CN103113824A - Film-forming polysiloxane emulsion and preparation method thereof - Google Patents
Film-forming polysiloxane emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN103113824A CN103113824A CN2013100272815A CN201310027281A CN103113824A CN 103113824 A CN103113824 A CN 103113824A CN 2013100272815 A CN2013100272815 A CN 2013100272815A CN 201310027281 A CN201310027281 A CN 201310027281A CN 103113824 A CN103113824 A CN 103113824A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- emulsion
- film
- acid
- organo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CCC(C)(CC)*1CCC(**)CC1 Chemical compound CCC(C)(CC)*1CCC(**)CC1 0.000 description 3
Landscapes
- Silicon Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses film-forming polysiloxane emulsion and a preparation method thereof. The preparation method of the film-forming polysiloxane emulsion comprises the following steps of: dissolving 0.02-20 parts by weight of composite surfactant to 100 parts of water; adding 10-60 parts by weight of organo-silicone monomers, shearing the organo-silicone monomers by a shearing and emulsifying stirrer, and homogenizing the organo-silicone monomers under 20Mpa-60Mpa to obtain organo-silicone monomer emulsion; raising the temperature of the organo-silicone monomer emulsion to 70 DEG C to 90 DEG C, adding 0.01-10 parts of catalyst for reacting for 4-6 hours, cooling the reaction liquid to 40 DEG C to 60 DEG C, adding 0.5-5 parts of a cationic surfactant and 0.05-20 parts of a cross-linking agent for reacting for 1-3 hours cooling the reaction liquid to 20 DEG C to 30 DEG C and adding acetic acid to neutralize the emulsion to be neutral so as to obtain the film-forming polysiloxane emulsion. The method for preparing the film-forming polysiloxane emulsion is less in steps, simple to operate, low in cost and high in conversion rate. The obtained film-forming polysiloxane emulsion can be placed for more than three months at normal temperature without layering or emulsion-breaking.
Description
Technical field
The present invention relates to the polysiloxane emulsion preparation field, particularly a kind of film-forming silicone emulsion and preparation method thereof.
Background technology
Can solidify and be cross-linked to form the organopolysiloxane of rubber or resin film in industrial circle widespread uses such as papermaking, weaving, slurry, coating, building, leather, medicine, makeup, and its Application Areas is in continuous expansion, it is very large to use potential.But the such film-forming silicone emulsion of most of preparation all needs to use metal compound as catalyst.Yet metal compound as catalyst is sayed existing problems from safety.
JP1981-36546 discloses a kind of silicon rubber emulsion compositions, comprising end by the polydimethylsiloxane of ethenyl blocking, the polysiloxane that contains the Si-H key, emulsifying agent, water and platinum catalyst, form emulsion through the homogeneous effect, heat this emulsion and form crosslinked latex, to wherein adding colloidal silica, thermal treatment obtains silicone elastomer.
JP-A12-169590 discloses a kind of curable formation silicon rubber emulsion compositions, comprising end by the polydimethylsiloxane of ethenyl blocking, the polysiloxane that contains the Si-H key, platinum class catalyzer, polyorganosiloxane resin, emulsifying agent, water and carbon black etc., form polysiloxane emulsion through the homogeneous effect, make it solidify to form silicone elastomer through thermal treatment.
US6593422 discloses a kind of crosslinked and emulsion non-crosslinked polyether silicon of containing, it comprises organopolysiloxane, the α that contains the non-crosslinked polyether silicon, contains the Si-H key, ω-diine, lower molecular weight line style or cyclic volatile methyl siloxanes, platinum class catalyzer and water, form emulsion through the homogeneous effect, form the cross linking polysiloxane particle after the thermal treatment.
US20110039087 discloses the emulsion of the crosslinked organopolysiloxane of a kind of swollen stream boron, and is terminal by polysiloxane, boride and the emulsifying agent of hydroxy-end capped polydimethylsiloxane, Si-H key comprising containing.
JP-A2005-306994 discloses a kind of emulsion compositions, and it comprises terminal by polydimethylsiloxane, trialkoxy silane or the tetraalkoxysilane of hydroxyl, alkoxyl group or aminoalkyl end-blocking and free metal compound as catalyst.
US2008-0328795 discloses a kind of crosslinkable polysiloxane coating composition, and it comprises terminal by the polydimethylsiloxane of ethenyl blocking, the organopolysiloxane that contains the Si-H key, platinum catalyst and optional inhibitor.
JP-A8-85760 discloses a kind of emulsion compositions, and it comprises the organoalkoxysilane that contains terminal alkoxy or hydroxy-end capped polydimethylsiloxane, the polysiloxane that contains the Si-H key, silicon-dioxide or polysilsesquioxane, contains amide group and carboxyl, organoalkoxysilane and the curing catalysts that contains epoxy group(ing) or amino.
US6491980B1 discloses a kind of silicon rubber emulsion compositions, comprising end by the polydimethylsiloxane of ethenyl blocking, enhancement silica filler, the water that contains montmorillonitic clay, emulsifying agent and organic hydrogen polysiloxanes linking agent and uranium class catalyzer.
In order to form at short notice the film that fully solidifies, must use the tin compound with high katalysis.Yet because the toxicity of tin compound, current industry avoids using tin compound.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of preparation method of film-forming silicone emulsion with not enough.
Another object of the present invention is to provide the film-forming silicone emulsion for preparing by above-mentioned preparation method.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of film-forming silicone emulsion comprises the steps:
(1) with 0.02～20 mass parts complexed surfactant with 100 mass parts water dissolution, add again 10～60 mass parts organo-siloxane monomers, shear 1～20min with the emulsification pretreatment stirrer, homogeneous obtains the organo-siloxane monomer emulsion under 20～60Mpa again.
(2) the organo-siloxane monomer emulsion is heated to 70～90 ℃, add 0.01～10 mass parts of catalyst, reaction 4～6h, be cooled to 40～60 ℃, add again 0.5～5 mass parts cats product and 0.05～20 mass parts linking agent, reaction 1～3h is cooled to 20～30 ℃ and adds in the acetic acid and emulsion to neutrality obtains film-forming silicone emulsion.
Complexed surfactant described in the step (1) is at least a in cats product, anion surfactant and the nonionogenic tenside.Described cats product comprises the cats products such as alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzyl alkyl-dimethyl based quaternary ammonium salt, monoalkyl quaternary ammonium salt, alkyl polyoxyethylene ylmethyl quaternary ammonium salt, N-alkyl diethanolamine salt, polyethylene polyamines salt, pyridinium salt, tetrahydroglyoxaline or morpholine.Described anion surfactant comprises alkyl-sulphate; alkylbenzene sulfonate; soap; alkyl hydrosulfate; the Voranol EP 2001 hydrogen sulfuric acid ester; the polyoxyethylene alkyl phenyl ether hydrogen sulfuric acid ester; N-acyl group taurine; the benzene sulfonamide acid esters; the polyoxyethylene alkyl phenyl ether sulphonate; the alpha-olefin sulphonate; the alkyl naphthalene sulfonic acid ester; alkyl diphenyl base ether disulfonate; dialkyl sulfosuccinate; the sulfo-succinic acid mono alkyl ester; the Voranol EP 2001 ester; the anion surfactants such as N-acyl amino hydrochlorate or alkyl phosphate.Described ionic surfactant pack is drawn together the nonionogenic tensides such as organopolysiloxane of isomery polyoxyethylenated alcohol, fatty acid methyl ester Soxylat A 25-7, Exxal 12 Soxylat A 25-7, glycerine list acid stearate, aliphatic acid polyethenoxy acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, glycerin fatty vinegar, polyglycerol fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester or polyoxyethylene modification.
Complexed surfactant is in order to mix the emulsification in water of organo-siloxane monomer to form stable water-based emulsion.There is emulsifying power in tensio-active agent, only otherwise hinder condensation reaction and the crosslinking reaction of organo-siloxane monomer, its kind is just had no particular limits.The consumption of water is as 100 mass parts in the step (1), and the amount of complexed surfactant is preferably 0.02～20 mass parts, more preferably 0.1～10 mass parts.If the consumption of tensio-active agent very little, the organo-siloxane monomer is failed emulsion dispersion in water, and the emulsion for preparing has bad package stability.Consumption is too many, and only can obtain small stability and improve, be uneconomic.
Complexed surfactant described in the step (1) is preferably cats product and nonionogenic tenside compound use.Preferred, described complexed surfactant is alkyl trimethyl quaternary ammonium salt and isomery polyoxyethylenated alcohol; The mass ratio of alkyl trimethyl quaternary ammonium salt and isomery polyoxyethylenated alcohol is preferably 30:70～80:20.If the ratio of alkyl trimethyl quaternary ammonium salt is less than 30, there are a large amount of responseless organo-siloxane monomers in the low conversion rate of letex polymerization in the product; If the ratio of isomery polyoxyethylenated alcohol is less than 20, the package stability of emulsion is poor, is unfavorable for the preservation of product.Described alkyl trimethyl quaternary ammonium salt is preferably octadecyl trimethyl ammonium chloride, and described isomery polyoxyethylenated alcohol is preferably isomerous tridecanol polyoxyethylene ether.
Organo-siloxane monomer described in the step (1) is preferably at least a in organic cyclopolysiloxane, hydroxy-end capped organopolysiloxane and the alkoxy end-capped organopolysiloxane.
Described organic cyclopolysiloxane is preferably the organic cyclopolysiloxane shown in the logical formula I:
Wherein, R
1, R
2Identical or different, R
1, R
2Be respectively hydrogen or 1～16 carbon atom alkyl, contain the phenyl that 1～6 carbon atom replaces; R
1, R
2Comprise alkyl, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, dodecyl; Thiazolinyl is such as vinyl and allyl group; Cycloalkyl is such as cyclopentyl, cyclohexyl, suberyl and methylcyclohexyl; Aryl is such as phenyl, naphthyl; Alkaryl is such as ortho-, meta-, p-tolyl, xylyl and ethylbenzene; Be preferably methyl, ethyl, n-propyl, sec.-propyl; Be particularly preferably methyl.N is 3～10 integer.
Preferably, described organic cyclopolysiloxane is octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxanes, 1,2,3,4-tetramethyl--1,2,3,4-tetrem thiazolinyl cyclotetrasiloxane, 1,2,3,4-tetramethyl--1,2,3,4-tetraphenyl cyclotetrasiloxane.
Described hydroxy-end capped organopolysiloxane and alkoxy end-capped organopolysiloxane are preferably the organic cyclopolysiloxane shown in the logical formula II:
Wherein, R
1, R
2Identical or different, R
1, R
2Be respectively the alkyl of hydrogen or 1～16 carbon atom, comprise alkyl, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, dodecyl; Thiazolinyl is such as vinyl and allyl group; Cycloalkyl is such as cyclopentyl, cyclohexyl, suberyl and methylcyclohexyl; Aryl is such as phenyl, naphthyl; Alkaryl is such as ortho-, meta-, p-tolyl, xylyl and ethylbenzene; Be preferably methyl, ethyl, n-propyl, sec.-propyl; Be particularly preferably methyl.R
3, R
4, R
5, R
6, R
7, R
8Identical or different, be respectively the alkyl of 1～20 carbon atom, comprise alkyl, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, dodecyl; Thiazolinyl is such as vinyl and allyl group; Cycloalkyl is such as cyclopentyl, cyclohexyl, suberyl and methylcyclohexyl; Aryl is such as phenyl, naphthyl; Alkaryl is such as ortho-, meta-, p-tolyl, xylyl and ethylbenzene; Be preferably methyl, ethyl, n-propyl, sec.-propyl; Be particularly preferably methyl.N is 1～1000 integer, is preferably 10～500, is particularly preferably 20～100.
The organo-siloxane monomer is main active reaction thing.The consumption of water is as 100 mass parts in the step (1), preferred 10～60 mass parts of the amount of organo-siloxane monomer, more preferably 20～40 mass parts.If the amount of organo-siloxane monomer very little, the performance of prepared polysiloxane emulsion can not guarantee; Measure too many meeting and cause the stability decreases of emulsion, the wild effects such as floating oil, layering occur easily.
Organo-siloxane monomer described in the step (1) is preferably octamethylcyclotetrasiloxane.
Catalyzer described in the step (2) is basic catalyst or an acidic catalyst.Described basic catalyst is preferably the basic catalysts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, salt of wormwood, yellow soda ash, Quilonum Retard, ammonium hydroxide or its aqueous solution.Described an acidic catalyst is preferably an acidic catalysts such as formic acid, acetic acid, lactic acid, propanedioic acid, fumaric acid, toxilic acid, oxyacetic acid, hydrochloric acid, Hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid.
Catalyzer is in order to promote the organo-siloxane monomer to carry out condensation reaction and crosslinking reaction and add.The consumption of water is as 100 mass parts in the step (1), preferred 0.01～10 mass parts of the amount of catalyzer, more preferably 0.03～3 mass parts.If the amount of catalyzer very little, the organo-siloxane monomer just can not react smoothly; Amount can cause the stability decreases of emulsion too much, is unfavorable for the storage of emulsion.
Cats product described in the step (2) comprises the cats products such as alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzyl alkyl-dimethyl based quaternary ammonium salt, monoalkyl quaternary ammonium salt, alkyl polyoxyethylene ylmethyl quaternary ammonium salt, N-alkyl diethanolamine salt, polyethylene polyamines salt, pyridinium salt, tetrahydroglyoxaline or morpholine.
Linking agent described in the step (2) is preferably tetramethoxy-silicane, tetraethoxysilane, Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane, methyl triacetoxysilane, phenyl triethoxysilane, vinyltriethoxysilane, β-(3,4-epoxy hexane)-triethoxyl silane, γ-(2,3-propylene oxide base) propyl trimethoxy silicane or silicon sol etc.Preferred, described linking agent is tetraethoxysilane.
Hydroxyl generation condensation reaction in linking agent hydroxyl or alkoxyl group and the polysiloxane forms silicon rubber and adds.The consumption of water is as 100 mass parts in the step (1), preferred 0.05～20 mass parts of the amount of linking agent, more preferably 0.1～10 mass parts.If the amount of linking agent very little, do not become the silicon rubber emulsion in the emulsion polymerization; Amount can cause emulsion a large amount of gels to occur too much, and so that emulsion is unstable.
Film-forming silicone emulsion of the present invention has excellent performance, can be widely used in the industrial circles such as papermaking, weaving, slurry, coating, building, leather, medicine, makeup.As can in the processing such as metal, plastics, rubber, glass, using as releasing agent; Can in the production processes such as washing composition, papermaking, paper pulp, sugaring, plating, chemical fertilizer, auxiliary agent, wastewater treatment, use as defoamer; In leather industry, as waterproofing agent for leather, leather gloss agent, fatting agent, softening agent and other auxiliary; In textile industry, as the fabric post-treatment agent, with feel and the surface property that improves fabric; In personal care industry, as the additive of hair conditioner, skin cream etc., to increase nursing efficacy.
The present invention has following advantage and effect with respect to prior art:
(1) to prepare the method steps of film-forming silicone emulsion few, simple to operate in the present invention, and cost is low, and transformation efficiency is high.
(2) the prepared film-forming silicone emulsion of the present invention does not add the metal catalysts such as tin, uranium, platinum, greatly improves the use safety of emulsion.
(3) the prepared film-forming silicone emulsion stability of the present invention is very good, and normal temperature is placed layering or breakdown of emulsion were not occured more than 3 months.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) in the 500mL glass cylinder, adds 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 109g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 80 ℃, add the 10g10wt% potassium hydroxide solution, reacted 6 hours, be cooled to 40 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 11.4g tetraethoxysilane, polyreaction 3 hours is cooled to 25 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is that 135.3 nanometers (median size is by the Brookhaven(90Plus/BI-MAS type) size distribution instrument is 25 ℃ of lower measurements), the transformation efficiency of organo-siloxane monomer is 85.0%.This emulsion non-volatile content under (referring to that 150 ℃ were heated 3 hours in 150 ℃/3 hours) heating in 150 ℃/3 hours is 33.3wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 2
(1) in the 500mL glass cylinder, adds 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 112.8g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 90 ℃, add the 10g10wt% potassium hydroxide solution, reacted 6 hours, be cooled to 40 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 7.6g tetraethoxysilane, polyreaction 3 hours is cooled to 20 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 113.6 nanometers, and the transformation efficiency of organo-siloxane monomer is 84.3%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 31.0wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 3
(1) in the 500mL glass cylinder, adds 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 116.6g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 70 ℃, add the 10g10wt% potassium hydroxide solution, reacted 6 hours, be cooled to 40 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 3.8g tetraethoxysilane, polyreaction 3 hours is cooled to 25 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 110.8 nanometers, and the transformation efficiency of organo-siloxane monomer is 82.9%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 29.3wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 4
(1) in the 500mL glass cylinder, adds 6.4g octadecyl trimethyl ammonium chloride and 12.4g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 94.3g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 80 ℃, add the 10g10wt% potassium hydroxide solution, reacted 6 hours, be cooled to 40 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 17.1g tetraethoxysilane, polyreaction 3 hours is cooled to 25 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 87.3 nanometers, and the transformation efficiency of organo-siloxane monomer is 89.9%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 35.3wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 5
(1) in the 500mL glass cylinder, adds 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 109g water dissolution, after dissolving fully, add 57.4g dimethyl siloxane mixed methylcyclosiloxane (DMC), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 80 ℃, add the 10g10wt% potassium hydroxide solution, reacted 6 hours, be cooled to 50 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 11.4g tetraethoxysilane, polyreaction 2 hours is cooled to 25 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 117.4 nanometers, and the transformation efficiency of organo-siloxane monomer is 84.0%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 32.8wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 6
(1) add 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7) in the 500mL glass cylinder, use the 109g water dissolution, after dissolving fully, adding 57.4g viscosity is 50～120mm
2The hydroxy-end capped polydimethylsiloxane of/s (DOW CORNING PMX-0156), stirring makes it to mix, and then shears (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, is formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 90 ℃, add the 10g10wt% potassium hydroxide solution, reacted 4 hours, be cooled to 50 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 11.4g tetraethoxysilane, polyreaction 3 hours is cooled to 30 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 78.6 nanometers, and the transformation efficiency of organo-siloxane monomer is 89.0%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 34.6wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 7
(1) in the 500mL glass cylinder, adds 3.4g cocounut oil alkyl polyoxyethylene ylmethyl ammonium chloride (AkzoNobel Ethoquad C/25) and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 109g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 70 ℃, add the 10g10wt% hydrochloric acid soln, reacted 5 hours, be cooled to 40 ℃, add 1.2g cocounut oil alkyl polyoxyethylene ylmethyl ammonium chloride and 11.4g tetraethoxysilane, polyreaction 3 hours is cooled to 25 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 116.3 nanometers, and the transformation efficiency of organo-siloxane monomer is 87.0%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 33.7wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 8
(1) in the 500mL glass cylinder, adds 3.4g sodium lauryl sulphate and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 109g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 80 ℃, add the 10g10wt% hydrochloric acid soln, reacted 6 hours, be cooled to 50 ℃, add 1.2g sodium lauryl sulphate and 11.4g tetraethoxysilane, polyreaction 2.5 hours is cooled to 25 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 247.5 nanometers, and the transformation efficiency of organo-siloxane monomer is 80.2%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 31.2wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 9
(1) in the 500mL glass cylinder, adds 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 109g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 90 ℃, add the 10g10wt% potassium hydroxide solution, reacted 5 hours, be cooled to 50 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 11.4g silicon sol, polyreaction 3 hours is cooled to 30 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 124.5 nanometers, and the transformation efficiency of organo-siloxane monomer is 86.3%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 29.8wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Embodiment 10
(1) in the 500mL glass cylinder, adds 3.4g octadecyl trimethyl ammonium chloride and 6.2g isomerous tridecanol polyoxyethylene ether (number of moles of ethylene oxide of adduction=7), use the 109g water dissolution, after dissolving fully, add 57.4g octamethylcyclotetrasiloxane (D4), stirring makes it to mix, then sheared (5000 rev/mins) 10 minutes in emulsification pretreatment stirrer high speed, be formed with the organic siloxane monomer pre-emulsion; The organosilane monomer pre-emulsion is transferred in the high pressure homogenizer, and homogeneous is 1 minute under the 30Mpa homogenization pressure, is formed with the organic siloxane monomer emulsion.
(2) the organo-siloxane monomer emulsion is heated to 70 ℃, add the 10g10wt% potassium hydroxide solution, reacted 6 hours, be cooled to 60 ℃, add 1.2g octadecyl trimethyl ammonium chloride and 11.4g phenyltrimethoxysila,e, polyreaction 1 hour is cooled to 20 ℃, adds in the 1.2g acetic acid to obtain film-forming silicone emulsion with emulsion to neutrality again.
The median size of this emulsion is 123.4 nanometers, and the transformation efficiency of organo-siloxane monomer is 81.7%.This emulsion non-volatile content under heating in 150 ℃/3 hours is 29.8wt%, has the non-volatile residue of film like.It is stable without separating that this emulsion kept at room temperature 3 months.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a film-forming silicone emulsion is characterized in that comprising the steps:
(1) with 0.02～20 mass parts complexed surfactant with 100 mass parts water dissolution, add again 10～60 mass parts organo-siloxane monomers, shear 1～20min with the emulsification pretreatment stirrer, homogeneous obtains the organo-siloxane monomer emulsion under 20～60Mpa again;
(2) the organo-siloxane monomer emulsion is heated to 70～90 ℃, add 0.01～10 mass parts of catalyst, reaction 4～6h, be cooled to 40～60 ℃, add again 0.5～5 mass parts cats product and 0.05～20 mass parts linking agent, reaction 1～3h is cooled to 20～30 ℃ and adds in the acetic acid and emulsion to neutrality obtains film-forming silicone emulsion.
2. the preparation method of film-forming silicone emulsion according to claim 1 is characterized in that:
Complexed surfactant described in the step (1) is at least a in cats product, anion surfactant and the nonionogenic tenside;
Organo-siloxane monomer described in the step (1) is at least a in organic cyclopolysiloxane, hydroxy-end capped organopolysiloxane and the alkoxy end-capped organopolysiloxane.
3. the preparation method of film-forming silicone emulsion according to claim 2 is characterized in that:
Described cats product comprises alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzyl alkyl-dimethyl based quaternary ammonium salt, monoalkyl quaternary ammonium salt, alkyl polyoxyethylene ylmethyl quaternary ammonium salt, N-alkyl diethanolamine salt, polyethylene polyamines salt, pyridinium salt, tetrahydroglyoxaline or morpholine;
Described anion surfactant comprises alkyl-sulphate, alkylbenzene sulfonate, soap, alkyl hydrosulfate, the Voranol EP 2001 hydrogen sulfuric acid ester, the polyoxyethylene alkyl phenyl ether hydrogen sulfuric acid ester, N-acyl group taurine, the benzene sulfonamide acid esters, the polyoxyethylene alkyl phenyl ether sulphonate, the alpha-olefin sulphonate, the alkyl naphthalene sulfonic acid ester, alkyl diphenyl base ether disulfonate, dialkyl sulfosuccinate, the sulfo-succinic acid mono alkyl ester, the Voranol EP 2001 ester, N-acyl amino hydrochlorate or alkyl phosphate;
Described ionic surfactant pack is drawn together the organopolysiloxane of isomery polyoxyethylenated alcohol, fatty acid methyl ester Soxylat A 25-7, Exxal 12 Soxylat A 25-7, glycerine list acid stearate, aliphatic acid polyethenoxy acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid ester, glycerin fatty vinegar, polyglycerol fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester or polyoxyethylene modification;
Described organic cyclopolysiloxane is the organic cyclopolysiloxane shown in the logical formula I:
Wherein, R
1, R
2Identical or different, R
1, R
2Be respectively hydrogen or 1～16 carbon atom alkyl, contain the phenyl that 1～6 carbon atom replaces; R
1, R
2Comprise alkyl, thiazolinyl, cycloalkyl, aryl and alkaryl; N is 3～10 integer;
Described hydroxy-end capped organopolysiloxane and alkoxy end-capped organopolysiloxane are the organic cyclopolysiloxane shown in the logical formula II:
Wherein, R
1, R
2Identical or different, R
1, R
2Be respectively the alkyl of hydrogen or 1～16 carbon atom, comprise alkyl, thiazolinyl, aryl, alkaryl; R
3, R
4, R
5, R
6, R
7, R
8Identical or different, be respectively the alkyl of 1～20 carbon atom, comprise alkyl, thiazolinyl, cycloalkyl, aryl, alkaryl; N is 1～1000 integer.
4. the preparation method of film-forming silicone emulsion according to claim 1 is characterized in that:
The consumption of the complexed surfactant described in the step (1) is 0.1～10 mass parts;
The consumption of the organo-siloxane monomer described in the step (1) is 20～40 mass parts.
5. the preparation method of film-forming silicone emulsion according to claim 1 is characterized in that:
Complexed surfactant described in the step (1) is cats product and nonionogenic tenside compound use;
Organo-siloxane monomer described in the step (1) is octamethylcyclotetrasiloxane.
6. the preparation method of film-forming silicone emulsion according to claim 5 is characterized in that:
Described complexed surfactant is alkyl trimethyl quaternary ammonium salt and isomery polyoxyethylenated alcohol, and the mass ratio of alkyl trimethyl quaternary ammonium salt and isomery polyoxyethylenated alcohol is 30:70～80:20.
7. the preparation method of film-forming silicone emulsion according to claim 1 is characterized in that:
Catalyzer described in the step (2) is basic catalyst or an acidic catalyst;
Cats product described in the step (2) comprises alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, benzyl alkyl-dimethyl based quaternary ammonium salt, monoalkyl quaternary ammonium salt, alkyl polyoxyethylene ylmethyl quaternary ammonium salt, N-alkyl diethanolamine salt, polyethylene polyamines salt, pyridinium salt, tetrahydroglyoxaline or morpholine;
Linking agent described in the step (2) is tetramethoxy-silicane, tetraethoxysilane, Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane, methyl triacetoxysilane, phenyl triethoxysilane, vinyltriethoxysilane, β-(3,4-epoxy hexane)-triethoxyl silane, γ-(2,3-propylene oxide base) propyl trimethoxy silicane or silicon sol.
8. the preparation method of film-forming silicone emulsion according to claim 7 is characterized in that:
Described basic catalyst is sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, salt of wormwood, yellow soda ash, Quilonum Retard, ammonium hydroxide or its aqueous solution;
Described an acidic catalyst is formic acid, acetic acid, lactic acid, propanedioic acid, fumaric acid, toxilic acid, oxyacetic acid, hydrochloric acid, Hydrogen bromide, sulfuric acid, nitric acid or phosphoric acid;
Described linking agent is tetraethoxysilane.
9. the preparation method of film-forming silicone emulsion according to claim 1 is characterized in that:
The consumption of the catalyzer described in the step (2) is 0.03～3 mass parts;
The consumption of the linking agent described in the step (2) is 0.1～10 mass parts.
10. film-forming silicone emulsion, it is characterized in that: described film-forming silicone emulsion prepares by each described preparation method of claim 1～9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100272815A CN103113824A (en) | 2013-01-18 | 2013-01-18 | Film-forming polysiloxane emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100272815A CN103113824A (en) | 2013-01-18 | 2013-01-18 | Film-forming polysiloxane emulsion and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103113824A true CN103113824A (en) | 2013-05-22 |
Family
ID=48412246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100272815A Pending CN103113824A (en) | 2013-01-18 | 2013-01-18 | Film-forming polysiloxane emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103113824A (en) |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421324A (en) * | 2013-07-31 | 2013-12-04 | 中科院广州化学有限公司 | Crosslinked polysiloxane/acrylic ester compound emulsion, and preparation method and application thereof |
| CN103755961A (en) * | 2013-12-20 | 2014-04-30 | 中科院广州化学有限公司 | Polysiloxane microemulsion, and preparation method and application thereof |
| CN103951826A (en) * | 2014-03-27 | 2014-07-30 | 中科院广州化学有限公司 | Method for preparing high molecular weight polysiloxane mini-emulsion from long-chain alkyl polyoxyethelene quaternary ammonium salt emulsifier |
| CN104086996A (en) * | 2014-06-25 | 2014-10-08 | 中科院广州化学有限公司 | Cationic silicon rubber micropowder, and preparation method and application thereof |
| CN104761722A (en) * | 2015-03-20 | 2015-07-08 | 中科院广州化学有限公司 | Cation polysiloxane Pickering emulsion, preparation method and application thereof |
| CN105879719A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Green preparation method of silicon rubber/silicon dioxide pervaporation membrane based on emulsion film forming |
| CN105879718A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Green preparation method of silicon rubber/organometallic compound pervaporation separating membrane based on membrane forming of emulsion |
| CN107746461A (en) * | 2017-10-31 | 2018-03-02 | 广州中国科学院工业技术研究院 | Cross-linking organosilicon miniemulsion and preparation method thereof, application |
| CN108192356A (en) * | 2017-12-31 | 2018-06-22 | 广州硅碳新材料有限公司 | A kind of carrier model organosilicon adhesion promoter and preparation method thereof |
| CN108359106A (en) * | 2018-03-26 | 2018-08-03 | 浙江新安化工集团股份有限公司 | A kind of preparation method of silicones microballoon lotion |
| CN109266058A (en) * | 2018-09-18 | 2019-01-25 | 湖南凯斯利新材料有限公司 | A kind of catalysis process and application method of aqueous inorganic nano paint |
| CN111116916A (en) * | 2019-12-18 | 2020-05-08 | 宁波辉宏新材料有限公司 | Method for preparing hydroxy silicone oil emulsion by emulsion polymerization of Si-OH terminated dimethyl siloxane oligomer |
| CN111286029A (en) * | 2020-03-15 | 2020-06-16 | 华中师范大学 | High-stability organic silicon emulsion and preparation method and application thereof |
| CN112080202A (en) * | 2020-09-22 | 2020-12-15 | 青岛联康油脂制品有限公司 | Water-based capsule pretreating agent and preparation method and use method thereof |
| CN114316610A (en) * | 2021-12-13 | 2022-04-12 | 南京瑞思化学技术有限公司 | Preparation method of organic silicon emulsion |
| CN114456707A (en) * | 2022-02-21 | 2022-05-10 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
| CN115028840A (en) * | 2022-04-12 | 2022-09-09 | 浙江新安化工集团股份有限公司 | Polysiloxane emulsion and preparation method and application thereof |
| CN115090827A (en) * | 2022-05-12 | 2022-09-23 | 浙江新安化工集团股份有限公司 | Mold release agent and preparation method thereof |
| CN115678424A (en) * | 2022-10-27 | 2023-02-03 | 东莞南玻太阳能玻璃有限公司 | Water-based anti-reflection coating liquid and preparation method and application thereof |
| CN116059135A (en) * | 2023-04-06 | 2023-05-05 | 山东安得医疗用品股份有限公司 | Water-blocking and bacteria-blocking skin protective agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139125A (en) * | 1996-03-07 | 1997-01-01 | 江西省科学院应用化学研究所 | Preparation of modified polhsiloxane emulsion |
| CN1513017A (en) * | 2001-05-29 | 2004-07-14 | Emulsion containing crosslinked and non-cross linked silicone polyethers | |
| JP2005306994A (en) * | 2004-04-21 | 2005-11-04 | Shin Etsu Chem Co Ltd | Silicone emulsion composition for forming coating film |
-
2013
- 2013-01-18 CN CN2013100272815A patent/CN103113824A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139125A (en) * | 1996-03-07 | 1997-01-01 | 江西省科学院应用化学研究所 | Preparation of modified polhsiloxane emulsion |
| CN1513017A (en) * | 2001-05-29 | 2004-07-14 | Emulsion containing crosslinked and non-cross linked silicone polyethers | |
| JP2005306994A (en) * | 2004-04-21 | 2005-11-04 | Shin Etsu Chem Co Ltd | Silicone emulsion composition for forming coating film |
Non-Patent Citations (1)
| Title |
|---|
| 莫建强等: "八甲基环四硅氧烷阳离子开环乳液聚合研究", 《日用化学工业》 * |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421324A (en) * | 2013-07-31 | 2013-12-04 | 中科院广州化学有限公司 | Crosslinked polysiloxane/acrylic ester compound emulsion, and preparation method and application thereof |
| CN103421324B (en) * | 2013-07-31 | 2016-01-13 | 中科院广州化学有限公司 | Cross linking polysiloxane/acrylic ester compound emulsion and preparation method thereof and application |
| CN103755961A (en) * | 2013-12-20 | 2014-04-30 | 中科院广州化学有限公司 | Polysiloxane microemulsion, and preparation method and application thereof |
| CN103951826B (en) * | 2014-03-27 | 2017-02-15 | 中科院广州化学有限公司 | Method for preparing high molecular weight polysiloxane mini-emulsion from long-chain alkyl polyoxyethelene quaternary ammonium salt emulsifier |
| CN103951826A (en) * | 2014-03-27 | 2014-07-30 | 中科院广州化学有限公司 | Method for preparing high molecular weight polysiloxane mini-emulsion from long-chain alkyl polyoxyethelene quaternary ammonium salt emulsifier |
| CN104086996A (en) * | 2014-06-25 | 2014-10-08 | 中科院广州化学有限公司 | Cationic silicon rubber micropowder, and preparation method and application thereof |
| CN105879718B (en) * | 2014-12-16 | 2019-02-22 | 江南大学 | A kind of silicon rubber based on emulsion film forming/metallo-organic compound infiltrating and vaporizing membrane environment-friendly preparation method thereof |
| CN105879719A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Green preparation method of silicon rubber/silicon dioxide pervaporation membrane based on emulsion film forming |
| CN105879718A (en) * | 2014-12-16 | 2016-08-24 | 江南大学 | Green preparation method of silicon rubber/organometallic compound pervaporation separating membrane based on membrane forming of emulsion |
| CN105879719B (en) * | 2014-12-16 | 2019-02-22 | 江南大学 | A kind of silicon rubber based on emulsion film forming/silica infiltrating and vaporizing membrane environment-friendly preparation method thereof |
| CN104761722A (en) * | 2015-03-20 | 2015-07-08 | 中科院广州化学有限公司 | Cation polysiloxane Pickering emulsion, preparation method and application thereof |
| CN107746461B (en) * | 2017-10-31 | 2020-12-01 | 广州中国科学院工业技术研究院 | Cross-linking type organic silicon miniemulsion and preparation method and application thereof |
| CN107746461A (en) * | 2017-10-31 | 2018-03-02 | 广州中国科学院工业技术研究院 | Cross-linking organosilicon miniemulsion and preparation method thereof, application |
| CN108192356A (en) * | 2017-12-31 | 2018-06-22 | 广州硅碳新材料有限公司 | A kind of carrier model organosilicon adhesion promoter and preparation method thereof |
| CN108192356B (en) * | 2017-12-31 | 2021-01-12 | 广州硅碳新材料有限公司 | Carrier type organic silicon adhesion promoter and preparation method thereof |
| CN108359106A (en) * | 2018-03-26 | 2018-08-03 | 浙江新安化工集团股份有限公司 | A kind of preparation method of silicones microballoon lotion |
| CN109266058A (en) * | 2018-09-18 | 2019-01-25 | 湖南凯斯利新材料有限公司 | A kind of catalysis process and application method of aqueous inorganic nano paint |
| CN111116916A (en) * | 2019-12-18 | 2020-05-08 | 宁波辉宏新材料有限公司 | Method for preparing hydroxy silicone oil emulsion by emulsion polymerization of Si-OH terminated dimethyl siloxane oligomer |
| CN111116916B (en) * | 2019-12-18 | 2022-06-28 | 宁波辉宏新材料有限公司 | Method for preparing hydroxyl silicone oil emulsion by using Si-OH end-capped dimethyl siloxane oligomer through emulsion polymerization |
| CN111286029A (en) * | 2020-03-15 | 2020-06-16 | 华中师范大学 | High-stability organic silicon emulsion and preparation method and application thereof |
| CN112080202A (en) * | 2020-09-22 | 2020-12-15 | 青岛联康油脂制品有限公司 | Water-based capsule pretreating agent and preparation method and use method thereof |
| CN114316610A (en) * | 2021-12-13 | 2022-04-12 | 南京瑞思化学技术有限公司 | Preparation method of organic silicon emulsion |
| CN114456707A (en) * | 2022-02-21 | 2022-05-10 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
| CN115028840A (en) * | 2022-04-12 | 2022-09-09 | 浙江新安化工集团股份有限公司 | Polysiloxane emulsion and preparation method and application thereof |
| CN115090827A (en) * | 2022-05-12 | 2022-09-23 | 浙江新安化工集团股份有限公司 | Mold release agent and preparation method thereof |
| CN115090827B (en) * | 2022-05-12 | 2023-08-15 | 浙江新安化工集团股份有限公司 | Release agent and preparation method thereof |
| CN115678424A (en) * | 2022-10-27 | 2023-02-03 | 东莞南玻太阳能玻璃有限公司 | Water-based anti-reflection coating liquid and preparation method and application thereof |
| CN115678424B (en) * | 2022-10-27 | 2023-11-17 | 东莞南玻太阳能玻璃有限公司 | Water-based anti-reflection coating liquid and preparation method and application thereof |
| CN116059135A (en) * | 2023-04-06 | 2023-05-05 | 山东安得医疗用品股份有限公司 | Water-blocking and bacteria-blocking skin protective agent and preparation method thereof |
| CN116059135B (en) * | 2023-04-06 | 2023-07-07 | 山东安得医疗用品股份有限公司 | Water-blocking and bacteria-blocking skin protective agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103113824A (en) | Film-forming polysiloxane emulsion and preparation method thereof | |
| CN103421324B (en) | Cross linking polysiloxane/acrylic ester compound emulsion and preparation method thereof and application | |
| CN101541889B (en) | Aqueous emulsions of silicone resins | |
| US5753751A (en) | Process for preparing self-curable alkenyl hydride siloxane copolymers and coating composition | |
| CN103848991B (en) | A kind of daily use chemicals silicon gel emulsion and its preparation method and application | |
| CA2314766A1 (en) | Antifoam formulation | |
| WO2016101568A1 (en) | Organic silicon composition, and preparation and use thereof | |
| CN101884852A (en) | Method for improving properties of polyether defoaming agent | |
| EP0989153A1 (en) | Emulsions containing ultrahigh viscosity silicone polymers | |
| CN102827479A (en) | Liquid silicone rubber | |
| EP2843002B1 (en) | Organopolysiloxane emulsion composition | |
| EP3178916A1 (en) | Defoaming agent for liquid detergent | |
| JP2011012264A (en) | Method for producing silicone coating and silicone molded article from photo crosslinkable silicone mixture | |
| CN107001634A (en) | The new crosslinking catalyst of silicon composition | |
| CN106414611A (en) | Addition-curable liquid silicone rubber composition | |
| CN103497339B (en) | The polydimethylsiloxane of hydroxy polyethers end-blocking and blue light emulsion thereof and blue light emulsion preparation method | |
| WO2013097167A1 (en) | Silicone surfactant, and preparation method and use thereof | |
| CN1968991A (en) | Emulsions of organopolysiloxane resins produced by emulsion polymerization | |
| CN103755961A (en) | Polysiloxane microemulsion, and preparation method and application thereof | |
| JPWO2018029966A1 (en) | Organopolysiloxane emulsion composition and resin composition | |
| CN110157198A (en) | Silicone composition and its manufacturing method | |
| CN101081931A (en) | Film-forming silicone emulsion composition | |
| CN104086996A (en) | Cationic silicon rubber micropowder, and preparation method and application thereof | |
| KR102132813B1 (en) | Method for manufacturing hydrosilyl group-containing organosilicon resin | |
| CN104031392B (en) | A kind of add-on type silica gel and its production and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130522 |