CN109971003B

CN109971003B - Preparation method of silicon resin nanoparticle dispersion and silicon resin nanoparticle dispersion

Info

Publication number: CN109971003B
Application number: CN201711437816.0A
Authority: CN
Inventors: 张川; 李保耀
Original assignee: Wanhua Chemical Group Co Ltd
Current assignee: Wanhua Chemical Group Co Ltd
Priority date: 2017-12-26
Filing date: 2017-12-26
Publication date: 2021-10-22
Anticipated expiration: 2037-12-26
Also published as: CN109971003A

Abstract

The invention belongs to the technical field of preparation of silicone resin nano particles, and provides a preparation method of a silicone resin nano particle dispersion and the silicone resin nano particle dispersion; the preparation method comprises the following steps: (1) dissolving hydrophobic silicone resin in a water-soluble organic solvent to obtain an organic solution; (2) rapidly mixing the organic solution and the antisolvent, and precipitating to obtain a silicon resin nanoparticle dispersion; the rapid mixing is such that the mixing system operates at reynolds numbers > 1600. The particle size of the silicone resin nanoparticles distributed in the silicone resin nanoparticle dispersion is 20nm to 1500 nm. The preparation method can realize the rapid (Reynolds number is larger than 1600) precipitation of the silicon resin material dissolved in the solvent flow, and obtain the silicon resin nano particles with uniform particle size distribution.

Description

Preparation method of silicon resin nanoparticle dispersion and silicon resin nanoparticle dispersion

Technical Field

The invention belongs to the technical field of preparation of silicone resin nanoparticles, and particularly relates to a preparation method of a silicone resin nanoparticle dispersion and the silicone resin nanoparticle dispersion.

Background

Silicone resin, named in 1901, is a silicone resin comprising the general formula R₁R₂Polymeric material of SiO. Unique properties of silicone resins include: the glass transition temperature is extremely low (-123 ℃), the surface tension is extremely low (20-21 mN/m), and the thermal stability, the air permeability and the hydrophobicity are good.

Due to these excellent properties and the many chemicals available to improve these properties, silicone resins have found widespread use in a number of areas. Industries that use silicone resins include: as foam control agents and lubricating oils and the like in the food industry; as a cook additive for pulp, defoamer, de-inking, etc. in the paper industry; as lubricants, softeners, foam control agents, hydrophobic coatings, etc. in the textile industry; as fabric care agents, foam control agents, softeners and the like in household cleaning; as an additive or adhesive with good wetting, durability, water repellency, foam control capability and adhesion in the coating field; as durable and weatherable sealants and adhesives, pressure sensitive adhesives, and the like in the construction industry; the good stability in temperature, humidity, bandwidth and corrosion protection aspects is utilized in the electronic industry; the composite silica/silica gel is used as a composite silica/silica gel material in the transportation industry and is used in the aspects of hoses, safety airbags, elastic connection of trains and buses, airplane sealing, safety devices and the like; as additives and lubricants in plastics manufacture, as agents in the personal care industry for skin, hair, sun and coloration, etc.; in addition, the method can also be used in industries such as mold manufacturing, photonics, medical equipment and pharmacy.

The patent document US8137699B2 ("processes and apparatus for preparing nanoparticie compositions with amphophilic polymers and the use") discloses a Process for preparing amphiphilic copolymer nanomaterials by flash deposition; the nanoparticles can be amphiphilic copolymers alone or can wrap target molecules with the amphiphilic copolymers. The inclusion of additive target molecules in the amphipathic copolymer nanoparticles may alter its water solubility characteristics, hydrodynamics and/or stability. Encapsulation of target molecules in amphiphilic copolymer nanoparticles can alter their water solubility characteristics, hydrodynamics, and/or stability. The method described in this patent document utilizes a defined impingement jet or multi-inlet vortex mixer to induce highly mixed nanoprecipitation of amphiphilic copolymer nanoparticles. However, the nano-precipitate prepared by flash deposition in this patent document is a micelle, and the preparation of silicone resin nano-particles is not mentioned.

Disclosure of Invention

The invention aims to provide a silicon resin nanoparticle dispersion and a preparation method thereof; by the preparation method, the silicon resin material dissolved in the solvent can be rapidly precipitated to obtain the silicon resin nano particles with uniform particle size.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method for preparing a dispersion of silicone nanoparticles, the method comprising the steps of:

(1) dissolving hydrophobic silicone resin in a water-soluble organic solvent to obtain an organic solution;

(2) rapidly mixing the organic solution and the antisolvent, and precipitating to obtain a silicon resin nanoparticle dispersion;

the rapid mixing is to make the mixing system operate at Reynolds number > 1600; it is preferred to operate the mixing system at 1600 < Reynolds number < 4000.

During the fast mixing process, a flash Precipitation (Rapid Precipitation) occurs. Flash deposition is a process in which materials are deposited for a short time in a rapid mixing process. And (3) rapidly mixing the organic solution and the anti-solvent through a closed impact type jet mixer, carrying out flash precipitation on the mixture, and precipitating to generate a silicon resin nanoparticle dispersion to obtain the silicon resin nanoparticles with uniform particle size.

After mixing with the antisolvent, the components dissolved in the water-soluble organic solvent cause the mixture to supersaturate and precipitate in a short time into a population of nanoparticles of uniform size, i.e., a nanoparticle dispersion. The method allows one skilled in the art to mix the organic solution stream and the antisolvent stream to produce stable, single or composite silicone nanoparticles of predictable size.

According to the preparation method provided by the present invention, preferably, the organic solution and the antisolvent are rapidly mixed in step (2) through a mixing process of dual nozzle impact jet.

In a preferred embodiment of the present invention, the preparation process of the single silicone nanoparticles or the multicomponent composite silicone nanoparticles involves a closed impingement jet mixer. The mixing process of the double-nozzle impact jet comprises the following steps: the organic solution stream and the antisolvent stream were mixed by passing through a closed impingement jet mixer.

Preferably, the closed impact mixer is provided with a mixing vessel, two inlet pipes through which the organic solution stream and the antisolvent stream are introduced into the mixing vessel, respectively, and one outlet pipe. As shown in FIG. 1, the two inlet pipes and one outlet pipe of the closed impingement jet mixer together with the mixing vessel form a "T-shaped" tunnel. Each inlet line can be connected to a syringe pump, which in the inlet line will provide a constant flow rate (harvard instruments PHD 2000). For example, a glass syringe (SGE Inc.) may be connected to each inlet tube, and two streams of solution are introduced into the mixing vessel through the two inlet tubes, respectively. The solution streams, entering the conical mixing vessel from the inlet pipe at a constant rate, impact each other. The diameter D of the wider end of the mixing vessel is typically from 2.0mm to 5.0mm, more preferably from 2.4mm to 4.8 mm.

Preferably, each of said inlet tubes has a diameter of from 0.25mm to 6mm, more preferably from 0.5mm to 2.0 mm; the outlet pipe of the mixing vessel has a diameter delta of 0.5mm to 2.5mm, more preferably 1.0mm to 2.0 mm.

The reynolds number is defined as the fluid flow rate multiplied by the average density of the fluid and the inlet flow diameter divided by the average fluid viscosity at the inlet flow, i.e., Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficients of the fluid, respectively, and d is the inlet flow diameter.

When the injection quantity Q is fixed in unit time, the relationship between the pipe diameter d and the flow velocity v in the pipe is as follows: v 4Q/(π d)²). When d becomes smaller, v is given as d²The multiple of (a) becomes large. Therefore, vd is constant/d. The smaller d, the larger vd, and the larger Re. When the injection flow rate of the injection pump (or the injector) is fixed, the smaller the pipe diameter of the inlet pipe is, the larger the Reynolds number is, so that the particle size of the final silicone nano particles is smaller and more uniform. The pipe diameter of the inlet pipe selected by the closed impact type jet mixer can ensure that the Reynolds number reaches more than 1600.

In a closed impingement jet mixer, the organic solvent stream is intensively and rapidly mixed with the anti-solvent stream. The rapid mixing is such that the mixing system operates at reynolds numbers > 1600. That is, a high supersaturation of the mixture may be induced between milliseconds. The reynolds number of the system can be determined by one skilled in the art by readily measuring the flow rate and kinematic viscosity of the inlet stream by methods well known in the art.

Under the condition of the Reynolds number, the mixed solute is precipitated from a supersaturated state, and nanoparticles with uniform particle size are generated. The nano particles are stable in property and keep a dispersed state when flowing out of the outlet pipe. The particles remain stable when the polymer (i.e., silicone) entraps the active species.

According to the preparation method provided by the invention, preferably, the hydrophobic silicone resin has a general formula of (R)₁R₂SiO) n, wherein,

R₁、R₂the same or different, each is independently selected from one or more of hydrogen, hydroxyl, alkyl, alkenyl, alkoxy, aryl, aralkyl, epoxy, thiol, amine, mercapto, amide, polyether, fatty acid ester, carboxylic acid, fatty acid amide, isocyanate, fluoro, halogen, epoxy, phenol and silanol; more preferably one or more selected from the group consisting of hydrogen, methyl, ethyl, propyl, vinyl, phenyl, methoxy, methylphenyl, ethylphenyl, acrylamide, acrylate, aminopolyether, epoxypolyether, methacrylic acid, anhydride, dimethylamine, acryloxy, fluoroether, fluorine and chlorine; n is a positive integer.

Preferably, the hydrophobic silicone resin is selected from one or more of polyalkyl silicone resin, polyaryl silicone resin, polyalkylaryl silicone resin and modified silicone resin. The polyalkyl silicone resin may be selected from polymethyl silicone resin and/or polyethyl silicone resin.

Preferably, the modified silicone resin is selected from one or more of epoxy modified silicone resin, polyester modified silicone resin and polyurethane modified silicone resin.

Preferably, the weight average molecular weight of the hydrophobic silicone resin is 280-100,000,000 g/mol, and more preferably 280-100,000 g/mol.

In the preparation method provided by the invention, the hydrophobic silicone resin has a wide variety of types, and can be purchased from commercial sources, including but not limited to: gelest companies (such as ALT-173, DBE-921, DMS-S27 and OE43), Dow Corning companies (such as 7091, 748 and Q3-3636), shin-Etsu chemical industries, Inc. (such as KE-66 and FER-7110), Mediterran advanced materials (such as RTV615, RTV630 and RTV162), Steyr chemistry (such as Silmer-G104 and Silmer-G222).

The hydrophobic silicone may have various types of structures including, but not limited to: linear structure, branched structure, comb-like structure, cyclic junctionA structural, two-dimensional or three-dimensional network structure, or various combinations of the above. And the silicone resin contains any number of functional groups R along the main chain and/or end groups and/or comb-like structure of the molecule₁And R₂。

The hydrophobic silicone may also be a hybrid silicone including, but not limited to, one or more of a siloxane-polyimide, siloxane-urea, and siloxane-epoxy.

According to the preparation method provided by the invention, the hydrophobic silicone resin forms nanoparticles independently, or forms nanoparticles together with auxiliary materials. Preferably, the organic solution in step (1) is further dissolved with auxiliary materials.

Preferably, the auxiliary material comprises: one or more of an active, an organic or inorganic imaging agent, a pigment, an ink, a pesticide, a herbicide, a fluorescent probe, a sunscreen agent, an antioxidant, a fragrance, and a flavor compound. After the auxiliary material is added into the water-soluble organic solvent, the prepared silicon resin nano particles can be applied to a plurality of fields. Of course, when the auxiliary material is added to the water-soluble organic solvent, the addition of other auxiliary agents (such as a compatibilizer, an accelerator, and the like) is also allowable. In an embodiment of the invention, the sunscreen agent is selected from octocrylene; the antioxidant is selected from DL-alpha tocopherol.

The silicone nanoparticles of the present invention are useful for the delivery of pharmaceutical agents in vivo. In these cases, preferably, the active substance is selected from a therapeutic or diagnostic agent.

Preferably, the therapeutic agent is selected from the group consisting of antineoplastic agents, anthelmintics, antibiotics, anticoagulants, antidepressants, antidiabetics, antiepileptics, antihistamines, antihypertensives, antimuscarinics, antimycobacterial agents, immunosuppressive agents, antithyroid agents, antiviral agents, anxiolytic sedatives, astringents, beta-adrenoceptor blocking agents, inotropic agents, contrast agents, corticosteroids, antitussives, diuretics, dopaminergic agents, hemostatic agents, immunological agents, lipid regulating agents, muscle relaxants, parasympathetic agents, parathyroid calcitonin, bisphosphonates, protease inhibitors, prostaglandins, radiopharmaceuticals, sex hormones, steroids, antiallergic agents, stimulants, sympathomimetic agents, thyroid agents, vasodilators, and xanthines, disulfides, antibacterial agents, antiviral agents, non-steroidal anti-inflammatory drugs, Analgesics, anticoagulants, anticonvulsants, antiemetics, antifungals, antihypertensives and their adjuvants, anti-inflammatory agents, antiprotozoal agents, antipsychotics, cardioprotective agents, cytoprotective agents, antiarrhythmics, hormones, immunostimulants, lipid lowering agents, platelet aggregation inhibitors, drugs for treating prostatic hyperplasia, drugs for treating rheumatic diseases or vascular agents.

Antineoplastic agents refer to moieties that have an effect on the growth, proliferation, invasion or survival of tumor cells or tumor tissue. Antineoplastic agents typically include disulfides, alkylating agents, antimetabolites, cytotoxic antibiotics, resistance modifiers, or various plant alkaloids and derivatives thereof. Other antineoplastic agents are also contemplated.

Specifically, the antineoplastic agent is selected from the group consisting of paclitaxel, etoposide, camptothecin, idarubicin, carboplatin, oxaliplatin, doxorubicin, mitomycin, amphenomycin, bleomycin, cytarabine, arabinoadenine, mercaptopolylysine, vincristine, busulfan, chlorambucil, levophenylalanine mustard, mercaptopurine, chlorophylline, procarbazine hydrochloride, dactinomycin, mitomycin, plicamycin, aminomaleimide, estramustine sodium, flutamide, leuprolide acetate, megestrol acetate, tamoxifen citrate, caprolactone, tricycloalkane, amsacrine, asparaginase, interferon, teniposide, vinblastine sulfate, vincristine sulfate, bleomycin, methotrexate, pentaerythrin, camarazepine, taxane, camptothecin, doxorubicin, daunomycin, and oxaliplatin, One or more of cisplatin, 5-fluorouracil and methotrexate.

The anti-inflammatory agent may be selected from one or more of indomethacin, ibuprofen, ketoprofen, flurbiprofen, diclofenac, piroxicam, tenoxicam, naproxen, aspirin and acetaminophen.

The sex hormone may be one or more selected from testosterone, estrogen, progestogen, and estradiol.

The antihypertensive agent may be selected from one or more of captopril, ramipril, terazosin, minoxidil and perazosin.

The antiemetic can be selected from one or two of ondansetron and granisetron.

The antibiotic may be selected from one or both of metronidazole and fusidic acid.

The antifungal agent can be one or more selected from itraconazole, ketoconazole, and amphotericin.

The steroid may be selected from one or more of triamcinolone acetonide, hydrocortisone, dexamethasone, prednisolone, and betamethasone.

The diagnostic agent may include, for example, a chelated metal ion for MRI imaging, a radionuclide such as⁹⁹Tc or¹¹¹In or one or more other biocompatible radionuclides.

According to the preparation method provided by the invention, the antisolvent is a liquid which is compatible with the water-soluble organic solvent and incompatible with the silicone resin. Preferably, the solvent in the anti-solution is water. In the anti-solution, a solute may or may not be added. If the solute is added, the amount of the solute in the anti-solution is 0 to 30 wt% of the amount of the hydrophobic silicone resin, and preferably 5 to 20 wt%.

In a preferred embodiment of the present invention, the anti-solution contains a stabilizer (i.e., solute).

Preferably, the amount of the stabilizer in the anti-solution is 0-30 wt%, more preferably 5-17 wt% of the amount of the hydrophobic silicone resin.

Preferably, the stabilizer is selected from one or more of a cationic surfactant, an anionic surfactant, a nonionic surfactant and an amphiphilic copolymer.

Preferably, the cationic surfactant is selected from one or more of octenidine dihydrochloride, cetyltrimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, 5-bromo-5-nitro-1, 3-dioxane, dioctadecyldimethylammonium chloride, cetrimide and dioctadecyldimethylammonium bromide.

Preferably, the anionic surfactant is selected from one or more of ammonium lauryl sulfate, sodium laureth sulfate, sodium myristate, sodium dioctyl sulfosuccinate, perfluorooctanesulfonate, sodium perfluorobutylsulfonate, sodium stearate, and linear alkylbenzene sulfonate.

Preferably, the nonionic surfactant is selected from one or more of polyoxyethylene glycol alkyl ether, polyoxyethylene propylene glycol alkyl ether, glucoside alkyl ether, polyoxyethylene glycol octylphenol ether, polyoxyethylene glycol alkylphenol ether, glycerin alkyl ester, sorbitan ester, and sorbitan stearate.

Preferably, the amphiphilic copolymer is a compound having a hydrophilic portion and a hydrophobic portion with a weight average molecular weight of more than 500 g/mol.

Preferably, the weight average molecular weight of the amphipathic copolymer is 500-50000g/mol, more preferably 1000-50000g/mol, and further preferably 3000-25000 g/mol.

The hydrophobicity as referred to in the present invention, for example: hydrophobic silicone means a material having a solubility in water of less than 0.1 to 0.01 wt% at 20 ℃. Hydrophilic means that the material has a solubility in water of greater than 1mg/mL at 20 ℃.

Typical amphiphilic copolymers are copolymers comprising a hydrophilic portion and a hydrophobic portion. Thus, in an amphiphilic stabilizer, if the polymer of the hydrophobic part is used alone, its solubility in aqueous media will be lower than 0.05 mg/mL; if the polymer of the hydrophilic moiety is used alone, its solubility in aqueous media will be greater than 1 mg/mL.

In the present invention, the amphiphilic copolymer may be a graft copolymer, a block copolymer or a random copolymer. Suitable hydrophobic blocks in the amphipathic copolymer include, but are not limited to, the following: one or more of an acrylate, a methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl versatate, vinyl propionate, vinyl formamide, vinyl acetamide, vinyl pyridine, vinyl imidazole, aminoalkyl, styrene, cellulose acetate phthalate, cellulose acetate succinate, hydroxypropyl methylcellulose phthalate, poly (D, L lactide), poly (D, L-lactide-co-glycolide), poly (hydroxybutyrate), poly (alkyl carbonate), poly (orthoester), polyester, poly (hydroxyvaleric acid), polydioxanone, poly (ethylene terephthalate), poly (malic acid), poly (propanoic acid), polyanhydride, polyphosphazene, and poly (amino acid).

The acrylate is preferably selected from one or more of methyl acrylate, ethyl acrylate, propyl acrylate, n-Butyl Acrylate (BA), isobutyl acrylate, 2-ethyl acrylate and t-butyl acrylate.

The methacrylate is preferably selected from one or more of ethyl methacrylate, n-butyl methacrylate and isobutyl methacrylate.

The aminoalkyl radical is preferably selected from the group consisting of aminoalkyl acrylates, aminoalkyl methacrylates and aminoalkyl (meth) acrylamides.

Suitable hydrophobic blocks also include: hydrophobic peptide polymers, copolymers based on poly (L-amino acids), poly (ethylene-vinyl acetate) ("EVA") copolymers, silicone rubber, polyethylene, polypropylene, polydienes (polybutadiene, polyisoprene and hydrogenated versions thereof), maleic anhydride copolymers of vinyl methyl ether and other vinyl ethers, polyamides (nylon 6,6), polyurethanes, poly (ester polyurethanes), poly (ether polyurethanes), poly (ester-ureas), poly (D, L-lactic acid) oligomers, poly (glycolic acid), copolymers of lactic acid and glycolic acid, poly (caprolactone), poly (valerolactone), polyanhydrides, poly (caprolactone) or copolymers of poly (lactic acid). For non-bio related applications, preferably the hydrophobic block is selected from polystyrene, polyacrylate or butadiene.

Suitable hydrophilic blocks in the amphipathic copolymer include, but are not limited to, the following: one or more of carboxylic acids, polyoxyethylene, polyethylene oxide, polyacrylamide, 2- (dimethylamino) ethyl methacrylate, diallyldimethyl ammonium chloride, vinylbenzyltrimethyl ammonium chloride, acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and styrene sulfonate, polyvinylpyrrolidone, starch and starch derivatives, copolymers of dextran and dextran derivatives, polypeptides, polyhyaluronic acid, alginic acid, polylactide, polyethyleneimine, polyolefins, polyacrylic acid, polyiminocarboxylic acid esters, gelatin, unsaturated olefinic monocarboxylic acids and unsaturated olefinic dicarboxylic acids.

The carboxylic acids are preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid.

The polypeptides are preferably selected from polylysine, polyarginine, polyglutamic acid.

In the present invention, the block means a diblock or triblock. Preferably, the block in the block copolymer used in the present invention is selected from one or more of polystyrene, polyethylene, polybutyl acrylate, polylactic acid, polycaprolactone, polyacrylic acid, polyoxyethylene and polyacrylamide.

Copolymers of polyethylene glycol and polycaprolactone, and poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) are typical examples of amphiphilic copolymers.

According to the preparation method provided by the invention, preferably, the water-soluble organic solvent is selected from tetrahydrofuran, dimethyl sulfoxide, ethanol, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ethylene glycol, propylene glycol, benzyl alcohol, dimethylacetamide, benzyl benzoate, C₂-C₆One or more of alkanol, 2-ethoxyethanol, 2-ethoxyethyl acetate, methyl acetate, ethyl acetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, acetone, glycerol, methyl ethyl ketone, dimethyl sulfone, caprolactam, decylmethylsulfoxide, N-diethyl-m-toluamide, 1-dodecylazacycloheptan-2-one, triacetin, dimethylformamide, pyridine, an organic acid, an organic base, acetonitrile, methanol and 1, 4-dioxane; more preferably one or more selected from tetrahydrofuran, dimethyl sulfoxide and ethanol.

The water-soluble organic solvent as described above can be purchased commercially from major suppliers such as Sigma-Aldrich, Baker and Mallinckrodt, and the like.

According to the preparation method provided by the invention, the volume ratio of the organic solution to the anti-solution is preferably 1: 50-1: 1, more preferably 1: 20-1: 1, and further preferably 1: 2-1: 1.

According to the preparation method provided by the invention, preferably, the dissolving amount of the hydrophobic silicone resin in the water-soluble organic solvent is less than 500mg/mL, more preferably 1-100 mg/mL, and further preferably 1-20 mg/mL.

The mass ratio of the auxiliary material to the hydrophobic silicone resin is 0: 1-1.5: 1, and preferably 0.1: 1-1.2: 1.

According to the preparation method provided by the invention, preferably, in the step (1), a cross-linking agent capable of performing a cross-linking reaction with the hydrophobic silicone resin is added.

Preferably, the cross-linking agent is selected from one or more of alkoxy silane, oxime silane, acetoxy silane, methyl orthosilicate, ethyl orthosilicate, peroxide and polyol cross-linking agent;

preferably, the alkoxysilane is methyltrimethoxysilane and/or trimethoxysilane;

preferably, the acetoxysilane is methyltriacetoxysilane;

preferably, the peroxide is 2, 4-dichlorobenzoyl peroxide;

preferably, the polyol-based cross-linking agent is selected from polyethylene glycol and/or trimethylolpropane;

preferably, the mass ratio of the cross-linking agent to the hydrophobic silicone resin is greater than 0 and less than 1:3, and more preferably 1:10 to 1: 3.

Preferably, the crosslinking reaction occurs in situ after mixing the organic solution and the antisolvent.

Certain reactive groups of silicone resins can undergo a crosslinking reaction, which can be achieved through several reaction routes, including but not limited to: radical crosslinking reaction, condensation crosslinking reaction, and addition crosslinking reaction. The crosslinking reaction may be catalyzed by chemical catalysts (including but not limited to ruthenium or platinum), heat, ultraviolet light exposure, or a combination thereof. The crosslinking reaction of the invention can occur immediately after the formation of the nano particles, and no new component or excitant is needed to be added; of course, the aftertreatment can also be carried out by adding catalysts or initiators as described above.

The invention also provides a silicon resin nanoparticle dispersion obtained by the preparation method; the silicone nanoparticles are distributed in the resulting silicone nanoparticle dispersion.

Preferably, the particle size of the silicone resin nanoparticles is 20nm to 1500nm, more preferably 50 nm to 800nm, and even more preferably 80 nm to 400 nm.

In the present invention, the particle size and particle size distribution can be controlled by selecting the kind of the water-soluble organic solvent, selecting the kind and concentration of the solute (including the silicone resin and the auxiliary material in the organic solution and the stabilizer in the antisolvent), the ratio of the organic solution and the antisolvent, and the flow rate of the resulting organic solution and antisolvent.

The stability of the silicone nanoparticles in the silicone nanoparticle dispersion is also within the control of the skilled worker, which can be achieved by the above-mentioned selection of the type of silicone, crosslinked or uncrosslinked system and stabilizer.

In some embodiments of the invention, the nanoparticles crosslink in situ and precipitate rapidly (flash-precipitate) after the two different solution streams are mixed. In the present invention, the silicone nanoparticles are generally not crosslinked before the flash process occurs.

The technical scheme of the invention has the beneficial effects that:

(1) the preparation method can realize rapid (Reynolds number is larger than 1600) precipitation of the silicon resin material dissolved in the water-soluble organic solvent, and silicon resin nano particles with uniform particle size distribution can be obtained; when the anti-solution contains the stabilizer, the prepared silicon resin nano particles have smaller particle size;

(2) the preparation method allows the silicone resin nanoparticles to be subjected to in-situ crosslinking while being continuously produced and dispersed, and the silicone resin nanoparticles obtained through crosslinking reaction have stable properties and keep a dispersed state.

Drawings

FIG. 1 shows a schematic view of a double nozzle impingement jet mixing process used in one embodiment of the production method of the present invention;

fig. 2 shows dynamic light scattering intensity weighted particle size distribution plots for the silicone nanoparticles of examples 1 and 4.

Fig. 3 shows SEM images of the silicone nanoparticles of example 1.

Detailed Description

In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.

1. The raw material sources are as follows:

vinyl polydimethylsiloxane, RTV615A, Mylar;

crosslinking agent, RTV615B, Meiji;

polysorbate 80, marketed under the name "Tween 80", a company of Sada America;

octocrylene, sold under the trade name "Parsol 340", by imperial corporation;

tetrahydrofuran, Shanghai Aladdin Biotechnology Ltd;

DL-alpha-tocopherol, Shanghai Allantin Biotechnology Ltd;

tricaprylin, Shanghai Allantin Biotechnology Ltd;

poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol), Mn 5800g/mol, under the trade name "Pluronic P-123", available from basf corporation.

2. The test method comprises the following steps:

(1) the instrument used for Dynamic Light Scattering (DLS) measurement is a Markov instrument Zetasizer Nano-ZSZEN 3600; the measurement procedure or test conditions were:

taking out a small amount of the silicon resin nano particle dispersion, and diluting the silicon resin nano particle dispersion with water to be nearly transparent; and (3) dropwise adding the mixture into a DLS sample pool, and testing the particle size and the particle size distribution coefficient of the nano particles by DLS at 25 ℃.

(2) The instrument used for Scanning Electron Microscope (SEM) measurement is FEI XL-30; the measurement procedure or test conditions were:

the silicone nanoparticles were dropped onto a carbon ribbon, allowed to dry overnight in a fume hood, then coated with a 5nm thick iridium layer, and SEM imaged at 5 kV.

3. Laboratory apparatus

Closed impingement jet mixer:

in each example, a closed impingement jet mixer was custom made by the equipment manufacturer and included the following components:

1) the main body of the mixing device is a piece of PTFE (McMaster-Carr) with dimensions of 6cm by 4cm by 5 cm. As shown in FIG. 1, the PTFE block has "T-shaped" channels therein. The mixing vessel used in the examples had a bore size of: d2 mm, D4 mm, δ 2 mm.

2)3 fittings (model P-302, flangeless fitting nut, 1/4-28 flat bottom, adapted for 1/8 "OD tube, IDEX Health & Science LLC) were attached to the mixing device body. Wherein, 2 connectors are respectively connected with the inlet at the upper part of the T-shaped pore channel, and 1 connector is connected with the outlet at the lower part of the T-shaped pore channel. The inlet fitting and tefzel (etfe) tubing (model 1530, 1/8 "OD x 1/16" ID, IDEX Health & Science LLC) were assembled by a flangeless ferrule (model P-300, IDEX Health & Science LLC), the tefzel (etfe) tubing being connected to a syringe fixed in a syringe pump. The outlet connector is assembled in a similar manner, except that a vessel such as a beaker is directly placed at the lower end of the Tefzel (ETFE) tube for sampling.

Example 1:

344mg of commercial vinyl polydimethylsiloxane was dissolved in 75.7mL of Tetrahydrofuran (THF) to form a tetrahydrofuran solution, and then 34.4mg of the crosslinking agent was added to the tetrahydrofuran solution and mixed well. The tetrahydrofuran solution was then placed in a 100mL glass syringe, mounted on a syringe pump (Harvard instruments PHD 2000) and connected to the solvent stream inlet of a closed impingement jet mixer for flash precipitation. A second 100mL glass syringe contained 75.7mL distilled water, fixed in the same syringe pump and connected to the anti-solvent stream inlet pipe of a closed impact mixer for flash process. The syringe pump pumps the solution from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 150mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 2000, with specific parameters: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, i.e. THF, was subsequently removed by membrane dialysis. As shown in fig. 2, dynamic light scattering measurements indicated that the silicone nanoparticles had a particle size of 156 nm. The SEM image of the obtained silicone resin nanoparticles is shown in FIG. 3, and the nanoparticles are uniform in size.

Example 2:

344mg of commercial vinyl polydimethylsiloxane was dissolved in 75.7mL of Tetrahydrofuran (THF) to form a tetrahydrofuran solution, and then 34.4mg of the crosslinking agent was added to the tetrahydrofuran solution and mixed well. The tetrahydrofuran solution was then filled in a 140mL polypropylene syringe (Monoject Model, Medtronic) which was mounted on a syringe pump (Harvard instruments PHD 2000) and connected to the solvent flow inlet of a closed impingement jet mixer used for flash precipitation. A second 140mL polypropylene syringe containing 75.7mL of distilled water was mounted in the same syringe pump and connected to the antisolvent flow inlet tube of the closed impingement jet mixer used in the flash precipitation process. The syringe pump pumps the solutions from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 220mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 3100, with specific parameters: v 1.5m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, i.e. THF, was subsequently removed by membrane dialysis. Dynamic light scattering measurements showed that the particle size of the silicone nanoparticles was 143 nm.

Example 3:

1376mg of commercial vinyl polydimethylsiloxane was dissolved in 75.7mL of Tetrahydrofuran (THF) to form a tetrahydrofuran solution, and 137.6mg of crosslinking agent was added to the tetrahydrofuran solution and mixed well. The tetrahydrofuran solution was then placed in a 100mL glass syringe, mounted on a syringe pump (Harvard instruments PHD 2000) and connected to the solvent stream inlet of a closed impingement jet mixer for flash precipitation. A second 100mL glass syringe containing 75.7mL of distilled water was mounted in the same syringe pump and connected to the anti-solvent stream inlet tube of the closed impingement jet mixer used for the flash precipitation process. The syringe pump pumps the solution from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 150mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 2000, with specific parameters: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, i.e. THF, was subsequently removed by membrane dialysis. Dynamic light scattering measurements showed that the particle size of the silicone nanoparticles was 278 nm. The obtained silicone resin nano particles are uniform in size.

Example 4:

344mg of vinyl polydimethylsiloxane was dissolved in 75.7mL of THF to form a tetrahydrofuran solution, and then 34.4mg of crosslinker was added to the tetrahydrofuran solution and mixed well. Then, the tetrahydrofuran solution was contained in a 100mL glass syringe, fixed to a syringe pump, and connected to the solvent flow inlet pipe of a closed impact jet mixer for the flash precipitation method. Dissolving 19.2mg of polysorbate 80, a nonionic surfactant, in 75.7mL of distilled water to form an aqueous polysorbate 80 solution; a second 100mL glass syringe containing an aqueous polysorbate 80 solution was fixed in the same syringe pump and connected to the anti-solvent stream inlet tube of a closed impingement jet mixer used for the flash precipitation process. The solution from the two syringes was pumped by the syringe pump into a closed impact jet mixer at a volumetric flow rate of 150mL/min with reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet stream flow rateDiameter) is about 2000, and the specific parameters are: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, i.e. THF, was subsequently removed by membrane dialysis. As shown in fig. 2, dynamic light scattering measurements indicated that the silicone nanoparticles had a particle size of 114 nm. The obtained silicone resin nano particles are uniform in size.

Example 5:

344mg of vinyl polydimethylsiloxane was dissolved in 75.7mL of THF to form a tetrahydrofuran solution, and then 34.4mg of crosslinker was added to the tetrahydrofuran solution and mixed well. Then, the tetrahydrofuran solution was contained in a 100mL glass syringe, fixed to a syringe pump, and connected to the solvent flow inlet pipe of a closed impact jet mixer for the flash precipitation method. Dissolving 57.6mg of polysorbate 80, a nonionic surfactant, in 75.7mL of distilled water to form an aqueous polysorbate 80 solution; a second 100mL glass syringe containing an aqueous solution of polysorbate 80 was mounted in the same syringe pump and connected to the anti-solvent stream inlet tube of a closed impingement jet mixer used for the flash precipitation process. The syringe pump pumps the solution from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 150mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 2000, with specific parameters: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, i.e. THF, was subsequently removed by membrane dialysis. Dynamic light scattering measurements showed that the particle size of the silicone nanoparticles was 82 nm. The obtained silicone resin nano particles are uniform in size.

Example 6:

344mg of vinyl polydimethylsiloxane was dissolved in 75.7mL of THF to form a tetrahydrofuran solution, and then 34.4mg of crosslinker was added to the tetrahydrofuran solution and mixed well. Then, the tetrahydrofuran solution was contained in a 100mL glass syringe, fixed to a syringe pump, and connected to the solvent flow inlet pipe of a closed impact jet mixer for the flash precipitation method.Dissolving 19.2mg of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (amphipathic copolymer) in 75.7mL of distilled water to form an aqueous poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) solution; a second 100mL glass syringe containing an aqueous solution of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) was mounted in the same syringe pump and connected to the anti-solvent stream inlet tube of a closed impingement jet mixer used in the flash process. The syringe pump pumps the solution from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 150mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 2000, with specific parameters: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, i.e. THF, was subsequently removed by membrane dialysis. Dynamic light scattering measurements showed that the particle size of the silicone nanoparticles was 122 nm. The obtained silicone resin nano particles are uniform in size.

Example 7:

344mg of vinyl polydimethylsiloxane was dissolved in 75.7mL of THF to form a tetrahydrofuran solution, and then 34.4mg of a crosslinking agent and 189.2mg of Octocrylene (OCR) were added to the tetrahydrofuran solution and mixed well. Then, the tetrahydrofuran solution was contained in a 100mL glass syringe, fixed to a syringe pump, and connected to the solvent flow inlet pipe of a closed impact jet mixer for the flash precipitation method. Dissolving 19.2mg of polysorbate 80, a nonionic surfactant, in 75.7mL of distilled water to form an aqueous polysorbate 80 solution; a second 100mL glass syringe containing an aqueous solution of polysorbate 80 was mounted in the same syringe pump and connected to the anti-solvent stream inlet tube of a closed impingement jet mixer used for the flash precipitation process. The syringe pump pumps the solution from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 150mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 2000, with specific parameters: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²S, andthe resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, THF, was then removed by membrane dialysis to produce composite silicone nanoparticles containing 50 wt% OCR. Dynamic light scattering measurements showed that the silicone nanoparticles had a particle size of 132 nm. The obtained silicone resin nano particles are uniform in size.

Example 8:

344mg of vinyl polydimethylsiloxane was dissolved in 75.7mL of THF to form a tetrahydrofuran solution, and then 34.4mg of a mixture of a crosslinking agent, 189.2mg of DL-alpha-tocopherol and tricaprylin (the mass ratio of the two in the mixture is 1:1) was added to the tetrahydrofuran solution and mixed well. Then, the tetrahydrofuran solution was contained in a 100mL glass syringe, fixed to a syringe pump, and connected to the solvent flow inlet pipe of a closed impact jet mixer for the flash precipitation method. Dissolving 19.2mg of polysorbate 80, a nonionic surfactant, in 75.7mL of distilled water to form an aqueous polysorbate 80 solution; a second 100mL glass syringe containing an aqueous solution of polysorbate 80 was mounted in the same syringe pump and connected to the anti-solvent stream inlet tube of a closed impingement jet mixer used for the flash precipitation process. The syringe pump pumps the solution from the two syringes into the closed impingement jet mixer at a volumetric flow rate of 150mL/min with a reynolds number (Re ═ ρ vd/μ, where v, ρ, μ are the flow rate, density and viscosity coefficient of the fluid, respectively, and d is the inlet flow diameter) of about 2000, with specific parameters: v 1m/s, d 0.002m, mu/[ mu ] 9.79X 10^-7m²And the resulting silicone nanoparticle dispersion was collected in a glass beaker at the outlet of the mixer. The solvent, THF, was then removed by membrane dialysis to prepare composite silicone nanoparticles containing 25 wt% DL- α -tocopherol. Dynamic light scattering measurements showed that the particle size of the silicone nanoparticles was 125 nm. The obtained silicone resin nano particles are uniform in size.

Comparative example 1:

1376mg of commercial vinyl polydimethylsiloxane was dissolved in 75.7mL of Tetrahydrofuran (THF) to form a tetrahydrofuran solution, and 137.6mg of crosslinking agent was added to the tetrahydrofuran solution and mixed well. Then, the tetrahydrofuran solution containing the silicone polymer and the crosslinking agent was poured into a beaker containing 75.7mL of distilled water, and the silicone polymer precipitated immediately. However, in water/THF solution: macroscopic clumps of agglomerates. Dynamic light scattering tests were not possible because the size of the silicone particles and visible agglomerates was too large.

It can be seen from the comparison between the examples and the comparative examples that the preparation method of the present invention can realize the rapid precipitation of the silicone resin material dissolved in the solvent flow, and can obtain the silicone resin nanoparticles with uniform particle size distribution, while the silicone resin polymer precipitated in the direct mixing manner of the comparative example 1 has the agglomeration of the silicone resin particles, the occurrence of the block agglomerates, the non-uniform distribution and the oversize particle size.

Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A preparation method of a silicon resin nanoparticle dispersion is characterized by comprising the following steps:

the rapid mixing is to make the mixing system operate at Reynolds number > 1600;

in the step (1), adding a cross-linking agent which can perform cross-linking reaction with the hydrophobic silicone resin; the cross-linking agent is selected from one or more of alkoxy silane, oxime silane, acetoxy silane, methyl orthosilicate, ethyl orthosilicate, peroxide and polyol cross-linking agent.

2. The method of claim 1, wherein the rapid mixing is such that the mixing system operates at 1600 < reynolds number < 4000.

3. The preparation method according to claim 1, wherein the organic solution and the antisolvent are rapidly mixed in step (2) by a mixing process of dual nozzle impact jet.

4. The method for preparing according to claim 3, wherein the mixing process of the dual nozzle impingement jet comprises the steps of: the organic solution stream and the antisolvent stream were mixed by passing through a closed impingement jet mixer.

5. The production method according to claim 4, wherein the closed impact mixer is provided with a mixing vessel, two inlet pipes and one outlet pipe, and the organic solution flow and the antisolvent flow are introduced into the mixing vessel through the two inlet pipes, respectively.

6. The method of claim 5, wherein each of the inlet pipes of the closed impingement jet mixer has a diameter of 0.25mm to 6 mm.

7. The method of claim 6, wherein each of the inlet pipes of the closed impingement jet mixer has a diameter of 0.5mm to 2.0 mm.

8. The method of claim 5, wherein the outlet tube of the closed impingement jet mixer has a diameter of 0.5mm to 2.5 mm.

9. The method of claim 8, wherein the outlet tube of the closed impingement jet mixer has a diameter of 1.0mm to 2.0 mm.

10. The method according to any one of claims 1 to 9, wherein the reaction mixture is heated to a temperature in the reaction mixtureThe hydrophobic silicone resin has a general formula of (R)₁R₂SiO) n, wherein,

R₁、R₂the same or different, each is independently selected from one or more of hydrogen, hydroxyl, alkyl, alkenyl, alkoxy, aryl, aralkyl, epoxy, thiol, amine, mercapto, amide, polyether, fatty acid ester, carboxylic acid, fatty acid amide, isocyanate, fluoro, halogen, epoxy, phenol and silanol; n is a positive integer.

11. The method of claim 10, wherein R is₁、R₂The same or different, each is independently selected from one or more of hydrogen, methyl, ethyl, propyl, vinyl, phenyl, methoxy, methylphenyl, ethylphenyl, acrylamide, acrylate, aminopolyether, epoxy polyether, methacrylic acid, anhydride, dimethylamine, acryloxy, fluoroether, fluorine and chlorine.

12. The method of claim 10, wherein the hydrophobic silicone resin is selected from one or more of polyalkyl silicone resin, polyaryl silicone resin, polyalkyl aryl silicone resin, and modified silicone resin.

13. The production method according to claim 12, wherein the modified silicone resin is one or more selected from the group consisting of an epoxy-modified silicone resin, a polyester-modified silicone resin, and a polyurethane-modified silicone resin.

14. The method of claim 10, wherein the hydrophobic silicone resin has a weight average molecular weight of 280 to 100,000,000 g/mol.

15. The method of claim 14, wherein the hydrophobic silicone resin has a weight average molecular weight of 280 to 100,000 g/mol.

16. The method according to any one of claims 1 to 9 and 11 to 15, wherein an auxiliary material is further dissolved in the organic solution of the step (1);

the auxiliary material includes: one or more of an active, an organic or inorganic imaging agent, a pigment, an ink, a pesticide, a herbicide, a fluorescent probe, a sunscreen agent, an antioxidant, a fragrance, and a flavor compound.

17. The method of claim 16, wherein the active agent is selected from a therapeutic agent or a diagnostic agent.

18. The production method according to any one of claims 1 to 9, 11 to 15, and 17, wherein the solvent in the anti-solution is water; the dosage of solute in the anti-solution is 0-30 wt% of the dosage of hydrophobic silicone resin.

19. The method according to claim 18, wherein the solute in the anti-solution is 5 to 20 wt% of the hydrophobic silicone resin.

20. The method of claim 18, wherein the solute in the antisolvent is a stabilizer;

the dosage of the stabilizer in the anti-solution is 0-30 wt% of the dosage of the hydrophobic silicone resin.

21. The method of claim 20, wherein the stabilizer is present in an amount of 5 to 17 wt% based on the amount of the hydrophobic silicone resin.

22. The method of claim 20, wherein the stabilizer is one or more selected from the group consisting of a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphiphilic copolymer.

23. The method of claim 22, wherein the cationic surfactant is selected from one or more of octenidine dihydrochloride, cetyltrimethylammonium bromide, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, 5-bromo-5-nitro-1, 3-dioxane, dioctadecyldimethylammonium chloride, cetrimide and dioctadecyldimethylammonium bromide;

the anionic surfactant is selected from one or more of ammonium lauryl sulfate, sodium dodecyl sulfate, sodium lauryl ether sulfate, sodium myristate sulfate, sodium dioctyl sulfosuccinate, perfluorooctane sulfonate, sodium perfluorobutyl sulfonate, sodium stearate and linear alkyl benzene sulfonate;

the nonionic surfactant is selected from one or more of polyoxyethylene glycol alkyl ether, polyoxyethylene propylene glycol alkyl ether, glucoside alkyl ether, polyoxyethylene glycol octylphenol ether, polyoxyethylene glycol alkylphenol ether, glycerin alkyl ester, sorbitan ester and sorbitan stearate;

the amphiphilic copolymer is a copolymer having a hydrophilic portion and a hydrophobic portion with a weight average molecular weight of 500-50000 g/mol.

24. The preparation method as claimed in claim 23, wherein the weight average molecular weight of the amphipathic copolymer is 1000-50000 g/mol.

25. The method as claimed in claim 24, wherein the weight average molecular weight of the amphipathic copolymer is 3000-25000 g/mol.

26. The method of any one of claims 1-9, 11-15, 17, 19-25, wherein the water-soluble organic solvent is selected from the group consisting of tetrahydrofuran, dimethylsulfoxide, ethanol, N-methyl-2-pyrrolidone, dimethylsulfoxide, ethylene glycol, propylene glycol, benzyl alcohol, dimethylacetamide, benzyl benzoate, C₂-C₆Alkyl alcohol of (2), 2-ethoxyethanol, 2-ethoxyethyl acetate, methyl acetateOne or more of ethyl acetate, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, acetone, glycerol, methyl ethyl ketone, dimethyl sulfone, caprolactam, decylmethylsulfoxide, N-diethyl-m-toluamide, 1-dodecylazacycloheptan-2-one, triacetin, dimethylformamide, pyridine, an organic acid, an organic base, acetonitrile, methanol and 1, 4-dioxane.

27. The method according to claim 26, wherein the water-soluble organic solvent is one or more selected from tetrahydrofuran, dimethylsulfoxide and ethanol.

28. The method according to any one of claims 1 to 9, 11 to 15, 17, 19 to 25, and 27, wherein the volume ratio of the organic solution to the anti-solution is 1:50 to 1: 1.

29. The method according to claim 28, wherein the volume ratio of the organic solution to the anti-solution is 1:20 to 1: 1.

30. The method according to claim 29, wherein the volume ratio of the organic solution to the anti-solution is 1:2 to 1: 1.

31. The method of claim 16, wherein the hydrophobic silicone resin is dissolved in the water-soluble organic solvent in an amount of <500 mg/mL;

the mass ratio of the auxiliary material to the hydrophobic silicone resin is 0: 1-1.5: 1.

32. The method according to claim 31, wherein the hydrophobic silicone resin is dissolved in the water-soluble organic solvent in an amount of 1 to 100 mg/mL;

the mass ratio of the auxiliary material to the hydrophobic silicone resin is 0.1: 1-1.2: 1.

33. The preparation method according to claim 32, wherein the amount of the hydrophobic silicone resin dissolved in the water-soluble organic solvent is 1 to 20 mg/mL;

34. The production method according to any one of claims 1 to 9, 11 to 15, 17, 19 to 25, 27, 29 to 33,

the alkoxy silane is methyl trimethoxy silane and/or trimethoxy silane;

the acetoxy silane is methyl triacetoxysilane;

the peroxide is 2, 4-dichlorobenzoyl peroxide;

the polyalcohol crosslinking agent is selected from polyethylene glycol and/or trimethylolpropane.

35. The production method according to claim 1, wherein the mass ratio of the crosslinking agent to the hydrophobic silicone resin is more than 0 and less than 1: 3.

36. The preparation method according to claim 35, wherein the mass ratio of the cross-linking agent to the hydrophobic silicone resin is 1:10 to 1: 3.

37. The method according to claim 1, wherein the crosslinking reaction occurs in situ after the organic solution and the antisolvent are mixed.

38. A silicone nanoparticle dispersion obtained by the production method according to any one of claims 1 to 37, wherein the silicone nanoparticles are distributed in the obtained silicone nanoparticle dispersion;

the particle size of the silicon resin nano particles is 20 nm-1500 nm.

39. The silicone nanoparticle dispersion of claim 38, wherein the silicone nanoparticles have a particle size of 50 nm to 800 nm.

40. The silicone nanoparticle dispersion of claim 39, wherein the silicone nanoparticles have a particle size of 80-400 nm.