by comprising the following steps:
the hydrophilic organosilicon elastomer compound is prepared from polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer, deionized water, an emulsifying agent, butanediol grafted modified silica powder and an initiator through initiation polymerization reaction;
wherein the mass ratio of the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer to deionized water is 0.3-0.6:1;
the mass ratio of the emulsifier to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.03:1;
the mass ratio of the butanediol grafted modified silica powder to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.05-0.2:1;
the mass ratio of the initiator to the polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer is 0.01-0.05:1.
Preferably, the hydrophilic silicone elastomer composite of the present invention has a coefficient of friction value of 0.15 to 0.18.
Preferably, the hydrophilic silicone elastomer composite of the present invention is prepared by the steps of: adding deionized water and an emulsifying agent into the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer, emulsifying and stirring uniformly to obtain emulsion, dispersing butanediol grafted modified silica powder into the emulsion, dropwise adding 10-20 ml/min of initiator solution with the mass percent concentration of 10-20% into a reaction system at the temperature of 60-80 ℃ to initiate polymerization reaction, preserving heat for 60-120 min after the dropwise adding, regulating a system to be neutral by using 10-20% alkaline solution with the mass percent concentration of 10-20% after the reaction is finished, cooling to room temperature, dehydrating, and drying at the temperature of 60-80 ℃ for 6-12 h to obtain the hydrophilic organosilicon elastomer compound.
Preferably, the emulsifier is one of octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether; the initiator is one of azo diisobutyl amidine hydrochloride or ammonium persulfate; the alkaline solution is one of ammonia water or sodium carbonate solution.
Preferably, the butanediol grafted modified silica powder is prepared by the following steps: spraying a mixture of a C=C double-bond silane coupling agent and an isocyanate-group silane coupling agent into the silica powder while stirring, wherein the mass ratio of the C=C double-bond silane coupling agent to the isocyanate-group silane coupling agent is 0.5-2:1, the total mass ratio of the silane coupling agent to the silica powder is 0.1-0.4:1, heating to 80-100 ℃ after the spraying is finished, and stirring and reacting for 3-6 hours to obtain the silane coupling agent synergistic modified silica powder; and continuously adding butanediol into the silica powder cooperatively modified by the silane coupling agent, and continuously stirring at the temperature for reaction for 30-60 minutes, wherein the molar ratio of the butanediol to the isocyanate-based silane coupling agent is 1-2:1, so as to obtain the butanediol grafted modified silica powder.
Preferably, the silane coupling agent with C=C double bond is selected from one of vinyl trimethoxy silane, vinyl triethoxy silane or vinyl tri (2-methoxyethoxy) silane; the silane coupling agent with isocyanate groups is one of isocyanate propyl trimethoxy silane or isocyanate propyl triethoxy silane.
The characteristic steps of another technical scheme of the invention are as follows: a method for preparing a hydrophilic silicone elastomer composite, comprising the steps of:
(1) Preparation of butanediol grafted modified silica powder
Spraying a mixed solution of a silane coupling agent with C=C double bonds and a silane coupling agent with isocyanate groups into the silica powder while stirring, wherein the mass ratio of the silane coupling agent with C=C double bonds to the isocyanate group silane coupling agent is 0.5-2:1, the total mass ratio of the silane coupling agent to the silica powder is 0.1-0.4:1, heating to 80-100 ℃ after the spraying is finished, and stirring and reacting for 3-6 hours to obtain the silane coupling agent synergistic modified silica powder; continuously adding butanediol into the silica powder cooperatively modified by the silane coupling agent, and continuously stirring at the temperature for reaction for 30-60 minutes, wherein the molar ratio of the butanediol to the isocyanate silane coupling agent is 1-2:1, so as to obtain butanediol grafted modified silica powder;
(2) Preparation of hydrophilic silicone elastomer composites
Adding deionized water and an emulsifying agent into the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer, wherein the mass ratio of the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer to the deionized water is 0.3-0.6:1, the mass ratio of the emulsifying agent to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.03:1, dispersing the butanediol grafted modified silica powder prepared in the step (1) into the emulsion after the emulsification and stirring are uniform, wherein the mass ratio of the butanediol grafted modified silica powder to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.05-0.2:1, the initiator solution with the mass percentage concentration of 10-20 ml/min is dripped into a reaction system at the temperature of 60-80 ℃ for initiating polymerization, the mass ratio of the initiator to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.05:1, the temperature of 60-80 ℃ is adjusted to be the neutral temperature after the reaction is 60-20 min, and the hydrophilic composite is prepared after the temperature is 60-80% of the reaction system is cooled, and the aqueous solution is cooled to the temperature is 10-20%, and the hydrophilic composite is cooled to the temperature is 60-12% after the temperature is kept to be 60-20% and the aqueous solution is cooled.
The silane coupling agent with C=C double bond in the step (1) is one of vinyl trimethoxy silane, vinyl triethoxy silane or vinyl tri (2-methoxyethoxy) silane; the silane coupling agent with isocyanate groups in the step 1 is one of isocyanate propyl trimethoxy silane or isocyanate propyl triethoxy silane.
The emulsifier in the step (2) is one of octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether; the initiator in the step (2) is one of azo diisobutyl amidine hydrochloride or ammonium persulfate; the alkaline solution in the step (2) is one of ammonia water or sodium carbonate solution.
The invention has the beneficial effects that:
1. the invention adopts a silane coupling agent containing C=C double bond and a silane coupling agent containing isocyanate group to carry out synergistic organic surface modification treatment on silica, so that two chemical functional groups, namely isocyanate group and vinyl group, are grafted on the surface of the silica. The advantage of this is: (1) the isocyanate groups on the surface of the silica react with hydroxyl groups in the butanediol to form-O-CO-NH-bonds, and the butanediol is grafted on the surface of the silica powder in a chemical bonding mode, so that the problem that the butanediol in the prior art is in a free state is solved; (2) the other group vinyl on the surface of the silica can be copolymerized with the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer to link the silica with the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer in a chemical bonding mode, so that the problem of poor interface bonding performance of the silica and the polymer in the prior art is solved.
2. According to the invention, the polydimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer, silica and butanediol are connected in a chemical bonding mode, and the prepared aqueous organosilicon elastomer compound has excellent dispersion performance and stability, so that the application range of the product in the cosmetic industry is greatly expanded.
Drawings
FIG. 1 is a scanning electron micrograph of the hydrophilic silicone elastomer composite obtained in example 4.
FIG. 2 is a scanning electron micrograph of the sample obtained in comparative example 1.
Detailed Description
The present invention will be further described with reference to examples and comparative examples, but in no way limit the scope of the present invention.
Example 1
1. Spraying a mixed solution of 0.5 kg of vinyl trimethoxy silane and 1.0 kg of isocyanato propyl triethoxy silane into 15 kg of silica powder while stirring, heating to 80 ℃ after the spraying is finished, and stirring and reacting for 6 hours to obtain the silane coupling agent synergistic modified silica powder; then continuously adding 0.365 kg of butanediol into the organic surface modified silica powder, and continuously stirring and reacting for 60 minutes at the temperature to obtain butanediol grafted modified silica powder;
2. adding 10 kg deionized water and 0.09 kg octyl phenol polyoxyethylene ether into 3.0 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (dakangning 9506 powder), emulsifying and stirring uniformly, taking 0.6 kg butanediol grafted modified silica powder prepared in the step (1), dispersing into the emulsion, dropwise adding 0.75 kg azobisisobutylammonium hydrochloride solution with the mass percent concentration of 20% into a reaction system at the temperature of 60 ℃ at the speed of 10 ml/min for initiating polymerization reaction, preserving heat for 120 minutes after the completion of the dropwise addition, regulating the system to be neutral by using an ammonia water solution with the mass percent concentration of 10%, cooling to room temperature, dehydrating, and drying at the temperature of 60 ℃ for 12 hours to obtain the hydrophilic organic silicon elastomer compound.
Example 2
1. Spraying a mixed solution of 1.0 kg of vinyl triethoxysilane and 0.5 kg of isocyanatopropyl trimethoxysilane into 3.75 kg of silica powder while stirring, heating to 100 ℃ after the spraying is finished, and stirring and reacting for 3 hours to obtain the silane coupling agent synergistic modified silica powder; then continuously adding 0.439 kg of butanediol into the organic surface modified silica powder, and continuously stirring and reacting for 30 minutes at the temperature to obtain butanediol grafted modified silica powder;
2. adding 10 kg deionized water and 0.06 kg nonylphenol polyoxyethylene ether into 6.0 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (dakangning 9506 powder), emulsifying and stirring uniformly, taking 0.3 kg butanediol grafted modified silica powder prepared in the step (1), dispersing into the emulsion, dropwise adding 0.6 kg ammonium persulfate solution with the mass percent concentration of 10% into a reaction system at the temperature of 80 ℃ at the speed of 20 ml/min for initiating polymerization reaction, preserving heat for 60 minutes after the completion of the dropwise addition, regulating the system to be neutral by using a sodium carbonate solution with the mass percent concentration of 20%, cooling to room temperature, dehydrating, and drying at the temperature of 80 ℃ for 6 hours to obtain the hydrophilic organic silicon elastomer compound.
Example 3
1. Spraying a mixed solution of 1.0 kg of vinyl tri (2-methoxyethoxy) silane and 1.0 kg of cyanate propyl trimethoxy silane into 10 kg of silica powder while stirring, heating to 90 ℃ after spraying, and stirring for reacting for 5 hours to obtain silane coupling agent synergistic modified silica powder; then 0.659 kg of butanediol is continuously added into the organic surface modified silica powder, and the reaction is continuously stirred for 45 minutes at the temperature, so that the butanediol grafted modified silica powder is prepared;
2. adding 10 kg deionized water and 0.09 kg nonylphenol polyoxyethylene ether into 4.5 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (Dow Corning 9506 powder), emulsifying and stirring uniformly, taking 0.45 kg butanediol grafted modified silica powder prepared in the step (1), dispersing into the emulsion, dropwise adding 0.9 kg ammonium persulfate solution with the mass percent concentration of 15% into a reaction system at the temperature of 70 ℃ for initiating polymerization reaction at the speed of 10 ml/min, preserving heat for 90 minutes after the completion of the dropwise addition, regulating the system to be neutral by using 15% ammonia water solution with the mass percent concentration, cooling to room temperature, dehydrating, and drying at the temperature of 70 ℃ for 9 hours to obtain the hydrophilic organic silicon elastomer compound.
Example 4
1. Spraying a mixed solution of 1.5 kg of vinyl triethoxysilane and 1.0 kg of isocyanato propyl triethoxysilane into 8.3 kg of silica powder while stirring, heating to 85 ℃ after the spraying is finished, and stirring and reacting for 4 hours to obtain the silane coupling agent synergistic modified silica powder; then continuously adding 0.547 kg of butanediol into the organic surface modified silica powder, and continuously stirring and reacting for 50 minutes at the temperature to obtain butanediol grafted modified silica powder;
2. adding 10 kg deionized water and 0.08 kg octyl phenol polyoxyethylene ether into 5.0 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (dakangning 9506 powder), emulsifying and stirring uniformly, taking 0.9 kg butanediol grafted modified silica powder prepared in the step (1), dispersing into the emulsion, dropwise adding 0.5 kg azobisisobutylamino hydrochloride solution with the mass percent concentration of 20% into a reaction system at the temperature of 75 ℃ for initiating polymerization reaction at the speed of 15 ml/min, preserving heat for 100 min after the completion of the dropwise addition, regulating the system to be neutral by using sodium carbonate solution with the mass percent concentration of 15%, cooling to room temperature, dehydrating, and drying at the temperature of 75 ℃ for 8 hours to obtain the hydrophilic organic silicon elastomer compound.
FIG. 1 is a scanning electron micrograph of a hydrophilic silicone elastomer composite prepared in this example. As can be seen from the electron microscope photograph: the silica particles are uniformly bound to the surface of the spherical silicone elastomer and do not exhibit a free state, which indicates that the butanediol grafted silica has good interfacial binding properties with the silicone elastomer (dimethylsiloxane/vinyl polydimethylsiloxane cross-linked polymer).
Comparative example 1
In comparative example 1, the procedure of example 4 in which the silane coupling agent having a c=c double bond and the silane coupling agent having an isocyanate group were added was deleted, and the other process conditions were unchanged, and the specific operation steps were as follows:
1. adding 0.547 kg of butanediol into 8.3 kg of silica powder while stirring, and stirring and reacting for 50 minutes at the temperature of 85 ℃ to obtain a silica powder and butanediol mixture;
2. adding 10 kg deionized water and 0.08 kg octyl phenol polyoxyethylene ether into 5.0 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (Dow Corning 9506 powder), emulsifying and stirring uniformly, dispersing 0.9 kg of the mixture of silica powder and butanediol obtained in the step (1) into the emulsion, stirring and preserving heat for 100 minutes at the temperature of 75 ℃, cooling to room temperature, dehydrating, and drying at the temperature of 75 ℃ for 8 hours to obtain the hydrophilic organic silicon elastomer compound.
FIG. 2 is a scanning electron micrograph of the sample obtained in comparative example 1. As can be seen from the electron microscope photograph: the sample exhibited silica in a partially free state.
Comparative example 2
In comparative example 2, the procedure of example 4 in which the silane coupling agent having a c=c double bond was added was deleted, and other process conditions were unchanged, and specific operation steps were as follows:
1. spraying 2.5 kg of isocyanatopropyl triethoxysilane liquid into 8.3 kg of silica powder while stirring, heating to 85 ℃ after spraying, and stirring for 4 hours to obtain silane coupling agent modified silica powder; then continuously adding 0.547 kg of butanediol into the organic surface modified silica powder, and continuously stirring and reacting for 50 minutes at the temperature to obtain butanediol grafted modified silica powder;
2. adding 10 kg deionized water and 0.08 kg octyl phenol polyoxyethylene ether into 5.0 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (Dow Corning 9506 powder), emulsifying and stirring uniformly, taking 0.9 kg butanediol grafted modified silica powder prepared in the step (1) to disperse into the emulsion, stirring and preserving heat for 100 minutes at the temperature of 75 ℃, cooling to room temperature, dehydrating, and drying at the temperature of 75 ℃ for 8 hours to obtain the hydrophilic organic silicon elastomer compound.
Comparative example 3
In comparative example 3, the procedure of the isocyanate group-containing silane coupling agent of example 4 was deleted, and the other process conditions were unchanged, and the specific operation steps were as follows:
1. spraying 2.5 kg of vinyl triethoxysilane liquid into 8.3 kg of silica powder while stirring, heating to 85 ℃ after spraying, and stirring for 4 hours to obtain silane coupling agent modified silica powder; then continuously adding 0.547 kg of butanediol into the organic surface modified silica powder, and continuously stirring and reacting for 50 minutes at the temperature to obtain a modified silica powder and butanediol mixture;
2. adding 10 kg deionized water and 0.08 kg octyl phenol polyoxyethylene ether into 5.0 kg polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer (dakangning 9506 powder), emulsifying and stirring uniformly, dispersing 0.9 kg modified silica powder/butanediol mixture prepared in the step (1) into the emulsion, dropwise adding 0.5 kg of 20% azodiisobutyl amidine hydrochloride solution at a mass percent concentration into a reaction system at a temperature of 75 ℃ for initiating polymerization reaction, preserving heat for 100 minutes after the completion of the dropwise adding, regulating the system to be neutral by using 15% sodium carbonate solution at a mass percent concentration, cooling to room temperature, dehydrating, and drying at a temperature of 75 ℃ for 8 hours to obtain the hydrophilic organosilicon elastomer compound.
Evaluation of Performance
The properties of one of the hydrophilic silicone elastomer composites obtained in examples and comparative examples were evaluated by the following property tests, and the test results are shown in table 1. As can be seen from Table 1, the silicone elastomer composite prepared by the invention has a low friction coefficient and good slip properties, and also has excellent dispersion properties and stability properties in an aqueous phase system.
Dispersion stability performance test: the organic silicon elastomer compound obtained by the experiment is added into distilled water to prepare a dispersion liquid with the mass percentage concentration of 20%, and layering or precipitation phenomenon is observed.
Friction performance test: the surface friction coefficient of the composite material was measured using a KES-SE type friction coefficient tester from KATO corporation of Japan. With a 0.5 mm interval fingerprint simulator, the traction is 0.5N and the simulator speed is 1 mm/s. The coefficient of friction value of the composite material is obtained through calculation of an instrument. The smaller the friction coefficient of the composite material is, the higher the dispersity of the material is, the roughness is reduced, and the comfort is good.
TABLE 1
| Name of the name | Coefficient of friction value | Dispersion stability |
| Example 1 | 0.15 | No delamination for 6 months |
| Example 2 | 0.18 | No delamination for 6 months |
| Example 3 | 0.16 | No delamination for 6 months |
| Example 4 | 0.11 | No delamination for 6 months |
| Comparative example 1 | 0.30 | Layering and precipitation for 2 weeks |
| Comparative example 2 | 0.26 | Layering for 1 month |
| Comparative example 3 | 0.23 | Layering for 1 month |
The deletion of the corresponding steps of comparative example 1 and comparative example 2 resulted in the production of a part of free silica, and the deletion of the corresponding step of comparative example 3 resulted in the production of free butanediol, which resulted in the decrease of the coefficient of friction value, while being disadvantageous in the dispersion stability of the slurry.
Claims (7)
1. A hydrophilic silicone elastomer composite characterized by: the hydrophilic organosilicon elastomer compound is prepared by initiating polymerization reaction of polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer, deionized water, an emulsifier, butanediol grafted modified silica powder and an initiator;
wherein the mass ratio of the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer to deionized water is 0.3-0.6:1;
the mass ratio of the emulsifier to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.03:1;
the mass ratio of the butanediol grafted modified silica powder to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.05-0.2:1;
the mass ratio of the initiator to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.05:1;
the butanediol grafted modified silica powder is prepared by the following steps: spraying a mixed solution of a C=C double-bond silane coupling agent and an isocyanate-group silane coupling agent into the silica powder while stirring, wherein the mass ratio of the C=C double-bond silane coupling agent to the isocyanate-group silane coupling agent is 0.5-2:1, the total mass ratio of the silane coupling agent to the silica powder is 0.1-0.4:1, heating to 80-100 ℃ after the spraying is finished, and stirring and reacting for 3-6 hours to obtain the silane coupling agent synergistic modified silica powder; continuously adding butanediol into the silica powder cooperatively modified by the silane coupling agent, and continuously stirring at the temperature for reaction for 30-60 minutes, wherein the molar ratio of the butanediol to the isocyanate silane coupling agent is 1-2:1, so as to obtain butanediol grafted modified silica powder; the silane coupling agent with C=C double bond is selected from one of vinyl trimethoxy silane, vinyl triethoxy silane or vinyl tri (2-methoxyethoxy) silane; the silane coupling agent with isocyanate groups is one of isocyanate propyl trimethoxy silane or isocyanate propyl triethoxy silane.
2. A hydrophilic silicone elastomer composite according to claim 1, characterized in that: the hydrophilic silicone elastomer composite has a coefficient of friction value of 0.15 to 0.18.
3. A hydrophilic silicone elastomer composite according to claim 1, characterized in that: the hydrophilic organosilicon elastomer compound is prepared by the following steps: adding deionized water and an emulsifying agent into the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer, emulsifying and stirring uniformly to obtain emulsion, dispersing butanediol grafted modified silica powder into the emulsion, dripping 10-20 ml/min of 10-20% initiator solution into a reaction system at the temperature of 60-80 ℃ to initiate polymerization reaction, preserving heat for 60-120 min after dripping, regulating the system to be neutral by using 10-20% alkaline solution after finishing the reaction, cooling to room temperature, dehydrating, and drying at the temperature of 60-80 ℃ for 6-12 h to obtain the hydrophilic organosilicon elastomer compound.
4. A hydrophilic silicone elastomer composite according to claim 3, characterized in that: the emulsifier is one of octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether; the initiator is one of azo diisobutyl amidine hydrochloride or ammonium persulfate; the alkaline solution is one of ammonia water or sodium carbonate solution.
5. A method of preparing the hydrophilic silicone elastomer composite of any one of claims 1-4, characterized by: the preparation method comprises the following steps:
(1) Preparation of butanediol grafted modified silica powder
Spraying a mixture of a C=C double bond silane coupling agent and an isocyanate group silane coupling agent into the silica powder while stirring, wherein the mass ratio of the C=C double bond silane coupling agent to the isocyanate group silane coupling agent is 0.5-2:1, the total mass ratio of the silane coupling agent to the silica powder is 0.1-0.4:1, heating to 80-100 ℃ after the spraying is finished, and stirring and reacting for 3-6 hours to obtain the silane coupling agent synergistic modified silica powder; continuously adding butanediol into the silica powder cooperatively modified by the silane coupling agent, and continuously stirring at the temperature for reaction for 30-60 minutes, wherein the molar ratio of the butanediol to the isocyanate silane coupling agent is 1-2:1, so as to obtain butanediol grafted modified silica powder;
(2) Preparation of hydrophilic silicone elastomer composites
Adding deionized water and an emulsifying agent into the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer, wherein the mass ratio of the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer to the deionized water is 0.3-0.6:1, the mass ratio of the emulsifying agent to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.03:1, emulsifying and stirring uniformly to prepare emulsion, dispersing the butanediol grafted modified silica powder prepared in the step (1) into the emulsion, wherein the mass ratio of the butanediol grafted modified silica powder to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.05-0.2:1, initiating polymerization reaction is carried out by dropwise adding an initiator solution with the mass percentage concentration of 10-20 ml/min into a reaction system at the temperature of 60-80 ℃, the mass percentage concentration of the initiator solution to the polydimethylsiloxane/vinyl polydimethylsiloxane crosslinked polymer is 0.01-0.05:1, the mass percentage of the initiator solution is cooled to the temperature of 60-80 ℃ for 60-80 min, and the hydrophilic composite is prepared by drying the aqueous solution after the temperature of 60-80% at the temperature of 60-80 ℃ for 60-60% after the temperature is cooled, and the aqueous solution is cooled to obtain the hydrophilic composite solution after the temperature is cooled to be 6-80% at the temperature of the neutral temperature of the reaction system.
6. The method for preparing a hydrophilic silicone elastomer composite according to claim 5, wherein: the silane coupling agent with C=C double bond in the step (1) is one of vinyl trimethoxy silane, vinyl triethoxy silane or vinyl tri (2-methoxyethoxy) silane; the silane coupling agent with isocyanate groups in the step 1 is one of isocyanate propyl trimethoxy silane or isocyanate propyl triethoxy silane.
7. The method for preparing a hydrophilic silicone elastomer composite according to claim 5, wherein: the emulsifier in the step (2) is one of octyl phenol polyoxyethylene ether or nonylphenol polyoxyethylene ether; the initiator in the step (2) is one of azo diisobutyl amidine hydrochloride or ammonium persulfate; the alkaline solution in the step (2) is one of ammonia water or sodium carbonate solution.
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| Effect of Isocyanate-Modified Fumed Silica on the Properties of Poly(butylene succinate) Nanocomposites;Jung Seop Lim等;《Journal of Applied Polymer Science》;第107卷;3598–3608 * |
| Grafting of hyperbranched polymers onto ultrafine silica: postgraft polymerization of vinyl monomers initiated by pendant azo groups of grafted polymer chains on the surface;Norio Tsubokawa等;《Progress in Organic Coatings》;第44卷;69–74 * |
| 超细二氧化硅表面接枝超支化聚合物研究;杨亮亮;《CNKI 工程科技Ⅰ辑》;摘要 * |
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