CN101230138A - Aqueous siliconiting polymer emulsion as well as preparation method and use thereof - Google Patents

Aqueous siliconiting polymer emulsion as well as preparation method and use thereof Download PDF

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CN101230138A
CN101230138A CNA2007100072283A CN200710007228A CN101230138A CN 101230138 A CN101230138 A CN 101230138A CN A2007100072283 A CNA2007100072283 A CN A2007100072283A CN 200710007228 A CN200710007228 A CN 200710007228A CN 101230138 A CN101230138 A CN 101230138A
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emulsion
alkyl
polymer
weight
silanization
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武利民
游波
黄煌
张扬
张宜荣
张勇
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Henkel AG and Co KGaA
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Priority to PCT/IB2008/000167 priority patent/WO2008090458A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/04—Homopolymers or copolymers of monomers containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen

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Abstract

The invention relates to aqueous silanized polymer emulsion and the preparation method and the application thereof. The emulsion of the invention contains a silanized polymer, a hydrolysable silanized compound, water, non-essential emulsifier and non-essential nano-silicon dioxide. By adopting the preparation method of the invention, stable aqueous silanized polymer emulsion can be prepared, the prepared aqueous silanized polymer emulsion has the solid content of smaller than or equal to 85 weight percent, especially, prepared polyorganosiloxane emulsion has the solid content of smaller than or equal to 75 weight percent, and the particle diameter of smaller than 3 micrometers, and can be laid stably at the room temperature. An elastomer can be formed through cross linking after water in the emulsion is volatilized. During the operation, the emulsion can be directly diluted through the water, and can be used for preparing coating, adhesive, sealant, printing ink, release agent, skin food, cleansing agent and so on.

Description

Aqueous siliconiting polymer emulsion and its production and application
Technical field
The present invention relates to a kind of stable Silanization polymer emulsion.More specifically, the present invention relates to a kind of aqueous siliconiting polymer emulsion, it comprises Silanization polymer; Water; Hydrolyzable silane compound; Nonessential nano silicon; With nonessential emulsifying agent.The invention still further relates to the preparation method and the application of described aqueous siliconiting polymer emulsion.Emulsion of the present invention can be used as raw material and is applied to fields such as coating, tackiness agent, seal gum, printing ink, releasing agent, skin care product, clean-out system.
Background technology
Silanization polymer, for example the end of the chain and or the polymkeric substance of the siliceous-oxyl of side chain owing to have the silicon-oxyl group that can react, can obtain cross-linked polymer with airborne water reaction self-crosslinking curing or with the solidifying agent reaction, this cross-linked polymer has excellent performance, is widely used in fields such as tackiness agent, seal gum, coating, printing ink, skin care product, clean-out system.But it is carrier with the organic solvent mostly when using, and along with the increasingly stringent to volatile organic content control, wishes the water-based emulsion of the above-mentioned polymkeric substance of preparation.
For water-insoluble polymer, a kind of method of the prior art is that normal employing " back emulsification " method prepares the aqueous polymer emulsion, promptly under high speed shear speed, the polymer dispersed that has prepared is prepared the aqueous polymer emulsion in water, emulsifying agent is adsorbed on polymkeric substance drop surface with oleophilic group, hydrophilic group stretches in the water, with electric charge repel each other or spatial masking hinder the polymer emulsion particle mutually near and coalescent again.Introduced a kind of high solids content silanization viscoelastic polymer emulsion as patent U.S.Patent Nos.6713558 and 6831128, adopted silanization polybutadiene polymers, softening agent, tensio-active agent, low molecular weight acid, water to prepare solid content more than 75%, median size aqueous polymer dispersion less than 5 μ m.But because polymer viscosity is generally higher; a large amount of emulsifying agent, monomerics or cosolvent must be added and just aqueous polymer dispersion can be obtained; because emulsifying agent or softening agent mostly are low-molecular weight compound; join the performance that can influence cross-linked polymer in the polymkeric substance in a large number; the adding of cosolvent has then increased content of volatile organic compound in the emulsion; be unfavorable for environment protection; and the aqueous polymer emulsion latex particle out-of-shape that adopts these class methods to obtain; broad particle distribution; be easy to generate and be separated, stability of emulsion is poor.
Another kind method is to form by " self-emulsifying " after introducing hydrophilic radical on the polymer molecule.Introduced a kind of water dispersion that has silanization Resins, epoxy as patent U.S.Patent No.5466729, this silanization Resins, epoxy is to adopt the silane and the Resins, epoxy reaction that contain hydrolysable group and secondary amine group to obtain, under high speed shear speed, directly be prepared into aqueous dispersions, can be used for metallic paint and glass binder.Dispersed phase particles is small-sized in the aqueous polymer emulsion of chemic modified method preparation, be about tens to the hundreds of nanometer, but preparation process is wayward, product cost is higher, and, product performance there is certain influence because the molecular structure of polymkeric substance changes in the aqueous polymer emulsion of this class methods preparation of employing.
Patent CN1140186A then introduced a kind of can be by the crosslinked high viscosity polysiloxane dispersion of condensation, addition or free radical reaction.Adding tensio-active agent and a spot of water are prepared into the gel of solid content greater than 75 weight % in the Silanization polymer.This polysiloxane aqueous dispersion can add a certain amount of silane and be cured, and the silane of adding plays solidifying agent and linking agent.Be different from emulsion, the high-solid level gel needs mobile fluidic occasion to use at some.
Patent CN200510133811.X has then introduced a kind of stable Silanization polymer emulsion and preparation method thereof, utilize the reactive group on nano-silica surface hydroxyl and the Silanization polymer molecular chain to interact, by the back emulsifying process, only need to add a small amount of or can prepare stable Silanization polymer emulsion without tensio-active agent, the adding of nano silicon also can improve the physical strength behind the emulsion film forming.But some Silanization polymer does not wish to add inorganic particulate in emulsion in preparation emulsion process.
Therefore, still need the Silanization polymer emulsion that provides stable.
The present invention adopts silane compound to act on the stable Silanization polymer of preparation separately, or can add nano silicon according to needs and act synergistically with silane compound and make.Utilize the electric charge and the bonding action of the silicon hydroxyl that above-mentioned polymkeric substance and silane or polymkeric substance and silane, nano silicon form in water to obtain stable Silanization polymer emulsion.Silane compound separately or silane compound and nano silicon act synergistically on and play tensio-active agent and function of stabilizer in the emulsion, in the solidification process that dries out, play the effect of solidifying agent and linking agent again gradually.
Summary of the invention
Therefore, the invention provides a kind of aqueous siliconiting polymer emulsion, it only needs to use a small amount of or can form stable emulsion without tensio-active agent, and moisture evaporation solidifies the cross-linking elasticity film that the back forms excellent performance.Described emulsion can be a kind of low VOC (VOC) emulsion.
The present invention also provides the method for simple, the versatile and flexible and described stabilized aqueous Silanization polymer emulsion of maneuverable preparation of a kind of technology.
The present invention also provides a kind of method of utilizing silane compound to prepare the stabilized aqueous Silanization polymer emulsion.
The present invention also provides a kind of method of utilizing silane compound and nano silicon synergy to prepare the stabilized aqueous Silanization polymer emulsion.
The present invention also provides a kind of nano silicon is dispersed in method in the Silanization polymer emulsion.
The present invention also provides described stable Silanization polymer emulsion to be applied to fields such as coating, tackiness agent, seal gum, printing ink, releasing agent, skin care product, clean-out system as raw material.
Description of drawings:
Fig. 1 is the sem photograph (SEM) that embodiment 1 contains the cross-linked polymer sample in cross section that obtains behind the Silanization polymer emulsion moisture evaporation of 7 weight % silane compounds, amplifies 20000 times, and the cross-linked polymer that as can be seen from the figure obtains is uniform film.
Fig. 2 contains the sem photograph (SEM) of the cross-linked polymer sample in cross section that obtains behind the Silanization polymer emulsion moisture evaporation of 10 weight % silane compounds and 8 weight % nano silicons for embodiment 2, amplify 20000 times, as can be seen from the figure nano silicon is dispersed in the cross-linked polymer.
Fig. 3 is the size distribution figure that embodiment 3 contains the Silanization polymer emulsion of 15 weight % silane compounds, and as can be seen from the figure, the median size of Silanization polymer emulsion is 340nm, and size distribution is narrower.
Fig. 4 adds the schematic flow sheet of silane thermal decomposition process synchronously for the present invention prepares stabilized aqueous Silanization polymer emulsion method A--, and wherein Silanization polymer at first mixes with other component, and then adds silane compound and finish emulsion process.
Fig. 5 adds the schematic flow sheet of silane thermal decomposition process in advance for the present invention prepares stabilized aqueous Silanization polymer emulsion method B--, and wherein silane compound and Silanization polymer are pre-mixed together, finishes emulsion process after having added other component again.
Fig. 6 prepares the schematic flow sheet that adds silane thermal decomposition process behind the stabilized aqueous Silanization polymer emulsion method C--for the present invention, and wherein Silanization polymer and other component are carried out pre-emulsification earlier, add silane compound at last to finish emulsion process.
Fig. 7 is for describing the synoptic diagram that the present invention prepares stabilized aqueous Silanization polymer emulsion process.
Detailed Description Of The Invention
It has been stable that the term that this paper relates to " Pickering emulsifying agent " refers in the emulsion preparation Emulsion effect and the solid minuteness particle that adds. Referring to
Pickering, S.U.J.Chem.Soc.Chem.Commun, 1907,91,2001; And B.P. Binks and is Langmuir S.0.Lumsdon, 2001,17,4540-4547.
The term that this paper relates to " polysiloxanes " is silicon-oxygen (Si-O) unit of a class to repeat Be main chain, directly link the polymer of organic group on the silicon atom.
The term that this paper relates to " Silanization polymer " refer to terminal and or side chain contain silane The polymer of functionalized group.
The term that this paper relates to " silanization polysiloxanes " refers to the silicon-oxygen of polymer to repeat (Si-O) unit is main chain, directly links organic group on the silicon atom, simultaneously the end of the chain and or side One base polymer of the siliceous oxyl of chain (≡ Si-O-R).
The term that this paper relates to " rear emulsification " divides after referring to prepare polymer with common process earlier again Be dispersed in the method for preparing the aqueous polymer emulsion in the water.
The term that this paper relates to " stable emulsion " is meant that emulsion is thermodynamically stable dispersion state, can stablize down in room temperature (25 ℃) and place more than 1 month, and range estimation does not have and is separated, and during emulsion keep its reactive behavior.
The term that this paper relates to " low VOC (VOC) " is meant that the content of volatile organic compounds in the emulsion is below 1 weight %.
The inventor finds, adopt have on the molecule-oxyl (OR, R is alkyl, and is as follows, except as otherwise noted), acyloxy (
Figure A20071000722800101
) silane compound or the alkyl cyclosiloxane of ketoxime base (O-N=CRR '), in water, can hydrolysis form silanol, or the further condensation of silanol forms silane oligomer or polysiloxane (see figure 7).The silanol that forms and/or the silicon hydroxyl on polysiloxane surface and or-oxyl and Silanization polymer molecular chain on reactive group for example silicon-oxyl (≡ Si-O-R) and/or silicon hydroxyl (≡ Si-OH) react, by the back emulsifying process, make a large amount of silicon hydroxyls of Silanization polymer latex particle surface adsorption, both can play stabilization to the polymer emulsion particle, can suppress the self-crosslinking of Silanization polymer in water again, in system, only need to add to add tensio-active agent on a small quantity or not, need not to add organic solvent, can obtain stable Silanization polymer emulsion.
The inventor also finds, in the Silanization polymer emulsion preparation process, also can add nano silicon simultaneously, utilizes nano silicon as the Pickering emulsifying agent, and the polymer emulsion particle is played further stabilization.
The inventor has finished the present invention based on above discovery.
Silanization polymer emulsion
Specifically, the invention provides a kind of aqueous siliconiting polymer emulsion, it comprises: (1) Silanization polymer; (2) water; (3) hydrolyzable silane compound; (4) nonessential nano silicon; (5) nonessential emulsifying agent.
The solid content of aqueous siliconiting polymer emulsion described in the present invention is preferably 20-85 weight %, more preferably 30-75 weight %; Especially, when Silanization polymer was the silanization polysiloxane, solid content was preferably 20-75 weight %, more preferably 30-75 weight %.The Silanization polymer emulsion of preparation can also thin up, is diluted to required degree according to the needs of concrete application.By the adjusting solid content, emulsifying agent consumption, emulsion adjuvant consumption etc., emulsion of the present invention can be prepared into emulsion oil-in-water or water-in-oil emulsion.
The average latex particle size of emulsion of the present invention, is measured by laser particle diameter tester preferably less than 1 micron preferably less than 3 microns.
The pH value of emulsion described in the present invention is preferably 4-10, more preferably 5-9.
Silanization polymer emulsion of the present invention can be cured as a kind of crosslinked elastomerics by moisture evaporation.The linking agent effect of film-forming polymer has been played in the adding of silane compound simultaneously in the emulsion.The adding of nano silicon can be played the effect that strengthens crosslinked back film-forming polymer physical strength in the emulsion.
Silanization polymer
Described Silanization polymer is preferably with the functionalized polymkeric substance of at least one silicon-oxyl (preferred silane oxygen base), and more preferably described Silanization polymer is the polymkeric substance that contains two silicon-oxyls.
More specifically, described Silanization polymer includes but not limited to: silicon-oxyl polyethers, silicon-oxyl polyester, silicon-oxyl polysiloxane, silicon-oxyl polyacrylic ester, silicon-oxyl polycarbonate, silicon-oxyl urethane, silicon-oxyl polymeric amide, silicon-oxyl polyimide, silicon-oxyl polyolefine and arbitrary combination thereof.
The limiting examples of described Silanization polymer comprises: methyldiethoxysilane polyoxyethylene ether, vinyl-dimethyl TMOS polyoxytrimethylene ether, triethoxysilicane alkanisation polydimethylsiloxane, vinyl-dimethyl TMOS polydimethylsiloxane, methylethyl methoxy silane polydimethylsiloxane, vinyl-dimethyl TMOS PSI, vinyl-dimethyl TMOS vibrin, vinyl diethoxy silane polyester, the methyl dimethoxysilane polyacrylate resin, the methyldiethoxysilane polycarbonate, methyl diacetoxy silylated polyurethane, triethoxysilicane alkanisation urethane, propyl group dimethoxy silanization polyimide, with methyldiethoxysilane polyethylene etc.Described Silanization polymer can be according to for example U.S.Patent Nos.5,300,608; 3,971,751; 4,374,237; 6,803,412; 5,986,014; 6,420,492; With disclosed general method preparation among the CN1100809C.
The viscosity of Silanization polymer of the present invention is preferably 0.01-10000Pa.s (25 ℃), more preferably 0.05-2000Pa.s (25 ℃).
The weight-average molecular weight of Silanization polymer of the present invention (Mw) is preferably 1000-200000, more preferably 5000-100000.Molecular weight distributing index (Mw/Mn) is preferably 1-3.By gel permeation chromatography.
In emulsion of the present invention, the content of described Silanization polymer is preferably the 20-84 weight % of emulsion total amount, 30-74 weight % more preferably, especially, when Silanization polymer is the silanization polysiloxane, the silanization polysiloxane is the 20-74 weight % of emulsion total amount, more preferably 30-74 weight %.
Hydrolyzable silane compound
Described hydrolyzable silane compound is to contain the silicoorganic compound that hydrolyzable forms the silicon oh group, and molecular formula is Y nSiX 4-n, wherein X is selected from: the C1-C16-oxyl (OR), the C1-C16 acyloxy (
Figure A20071000722800121
), C3-C16 ketoxime base (O-N=CRR ') and arbitrary combination thereof, Y is selected from: hydrogen (H), hydroxyl (OH), C1-C16 alkyl (R), amino (NH 2), C1-C16 hydroxylamine base (NHR ,-NRR '), C1-C16 brine alkyl (RZ, Z are halogen atom), C1-C16 mercapto alkyl (RSH), the C1-C16 hydroxyl alkyl (ROH), C1-C16 ammonia alkyl (RNH), C3-C16 epoxy alkyl ( ), C4-C16 acryloyl-oxy alkyl (CH 2=CRCOOR '-), (alkyl) phosphoric acid ester alkyl (R of C3-C16 3PO 4) and arbitrary combination etc., R and R ' are identical or different, are the alkyl of hydrogen or certain carbon number range, and its carbon number or carbon number sum satisfy the carbon number range of above-mentioned group, and n is the integer of 0-3;
Described hydrolyzable silane compound also can be for containing the organosilicon ring compound that hydrolyzable forms the group of silicon hydroxyl
Figure A20071000722800123
Wherein R and R ' are respectively the alkyl of hydrogen or C1-C10, and m is the integer of 3-10.
Above-described alkyl is preferably alkyl.
More specifically, described silane compound is selected from silicol, alkyl-oxyl silane, alkyl cyclosiloxane, amino-oxyl silane, brine alkyl-oxyl silane, mercapto alkyl-oxyl silane, hydroxyl alkyl-oxyl silane, ammonia alkyl-oxyl silane, epoxy alkyl-oxyl silane, (methyl) acryloyl-oxy alkyl-oxyl silane, alkyl acyloxy silane, alkyl ketoximinosilanes, (alkyl) phosphoric acid ester hydrocarbyl si lanes and arbitrary combination thereof.
The limiting examples of described silane compound comprises: γ-chloropropyl triethoxysilane, the chloropropyl methyldiethoxysilane, the bromopropyl methyldiethoxysilane, tetraethoxysilane, four n-butoxy silane, methyldiethoxysilane, methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane, dimethyldiethoxysilane, propyl trimethoxy silicane, allyltriethoxysilane, methylethyl dimethoxy silane, phenyl triethoxysilane, phenyl tripropoxy silane, phenyl three isopropoxy silane, phenyl three n-butoxy silane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, the aminomethyl phenyl diethoxy silane, the ethylphenyl diethoxy silane, decamethylcyclopentaandoxane, diethyl phosphoric acid ester ethyl triethoxysilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-An Bingjisanyiyangjiguiwan, γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane, γ-(β-aminoethyl)-aminopropyl trimethoxysilane, γ-(beta-hydroxyethyl aminoethyl)-aminopropyl methyl dimethoxysilane, N, N-diethyl-γ-amine propyl trimethoxy silicane, N-methyl-3-aminopropyl trimethoxysilane, 3-cyclohexyl-aminopropyl methyl dimethoxysilane, γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl-triethoxysilicane, γ-glycidyl ether oxygen base propyl group methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy methyl dimethoxysilane, 3-urea groups propyl trimethoxy silicane, gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, anilinomethyl triethoxysilane, the hydroxyethyl dimethyl phenyl silane, the dihydroxypropyl dimethylsilane, the tetrem acyloxy silane, methyl triacetoxysilane, methyl three propionyloxy silane, the triphenyl acetoxysilane, the vinyl tributanoximo silane, methyl tri acetylacetonate oximino silane, chloropropyl tributanoximo silane etc.
In emulsion of the present invention, the content of described hydrolyzable silane compound is preferably the 1-20 weight % of emulsion total amount, more preferably 1-15 weight %.
Water
Be preferably the 15-78 weight % of emulsion total amount, more preferably 20-68 weight % at water-content described in the emulsion of the present invention.Especially, when Silanization polymer was the silanization polysiloxane, the water yield was the 25-78 weight % of emulsion total amount, more preferably 25-68 weight %.
Emulsifying agent
The emulsifying agent that is suitable among the present invention can be any conventional emulsifier that the Silanization polymer in the aqueous siliconiting polymer emulsion is played stabilization.Preferably, described emulsifying agent is selected from anion surfactant, nonionogenic tenside and arbitrary combination thereof.More preferably, to be selected from the HLB value be nonionogenic tenside and the arbitrary combination thereof of 3-50 for the anion surfactant of 3-50, HLB value to described emulsifying agent.
More specifically, emulsifying agent of the present invention preferably from the alkyl-sulphate of the alkylbenzene sulfonate of C8-C22 alkylsulfonate, C8-C22, C8-C22, phosphate ester salt, polyether surfactant for example C8-C22 poly alkyl alcohol ethylene oxide ether and C8-22 alkylphenol polyoxyethylene ether, C8-C22 fatty amide-polyoxyethylene, contain emulsified Silanization polymer segmental wetting ability block polymer and arbitrary combination thereof.The limiting examples of described emulsifying agent comprises: sodium laurylsulfonate (HLB=11-12), sodium cetanesulfonate (HLB=12.1), Sodium dodecylbenzene sulfonate (HLB=14.8), Witco 1298 Soft Acid ammonium (HLB=14.8), Witco 1298 Soft Acid isopropylamine (HLB=11.7), sodium octyl sulfate (HLB=42.0), the Witco 1298 Soft Acid triethanolamine salt, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, polyoxyethylene nonyl phenyl ethene (4) ether sodium sulfate, polyoxyethylene nonyl phenyl ethene (4) ether ammonium sulfate, sodium octyl sulfate (HLB=42), Sodium Lauryl Sulphate BP/USP (HLB=42.0), Texapon Special (HLB=42.0), lauryl sulfate monoethanolamine (HLB=42.0), lauryl polyoxyethylene ether (2) ammonium sulfate (HLB=42.0), C12-15 alkyl polyethylene oxides (1-4) ether ammonium sulfate (StandapolAP-60, Witcolate AE-3, HLB=42.0), lauryl polyoxyethylene (4) ether phosphate sodium (HLB=42.0), tridecyl polyoxyethylene (6) ether phosphate (HLB=42.0), oil base polyoxyethylene (3) ether phosphate (HLB=42.0), polyoxyethylene nonyl phenyl ethene (9) ether phosphate sodium (HLB=42.0), binonylphenol polyoxyethylene (10) ether phosphate (HLB=42.0), sulfo-succinic acid diisobutyl ester sodium (HLB=42.0), sulfo-succinic acid two natrium valericums (HLB=42.0), sulfo-succinic acid lauryl disodium (HLB=42.0), sulfo-succinic acid two cyclohexyl sodium (HLB=42.0), the two tridecane ester sodium (HLB=42.0) of sulfo-succinic acid, sulfo-succinic acid lauryl polyoxyethylene (1-4) ether-ether disodium (Alconate L-3 for example, HLB=42.0), sulfo-succinic acid oleylamide polyoxyethylene (2) ether-ether disodium (HLB=42.0), sulfo-succinic acid polyoxyethylene nonyl phenyl ethene (10) ether-ether disodium (HLB=42.0), oil base acid amides disodium sulfosuccinate (HLB=42.0), single N-coco group acid amides disodium sulfosuccinate (HLB=42.0), lauryl polyoxyethylene (2) ether (HLB=9.5), lauryl polyoxyethylene (7) ether (HLB=11.0), lauryl polyoxyethylene (12) ether (HLB=14.8), lauryl polyoxyethylene (15) ether (HLB=15.5), lauryl polyoxyethylene (23) ether (HLB=16.9), C9-11 alkyl polyethylene oxides (6) ether (Neodol 91-6 for example, HLB=12.5), C12-14 alkyl polyethylene oxides (7) ether (Imbentin-AG/124/070 for example, Marlipal, HLB=12.0), C12-15 alkyl polyethylene oxides (12) ether (Alkasurf LA-12 for example, Tergitol 25-L-12, HLB=14.4), tridecyl polyoxyethylene (6) ether (HLB=11.4), tridecyl polyoxyethylene (10) ether (HLB=13.8), tridecyl polyoxyethylene (15) ether (HLB=15.5), hexadecyl polyoxyethylene (15) ether (HLB=15.5), hexadecyl polyoxyethylene (20) ether (HLB=17.0), hexadecyl polyoxyethylene (30) ether (HLB=19.5), different hexadecyl polyoxyethylene (20) ether (HLB=15.7), 16/octadecyl polyoxyethylene (12) ether (Incropol CS-12 for example, HLB=12.0), 16/octadecyl polyoxyethylene (30) ether (Incropol CS-30 for example, HLB=16.7), stearyl polyoxyethylene (20) ether (HLB=15.3), stearyl polyoxyethylene (40) ether (HLB=17.4), oleyl alcohol polyoxyethylene (20) ether (HLB=15.5), polyoxyethylene nonyl phenyl ethene (9) ether (HLB=13.5), polyoxyethylene nonyl phenyl ethene (10) ether (HLB=14.0), polyoxyethylene nonyl phenyl ethene (12) ether (HLB=14.6), polyoxyethylene nonyl phenyl ethene (30) ether (HLB=17.5), polyoxyethylene nonyl phenyl ethene (40) ether (HLB=18.0), polyoxyethylene nonyl phenyl ethene (70) ether (HLB=18.7), polyoxyethylene nonyl phenyl ethene (5) ether (HLB=10.0), polyoxyethylene nonyl phenyl ethene (8) ether (HLB=12.4), polyoxyethylene nonyl phenyl ethene (10) ether (HLB=13.3), polyoxyethylene nonyl phenyl ethene (30) ether (HLB=18.1), polyoxyethylene nonyl phenyl ethene (100) ether (HLB=19.1), coco amine polyoxyethylene (15) ether (HLB=15.7), ethylenediamine polyoxyethylene polyoxytrimethylene polyoxyethylene block polyether (HLB=12-18), two lauric acid ethylene glycol (8) esters (HLB=10.8), two lauric acid ethylene glycol (20) esters (HLB=10.8), stearic acid ethylene glycol (40) ester (HLB=16.9), stearic acid ethylene glycol (100) ester (HLB=18.5), polyoxyethylene (20) Zerol (HLB=13.1), polyoxyethylene (5) sorbitan monooleate (HLB=10.0)
In the emulsion of the present invention, described emulsifying agent consumption is preferably the 0-4 weight % of emulsion total amount, more preferably 0-2 weight %.
Nano silicon
In emulsion of the present invention, described nano silicon preferable particle size is 10-300nm, and more preferably particle diameter is 10-200nm.The BET specific surface area of described nano silicon is preferably 30m 2/ g to 400m 2/ g.
In the emulsion of the present invention, described nano silicon is the hydroxyl nano silicon in surface, hydrophilic nano silicon-dioxide for example, and its non-limiting example comprises nano silica powder, precipitator method nano silicon for example, fumed nano silicon-dioxide; Or the nano silicon water-sol.The limiting examples of described hydrophilic nano silicon-dioxide comprises: for example, and the nano silicon water-sol Nyacol that German EKA chemical company produces
Figure A20071000722800161
9950, Nyacol
Figure A20071000722800162
2040, Nyacol
Figure A20071000722800163
830C, Nyacol
Figure A20071000722800164
2034DI, Bindzil
Figure A20071000722800165
CC40, Bindzil
Figure A20071000722800166
CC30; The nano silicon water-sol CH83-120 of Jiangsu Jiangyin Guobang Chemical Co., Ltd., CH83-125, CH83-130; The nano silicon water-sol GS-15 of Zhejiang Province Yuda Chemical Co., Ltd, GS-20, GS-25, GS-30, GS-40, GS-301, GS-302, GS-303, GS-304, GS-305; The precipitator method nano silicon Ultrasil that Germany Degussa company produces 360, S320DS, S325C; The fumed nano silicon-dioxide Aerosil that Germany Degussa company produces
Figure A20071000722800168
R816, Aerosil
Figure A20071000722800169
130, Aerosil 150, Aerosil
Figure A200710007228001611
200, Aerosil
Figure A200710007228001612
300, Aerosil
Figure A200710007228001613
380; The fumed nano silicon-dioxide CAB-O-SIL that U.S. Cabot company produces
Figure A200710007228001614
M-5, CAB-O-SIL
Figure A200710007228001615
H-5, CAB-O-SIL
Figure A200710007228001616
HS-5; The fumed nano silicon-dioxide N20 that Germany Wacker company produces; The fumed nano silicon-dioxide QS20LS that produces with Japanese TOKUYAMA company, QS102, QS40, DM-10 etc.
In the emulsion of the present invention, the consumption of described nano silicon is preferably the 0-20 weight % of emulsion total amount, more preferably 0-10 weight %.
Emulsion adjuvant
(for example wish to increase the wetting ability of polymkeric substance, the denseness of emulsion, the stability of emulsion etc. time) if desired, emulsion of the present invention can also comprise various suitable emulsion adjuvants, as long as they bring adverse influence to emulsion of the present invention indistinctively.The non-limiting example of described emulsion adjuvant comprises wetting ability auxiliary agent, thickening material, stablizer, pH regulator agent and combination arbitrarily thereof.
More specifically, wherein said wetting ability auxiliary agent is preferably from water-soluble high-molecular compound, more preferably from Polyvinylpyrolidone (PVP), polyoxyethylene glycol, polyvinyl alcohol, polyvinyl methyl ether and combination arbitrarily thereof.
Described thickening material is preferably from water-based thickener, more preferably from Walocel MT 20.000PV, Natvosol, wilkinite, activated clay and combination arbitrarily thereof.
The stablizer of described emulsion comprises thermo-stabilizer, freeze-thaw stabiliser.
Described PH conditioning agent comprises low-molecular-weight acid, alkali, salt and combination arbitrarily thereof.More preferably from hydrochloric acid, sulfuric acid, nitric acid, ammoniacal liquor, volatile salt, yellow soda ash, ammonium chloride and combination arbitrarily thereof.
The consumption of emulsion adjuvant is preferably the 0-5 weight % of emulsion total amount, more preferably the 0-3 weight % of emulsion total amount.
Other nonessential component
Emulsion of the present invention can also comprise other optional component, as long as they and consumption thereof bring adverse influence to emulsion of the present invention indistinctively.Non-limiting example comprises color stuffing, defoamer, flow agent, antiaging agent, tackifier, uv-absorbing agent etc. and combination arbitrarily thereof.
More specifically, wherein said optional component is conventional pigment in the products such as coating, tackiness agent, seal gum, makeup, filler (comprising the inorganic substance to system inert nano particle form of the present invention, for example nano silicon, nano titanium oxide, nano aluminium oxide, nano-sized iron oxide, nano zircite, nano zine oxide, nano-calcium carbonate etc.), defoamer, flow agent, antiaging agent, tackifier, uv-absorbing agent etc. and combination arbitrarily thereof.
The preparation method of aqueous siliconiting polymer emulsion
The present invention has adopted specific silane compound to prepare the stabilized aqueous Silanization polymer emulsion, and can prepare in several ways, simple, the versatile and flexible and operation easily of technology.
In the preparation method's of a Silanization polymer emulsion of the present invention embodiment A (this paper abbreviates " adding silane thermal decomposition process synchronously " as), described method comprises following steps (referring to Fig. 4):
(1) Silanization polymer, nonessential emulsifying agent and nonessential emulsion adjuvant blend form component AI;
(2) not necessarily, silane compound, water and nonessential nano silicon are mixed, form component AII;
(3) under agitation condition, in the component AI that step (1) obtains, add the component AII that obtains in the step (2), or add silane compound, water and nonessential nano silicon synchronously respectively, carry out back emulsification; With
(4) not necessarily, after back emulsification was finished, regulating emulsion pH was 4-10, to prepare described Silanization polymer emulsion.
In this preparation method, control each amounts of components to prepare stable oil-in-water-type or water-in-oil-type Silanization polymer emulsion.Total amount in emulsion, preferred each amounts of components of control is: Silanization polymer 20-84 weight %, especially, when Silanization polymer is the silanization polysiloxane, the silanization polysiloxane is the 20-74 weight % of emulsion total amount, more preferably 30-74 weight %; Silane compound 1-20 weight %; Water 15-78 weight %, especially, when Silanization polymer is the silanization polysiloxane, water 25-78 weight %, more preferably 25-68 weight %; Emulsifying agent 0-4 weight %; Nano silicon 0-20 weight %; With emulsion adjuvant 0-5 weight %.
In step (1), preferably under 20-95 ℃ temperature, in super mixer, preferably under the 1000-3000rpm rotating speed, preferably stir and came blend Silanization polymer, nonessential emulsifying agent and nonessential emulsion adjuvant in 1-30 minute.
In step (2), preferably under 0-95 ℃ temperature, in mixing tank, preferably under the 100-3000rpm rotating speed, preferably stirred 1-30 minute, form the even component AII that comprises silane compound and water and nonessential nano silicon.
In step (3), hierarchy of control temperature is preferably under 20-95 ℃ temperature, in super mixer, under preferred 2000-5000rpm rotating speed, preferably added the described even component AII that comprises silane compound and water and nonessential nano silicon uniformly that is pre-mixed at 0.05-3 hour; More preferably, added the back and continued hierarchy of control temperature preferably 20-95 ℃ temperature, and preferably under the 1000-5000rpm rotating speed preferred the continuation stirred 0.05-2 hour, with emulsion process after finishing.
Also can be that hierarchy of control temperature preferably under 20-95 ℃ temperature, under the 2000-5000rpm rotating speed, preferably at 0.05-3 hour, is added silane compound, water and nonessential nano silicon respectively synchronously in step (3).More preferably, add the back and continue hierarchy of control temperature preferably 20-95 ℃ temperature, and preferably under the 1000-5000rpm rotating speed preferred the continuation stirred 0.05-2 hour, with emulsion process after finishing.
In step (4), preferably adopt the pH regulator agent to regulate the pH value of Silanization polymer emulsion, the non-limiting example of preferred pH regulator agent comprises low-molecular-weight acid, alkali, salt and combination arbitrarily thereof.The limiting examples of the pH regulator agent that is suitable for comprises hydrochloric acid, sulfuric acid, nitric acid, ammoniacal liquor, volatile salt, yellow soda ash, ammonium chloride etc.The consumption of pH regulator agent is an amount of to required ph value of emulsion.
This preparation method A preferably is applicable to and (for example: γ-An Bingjisanyiyangjiguiwan adopts water-soluble silicon hydride compounds or its oligomer, γ-(β-aminoethyl) aminopropyl trimethoxysilane, diethyl phosphoric acid ester ethyl triethoxysilane) Silanization polymer emulsion preparation process.
In another embodiment B of the preparation method of Silanization polymer emulsion of the present invention (this paper abbreviates " adding silane thermal decomposition process in advance " as), described method comprises following steps (referring to Fig. 5):
(1) Silanization polymer, silane compound, nonessential emulsifying agent and nonessential emulsion adjuvant blend are formed B component I;
(2) water and nonessential nano silicon blend are formed B component II;
(3) under agitation condition, in the miscellany BI that step (1) obtains, add the B component II that obtains in the step (2), to carry out back emulsification; With
(4) not necessarily, after emulsification was finished, the adjusting ph value of emulsion was 4-10, to prepare described Silanization polymer emulsion.
In this preparation method, control each amounts of components according to each amounts of components scope same as described above, to prepare stable oil-in-water-type or water-in-oil-type Silanization polymer emulsion.
In step (1), preferably under 20-95 ℃ temperature, in super mixer, preferably under the 1000-3000rpm rotating speed, preferably stir and came blend Silanization polymer, silane compound, nonessential emulsifying agent and nonessential emulsion adjuvant in 1-30 minute, to form B component I.
In step (2), preferably under 20-95 ℃ temperature, in super mixer, preferably under the 1000-3000rpm rotating speed, preferably stirred 1-30 minute and/or preferred ultra-sonic dispersion 2-20 minute, form the even B component II that comprises water and nonessential nano silicon.
In step (3), preferably under 20-95 ℃ temperature, under the 2000-5000rpm rotating speed, preferably added the B component II that comprises water and nonessential nano silicon uniformly that is pre-mixed of step (2) at 0.05-3 hour.More preferably, add the back and continue hierarchy of control temperature, and preferably under the 1000-5000rpm rotating speed, continue to stir 0.05-2 hour, with emulsion process after finishing preferably at 20-95 ℃.
In step (4), preferably adopt aforesaid pH regulator agent to regulate the pH value of Silanization polymer emulsion.The consumption of pH regulator agent is an amount of to required ph value of emulsion.
This preparation method B preferably is applicable to and adopts silane compound () the Silanization polymer emulsion preparation process for example: Union carbide A-162, aminomethyl phenyl dimethoxy silane that has better consistency with polymkeric substance.
In another embodiment C of the preparation method of Silanization polymer emulsion of the present invention (this paper abbreviates " silane thermal decomposition process is added in the back " as), described method comprises following steps (referring to Fig. 6):
(1) Silanization polymer, nonessential emulsifying agent and nonessential emulsion adjuvant are carried out blend, form component CI;
(2) under agitation condition, add water and nonessential nano silicon among the component CI that in step (1), obtains, form component CII;
(3) under agitation condition, add silane compound among the component CII that in step (2), obtains to carry out back emulsification; With
(4) not necessarily, after back emulsification was finished, regulating emulsion pH was 4-10, to prepare described Silanization polymer emulsion.
In this preparation method, control each amounts of components according to each amounts of components scope same as described above, to prepare stable oil-in-water-type or water-in-oil-type Silanization polymer emulsion.
In step (1), preferably under 20-95 ℃ temperature, in super mixer, preferably under the 1000-3000rpm rotating speed, preferably stir 1-30 minute with Silanization polymer, nonessential emulsifying agent and nonessential emulsion adjuvant mixing formation component CI.
In step (2), hierarchy of control temperature is preferably at 20-95 ℃, under preferred 2000-5000rpm rotating speed, preferably adds being pre-mixed uniform water and nonessential nano silicon to form component CII at 0.05-3 hour in CI in super mixer.More preferably, add the back and continue hierarchy of control temperature, and preferably under the 1000-5000rpm rotating speed, preferably continue to stir 0.05～2 hour preferably at 20-95 ℃.
In step (3), hierarchy of control temperature preferably under 20-95 ℃ temperature, under preferred 2000-5000rpm rotating speed, was preferably added silane compound at 0.05-3 hour in super mixer.More preferably, add the back and continue hierarchy of control temperature preferably 20-95 ℃ temperature, and preferably under the 1000-5000rpm rotating speed preferred the continuation stirred 0.05～2 hour, with emulsion process after finishing.
In step (4), preferably adopt aforesaid pH regulator agent to regulate the pH value of Silanization polymer emulsion.The consumption of pH regulator agent is an amount of to required ph value of emulsion.
This preparation method C is widely applicable for the Silanization polymer emulsion preparation process that adopts silane compound, can simplify the process of adding silane compound, the problem that the silicon hydroxyl of minimizing in the emulsion preparation process is cross-linked with each other is particularly useful for existing the emulsion preparation process of complicated treatment step such as heating.
Adopt above-mentioned three kinds of methods all can prepare aqueous siliconiting polymer emulsion.
The preparation process of emulsion of the present invention does not have special requirement to pressure, as long as it can not influence the preparation process of emulsion of the present invention significantly unfriendly.Other processing condition of not mentioning in the preparation process of the invention described above emulsion but may relating to can be with the preparation condition of conventional Silanization polymer emulsion.For example referring to U.S.Patent Nos.6713558 and 6831128.
Aqueous siliconiting polymer emulsion that the present invention proposes and preparation method thereof has the following advantages:
(1) owing to has-oxyl on the hydrolyzable silane compound molecule, acyloxy, ketoxime base etc., in water, can hydrolysis form silanol or polysiloxane, the silicon hydroxyl on surface and or-oxyl and Silanization polymer molecular chain on the silicon-oxyl and or the interaction of silicon hydroxyl, by the back emulsifying process, make the polymer emulsion particle surface adsorb a large amount of silicon hydroxyls, both can play stabilization, can suppress the self-crosslinking of Silanization polymer in water again the polymer emulsion particle.Silane plays tensio-active agent and function of stabilizer in emulsion, play solidifying agent and linking agent when moisture evaporation again.Only need in the whole system to add on a small quantity or need not add tensio-active agent nor need to add organic solvent, can obtain stable Silanization polymer emulsion.
(2) in the emulsion preparation process, allow to add simultaneously nano silicon, utilize nano silicon the polymer emulsion particle to be played further stabilization as the Pickering emulsifying agent.
(3) adopt the inventive method, also nano silicon can be dispersed in the Silanization polymer, nano silicon need not surface modification and directly adds in the Silanization polymer, and good with the Silanization polymer consistency, the adding of nano silicon has strengthened the physical strength of cross-linked elastomer.
(4) Zhi Bei Silanization polymer emulsion solid content≤85 weight %, especially, emulsion solid content when Silanization polymer is the silanization polysiloxane≤75 weight %, preferred 20-75 weight %, and median size at room temperature can be stablized and place more than one month less than 3 μ m.During use directly water be diluted to required degree easily.
(5) Silanization polymer emulsion of the present invention can be cured as a kind of crosslinked elastomerics by moisture evaporation, and its satisfactory mechanical property is particularly useful for preparing coating, tackiness agent and seal gum.
(6) employing that proposes of the present invention preparation method that adds described silane compound has synchronous interpolation silane thermal decomposition process, adds silane thermal decomposition process in advance, silane thermal decomposition process is added in the back, three kinds of methods all can prepare the stabilized aqueous Silanization polymer emulsion, simple, the versatile and flexible and operation easily of technology.
The application of emulsion of the present invention
The stable low VOC silanes fluidized polymer emulsion of the present invention's preparation, can be used as the raw material of coating, tackiness agent, seal gum, printing ink, releasing agent, skin care product, clean-out system etc., and can be used for the said products according to the conventional application method of Silanization polymer emulsion.This emulsion can directly be diluted with water to required degree according to concrete purposes in use.
Unless otherwise, all per-cents used herein and ratio all by weight, each components contents is all in the gross weight of emulsion in the emulsion.
The publication that this paper quotes is incorporated herein by reference for all purposes.
Embodiment
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Below among each embodiment each step of preparation emulsion all under normal pressure, carry out, temperature is a normal temperature, unless otherwise.
The Silanization polymer emulsion performance characterization that the present invention makes is as follows:
Polymer viscosity by the rotary viscometer of the NDJ-1A of Chinese Shen De Technology Dev Company Ltd. 25 ℃ ± 1 ℃ mensuration.
Polymericular weight and distribution thereof are measured by the Waters Breeze 1515 efficient gel permeation chromatographs of U.S. Waters company.
The BET specific surface area of nano silicon adopts ASAP 2010 analysers to measure nitrogen absorption when 77K, and adopts Barrett-Emmett-Teller (BET) method to calculate acquisition.
The emulsion median size is measured by the laser particle diameter tester of the Coulter N4Plus of U.S. Beckman company.
Polymkeric substance pattern after crosslinked is observed by the XL30 scanning electron microscope (SEM) of Philips company and is obtained.
Polymkeric substance tensile property after crosslinked, shearing resistance are measured by the DXLL-10000 electronics pulling experiment machine of Shanghai chemical, and sample is pressed the long 20mm of ASTM-D412 standard fabrication, draw speed 50mm/min.
Polymkeric substance shore hardness after crosslinked is measured by the TH-200 Shore durometer of Tianjin Time Inc. of Time Incorporation.
Each test is all carried out under envrionment conditions, except as otherwise noted.
Embodiment 1:
Aqueous siliconiting polymer emulsion prescription 1 (method B)
Form consumption (gram)
Vinyl three ('beta '-methoxy oxyethyl group) silane 7.0
The end capped polydimethylsiloxane 33.0 of vinyl diethoxy silane
Water 57.0
Lauryl polyoxyethylene (2) ether ammonium sulfate 2.0
Hexadecyl polyoxyethylene (30) ether 1.0
Polyoxyethylene (5) sorbitan monooleate 0.5
In the high speed dispersion still, (weight-average molecular weight 12000 is referring to U.S.Patent No.3,971,751 to add the end capped polydimethylsiloxane of 33.0 gram vinyl diethoxy silanes.Silante terminated being meant described in this embodiment and following examples all used described Silante terminated at two ends of polymer chain), 7.0 gram vinyl three ('beta '-methoxy oxyethyl group) silane, 2.0 gram lauryl polyoxyethylene ether (2) ammonium sulfate, 1.0 gram hexadecyl polyoxyethylene (30) ethers, 0.5 gram polyoxyethylene (5) sorbitan monooleate, the 2000rpm rotating speed stirs and mixed in 10 minutes under the room temperature; Under the 3000rpm rotating speed, controlled temperature 30-40 ℃, Dropwise 5 7.0 gram water at the uniform velocity in 2 hours; After dripping off, under room temperature, 2000rpm rotating speed, continue to stir 0.5 hour, can obtain aqueous siliconiting polymer emulsion.
The aqueous siliconiting polymer emulsion solid content of preparation is 39 weight %, emulsion particle median size 580nm, and the aqueous siliconiting polymer emulsion adhering glass that adopts present embodiment to prepare, shearing resistance is 2.5MPa.Silane compound addition 7 weight %, emulsion at room temperature can be stablized and places more than half a year, but thin up during use.
Embodiment 2:
Aqueous siliconiting polymer emulsion prescription 2 (method B)
Form consumption (gram)
Isobutyl-triethoxyl silane 10.0
The 50 weight % nano silicon water-sols 16.0
The end capped polydimethylsiloxane 59.0 of triethoxyl silane
Sodium lauryl sulphate 0.5
Rhodia?CO436 0.5
Rhodia?CA897 0.5
Water 14.0
10 weight % hydrochloric acid are to pH=8
In the high speed dispersion still, add the end capped polydimethylsiloxane of 59.0 gram triethoxyl silanes (weight-average molecular weight 60000, Henkel Kommanditgesellschaft Auf Aktien, the Dusseldorf, Germany, referring to U.S.Patent No.5,300,608), 10.0 gram isobutyl-triethoxyl silane, 0.5 gram sodium lauryl sulphate, 0.5 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company) and 0.5 gram Rhodia CA897 (nonionogenic tenside, polyoxyethylene (40) nonyl phenolic ether, Rhodia company), 2000rpm rotating speed stirring at room temperature mixed in 10 minutes; Under the 3000rpm rotating speed, controlled temperature 50-60 ℃, at the uniform velocity drip 14.0 gram water and 16.0 grams, the 50 weight % nano silicon water-sol (Nyacol in 2 hours 9950, EKA chemical company, median size 100nm) mixed solution; After dripping off, keep 50-60 ℃ of temperature, under the 2000rpm rotating speed, continue to stir 0.5 hour; Add 10 weight % hydrochloric acid,, can obtain aqueous siliconiting polymer emulsion to pH=8.
The aqueous siliconiting polymer emulsion solid content of preparation is 74 weight %, emulsion particle median size 1200nm, and the aqueous siliconiting polymer emulsion of employing present embodiment preparation is drying and forming-film at room temperature, and the shore hardness of filming is 35.Silane compound addition 10 weight %, nanometer titanium dioxide silicone content 8 weight %, emulsion at room temperature can be stablized and places more than one month, but thin up during use.
Embodiment 3:
Aqueous siliconiting polymer emulsion prescription 3 (method A)
Form consumption (gram)
Ten diformazan basic rings, six siloxanes 2.0
Methyldiethoxysilane 13.0
The end capped urethane 35.0 of methyl dimethoxysilane
ICI?Span?20 1.0
ICI?Brij?97 0.8
ICI?Brij?30 0.2
Polyoxyethylene glycol 8,000 2.0
Water 46.0
In Scattered Kettle, it is stand-by to put into minim pipette after adding 2.0 grams ten diformazan basic rings six siloxanes, 13.0 gram methyldiethoxysilane and 46.0 gram water at room temperature mix; In the high speed dispersion still, add the end capped urethane of 35.0 gram methyl dimethoxysilanes (weight-average molecular weight 2200, referring to U.S.Patent No.4,374,237), 1.0 gram ICI Span, 20 (ICI company tensio-active agents), 0.8 gram ICI Brij, 97 (ICI company tensio-active agents), 0.2 gram ICI Brij30 (ICI company tensio-active agent) and 2.0 gram polyoxyethylene glycol 8000, stirring mixed in 30 minutes under 3000rpm rotating speed, room temperature; Under the 3000rpm rotating speed, in 2 hours, at the uniform velocity drip above-mentioned silane mixture liquid under the room temperature; Drip off and under the 3000rpm rotating speed, continue under the room temperature of back to stir 0.5 hour, can obtain aqueous siliconiting polymer emulsion.
The aqueous siliconiting polymer emulsion solid content of preparation is 49 weight %, emulsion particle median size 340nm, and the bonding aluminium flake of aqueous siliconiting polymer emulsion that adopts present embodiment to prepare, shearing resistance is 3.1MPa.Silane compound addition 15 weight %, emulsion at room temperature can be stablized and places more than half a year, but thin up during use.
Embodiment 4:
Aqueous siliconiting polymer emulsion prescription 4 (method A)
Form consumption (gram)
The 30 weight % nano silicon water-sols 10.0
Vinyltriethoxysilane 2.0
The end capped polyoxytrimethylene ether 50.0 of methyl dimethoxysilane
Sulfo-succinic acid lauryl polyoxyethylene (1-4) ether-ether disodium 0.2
Sodium cetanesulfonate 0.2
Lauryl polyoxyethylene (2) ether 0.1
Polyoxyethylene nonyl phenyl ethene (30) ether 0.2
Water 37.0
2 weight % nitric acid are to pH=6
In Scattered Kettle, add 10.0 grams, the 30 weight % nano silicon water-sol (Nyacol
Figure A20071000722800271
2040, German EKA chemical company, median size 20nm), that 2.0 gram vinyltriethoxysilanes and 37.0 gram water are put into minim pipette in mixed at room temperature after evenly is stand-by; In the high speed dispersion still, add the end capped polyoxytrimethylene ether of 50.0 gram methyl dimethoxysilanes (the viscosity 12Pa.s under 25 ℃ of temperature, referring to U.S.Patent No.3,971,751), 0.2 gram sulfo-succinic acid lauryl polyoxyethylene (1-4) ether-ether disodium, 0.2 gram sodium cetanesulfonate, 0.1 gram lauryl polyoxyethylene (2) ether and 0.2 gram polyoxyethylene nonyl phenyl ethene (30) ether, 60-80 ℃, under the 3000rpm rotating speed, stir and mixed in 10 minutes; Under the 4000rpm rotating speed, controlled temperature 60-80 ℃, at the uniform velocity drip the uniform mixture of the above-mentioned nano silicon water-sol, silane and water in 2 hours; Drip off the back and keep 60-80 ℃, under the 3000rpm rotating speed, continue again to stir 1 hour; Add 2 weight % salpeter solutions to pH=6, can obtain aqueous siliconiting polymer emulsion.
The aqueous siliconiting polymer emulsion solid content of preparation is 55 weight %, emulsion particle median size 900nm, silane compound addition 2 weight %, nanometer titanium dioxide silicone content 3 weight %, emulsion at room temperature can be stablized and places more than one month, but thin up during use.
Embodiment 5:
Aqueous siliconiting polymer emulsion prescription 5 (method B)
Form consumption (gram)
γ-glycidyl ether oxygen base propyl trimethoxy silicane 5.0
Fumed nano silica 1 .0
The end capped polyester 30.0 of vinyl diethoxy silane
Triton X-305 (70 weight %) 0.2
Triton?X-100 0.3
Water 64.0
In Scattered Kettle, add 1.0 gram fumed nano silicon-dioxide (CAB-O-SIL
Figure A20071000722800281
M-5, particle size range 200-300nm, Cabot company, Massachusetts, United States), 64.0 gram water, high speed dispersion is 15 minutes under 80-95 ℃, 3000rpm rotating speed, ultra-sonic dispersion formed the nano silicon aqueous dispersions in 10 minutes again, it is stand-by to put into minim pipette; In the high speed dispersion still, add 5.0 gram γ-glycidyl ether oxygen base propyl trimethoxy silicanes, 30.0 (polyester is a neopentyl glycol to the end capped polyester of gram vinyl diethoxy silane, hexanodioic acid, the polycondensate of Tetra hydro Phthalic anhydride, the end capped polyester viscosity of vinyl diethoxy silane 23Pa.s under 25 ℃ of temperature, weight-average molecular weight 4000, referring to U.S.Patent No.6,803,412), 0.2 gram Triton X-305 (70 weight %) (nonionogenic tenside, HLB=17.3, nonylphenol ethoxylate, Dow Chemical company tensio-active agent) and the Triton X-100 (nonionogenic tenside of 0.3 gram Dow Chemical company, HLB=13.4, nonyl phenol ethoxylate, Dow Chemical company tensio-active agent), at 80-95 ℃, under the 2000rpm rotating speed, stir and mixed in 30 minutes; Under the 2500rpm rotating speed, controlled temperature 80-95 ℃, in 1 hour, at the uniform velocity drip the nano silicon aqeous suspension; After dripping off, controlled temperature 80-95 continues to stir 0.5 hour under the 3000rpm rotating speed, can obtain aqueous siliconiting polymer emulsion.
The aqueous siliconiting polymer emulsion solid content of preparation is 35 weight %, emulsion particle median size 1900nm, silane compound addition 5 weight %, nanometer titanium dioxide silicone content 1 weight %, emulsion at room temperature can be stablized and places more than one month, but thin up during use.
Embodiment 6:
Aqueous siliconiting polymer emulsion prescription 6 (method A)
Form consumption (gram)
Dimethyldiethoxysilane 10.0
Vinyl three ('beta '-methoxy oxyethyl group) silane 10.0
The PSI 50.0 that the ethyl dimethoxy is Silante terminated
Sodium dodecylbenzene sulfonate 0.3
Polyvinylpyrolidone (PVP) 1.0
Water 29.0
In Scattered Kettle, at room temperature add 10.0 gram dimethyldiethoxysilanes, 10.0 gram vinyl three ('beta '-methoxy oxyethyl group) silane and 29.0 gram water, obtain the uniform mixture of silane compound and water after the mixing, it is stand-by to put into minim pipette; In the high speed dispersion still, add Silante terminated PSI (the viscosity 90000mm under 25 ℃ of temperature of 50.0 gram ethyl dimethoxys 2/ s, weight-average molecular weight 100000, referring to U.S.Patent No.5,300,608), 0.3 gram Sodium dodecylbenzene sulfonate and 1.0 gram Polyvinylpyrolidone (PVP) (trade mark K30,98 weight %, the homopolymer of vinyl pyrrolidone, weight-average molecular weight 44000-54000), under the 3000rpm rotating speed, stir under the room temperature and mixed in 30 minutes; Under the 4000rpm rotating speed, at the uniform velocity drip the uniform mixture of above-mentioned silane and water at room temperature 2 hours; At room temperature under the 3000rpm rotating speed, continue to stir after dripping off to obtain aqueous siliconiting polymer emulsion in 1 hour.
The aqueous siliconiting polymer emulsion solid content of preparation is 61 weight %, emulsion particle median size 400nm, and silane compound addition 20 weight % can stablize under the emulsion room temperature and place more than half a year, but thin up during use.
Embodiment 7:
Aqueous siliconiting polymer emulsion prescription 7 (method B)
Form consumption (gram)
Precipitator method nano silicon 15.0
N-octyl triethoxyl silane 2.0
Propyl-triethoxysilicane 3.0
The end capped polyacrylic ester 40.0 of methyldiethoxysilane
Sulfo-succinic acid two natrium valericums 0.2
Polyoxyethylene nonyl phenyl ethene (9) ether 0.8
Water 39.0
1 weight % ammoniacal liquor is to pH=8
In Scattered Kettle, add 15.0 gram precipitator method nano silicon (Ultrasil
Figure A20071000722800301
360, specific surface area 50m 2/ g, tap density 220g/l, Degussa company), 39.0 gram water, high speed dispersion is 20 minutes under 90-95 ℃, 3000rpm rotating speed, ultra-sonic dispersion formed the nano silicon aqueous dispersions in 5 minutes to put into minim pipette stand-by again; In the high speed dispersion still, add the end capped polyacrylic ester of 40.0 gram methyldiethoxysilane (weight-average molecular weight 110000, referring to U.S.Patent Nos.5,986,014 and 6,420,492), 2.0 gram n-octyl triethoxyl silanes, 3.0 gram propyl-triethoxysilicanes, 0.2 gram sulfo-succinic acid two natrium valericums and 0.8 gram polyoxyethylene nonyl phenyl ethene (9) ether, the 3000rpm rotating speed stirs down and mixed in 30 minutes under the room temperature; Under the 4000rpm rotating speed, controlled temperature 90-95 ℃, at the uniform velocity drip above-mentioned nano silicon aqueous dispersions in 1 hour; Drip off the back and keep 90-95 ℃ of temperature, under the 3000rpm rotating speed, continue to stir 1 hour; Add 1 weight % ammoniacal liquor to pH=8, can obtain aqueous siliconiting polymer emulsion.
The aqueous siliconiting polymer emulsion solid content of preparation is 59 weight %, emulsion particle median size 2670nm, silane compound addition 5 weight %, nanometer titanium dioxide silicone content 15 weight %, emulsion at room temperature can be stablized and places more than three months, but thin up during use.
Embodiment 8:
Aqueous siliconiting polymer emulsion prescription 8 (method A)
Form consumption (gram)
Chloropropyl methyldiethoxysilane 1.0
N-hexyl Trimethoxy silane 1.0
The end capped polydimethylsiloxane 40.0 of vinyl-dimethyl TMOS
Activated clay thickening material 2.0
Water 55.0
In Scattered Kettle, add 1.0 gram chloropropyl methyldiethoxysilane, 1.0 gram n-hexyl Trimethoxy silanes and 55.0 gram water, 50-65 ℃ of ultra-sonic dispersion 10 minutes, it was stand-by to put into minim pipette; In the high speed dispersion still, add the end capped polydimethylsiloxane of 40.0 gram vinyl-dimethyl TMOSs (weight-average molecular weight 12000, Henkel Kommanditgesellschaft Auf Aktien, the Dusseldorf, Germany is referring to U.S.Patent No.5,300,608) and 2.0 gram activated clay thickening materials, stir with the 3000rpm rotating speed under the room temperature and mixed in 30 minutes; Under the 4000rpm rotating speed, controlled temperature 50-65 ℃, at the uniform velocity drip the uniform mixture of silane compound and water in 2 hours; Drip off the back and keep 50-65 ℃ of temperature, under the 3000rpm rotating speed, continue to stir half an hour, can obtain aqueous siliconiting polymer emulsion.
The aqueous siliconiting polymer emulsion solid content of preparation is 44 weight %, emulsion particle median size 2570nm, and silane compound addition 2 weight %, emulsion at room temperature can be stablized and places more than half a year, but thin up during use.
Embodiment 9:
Aqueous siliconiting polymer emulsion prescription 9 (method C)
Form consumption (gram)
The end capped polyoxytrimethylene ether 47.2 of methyl dimethoxysilane
Rhodia?CO436 1.1
Rhodia?CA897 1.0
Fumed nano silicon-dioxide 4.1
Ethylene glycol 2.0
γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane 5.2
Deionized water 40.0
In the 250ml beaker, take by weighing deionized water 40.0 grams, add fumed nano silicon-dioxide (Cabot H-5 does not carry out surface treatment, 300 ± 25 meters of specific surface areas 2/ gram, Shanghai good fortune Xiang chemical industry company limited) 4.1g, be uniformly dispersed in 15 minutes at 40-50 ℃ of ultra-sonic dispersion, it is stand-by to put into minim pipette.In the 250ml beaker, add the end capped polyoxytrimethylene ether of 47.2g methyl dimethoxysilane (the dynamic viscosity 8000mPa.s under 25 ℃ of temperature, Henkel Kommanditgesellschaft Auf Aktien, the Dusseldorf, Germany), 1.1 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company), 1.0 gram Rhodia CA897 (nonionogenic tenside, polyoxyethylene (40) nonyl phenolic ether, Rhodia company) and 2.0 gram ethylene glycol (AR, Shanghai Ling Feng chemical reagent company limited), at room temperature following stirring of 1500rpm rotating speed mixed in 10-20 minute; Under the 3000rpm rotating speed, controlled temperature is not higher than 90 ℃, at the uniform velocity drips the uniform dispersion liquid of above-mentioned ultra-sonic dispersion in 30 minutes to 1 hour; After dripping off, keep temperature not to be higher than 90 ℃, under the 3000rpm rotating speed, continue to stir 0.5 hour; Add 5.2 gram γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilanes, Nanjing dawn chemistry company limited), stir instrument Speedmixer with high speed shear TM(FlacktekInc) stir three times at 3000rpm * 10s, can obtain aqueous siliconiting polymer emulsion.
The gained emulsion solid content is 60 weight %, Silanization polymer content 47 weight %, silane compound addition 5 weight %, nanometer titanium dioxide silicone content 4 weight %.Emulsion is at room temperature placed 3 months emulsions and kept stable, keeps steady in 60 ℃ of placement 5 Tian Bao and decides, and is stable with 3000rpm maintenance in centrifugal 30 minutes at whizzer, places the maintenance of one day recovery normal temperature (25 ℃) at-30 ℃ and stablizes; Be substrate bonding with aluminium air set after 17 days shearing resistance be 0.75Mpa.But thin up when this emulsion is used.
Embodiment 10:
Aqueous siliconiting polymer emulsion prescription 10 (method C)
Form consumption (gram)
The end capped polyoxytrimethylene ether 44.2 of methyl dimethoxysilane
Rhodia?CO436 2.1
Rhodia?CA897 1.0
Fumed nano silicon-dioxide 4.0
Ethylene glycol 1.0
Cetomacrogol 1000 0 2.0
Glycidoxy-propyltrimethoxy silane 4.6
Deionized water 40.2
In the 250ml beaker, take by weighing deionized water 40.2 grams, add fumed nano silicon-dioxide (Cabot
Figure A20071000722800331
H-5 does not carry out surface treatment, 300 ± 25 meters of specific surface areas 2/ gram, Shanghai good fortune Xiang chemical industry company limited) 4.0g, be uniformly dispersed in 15 minutes at 40-50 ℃ of ultra-sonic dispersion, it is stand-by to put into minim pipette.In the 250ml beaker, add the end capped polyoxytrimethylene ether of 44.2g methyl dimethoxysilane (the dynamic viscosity 8000mPa.s under 25 ℃ of temperature, Henkel Kommanditgesellschaft Auf Aktien, the Dusseldorf, Germany), 2.1 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company), 1.0 gram RhodiaCA897 (nonionogenic tenside, polyoxyethylene (40) nonyl phenolic ether, Rhodia company), 1.0 gram ethylene glycol (AR, Shanghai Ling Feng chemical reagent company limited) and 2.0 cetomacrogol 1000s 0 (China (medicine) Shanghai chemical reagent company limited) at room temperature following stirring of 1500rpm rotating speed mixed in 10-20 minute; Under the 3000rpm rotating speed, controlled temperature is not higher than 90 ℃, at the uniform velocity drips the good dispersion liquid of above-mentioned ultra-sonic dispersion in 30 minutes to 1 hour; After dripping off, keep temperature not to be higher than 90 ℃, under the 3000rpm rotating speed, continue to stir 0.5 hour; Add 4.6 gram glycidoxy-propyltrimethoxy silanes (the precious chemical industry of Hangzhou silicon company limited), stir instrument Speedmixer with high speed shear TM(Flacktek Inc.) stirs three times at 3000rpm * 10s, can obtain aqueous siliconiting polymer emulsion.
The gained emulsion solid content is 59 weight %, Silanization polymer content 44 weight %, silane compound addition 5 weight %, nanometer titanium dioxide silicone content 4 weight %; The emulsion particle median size is 439nm.Emulsion is placed in room temperature and is kept stable more than 3 months, places 5 Tian Bao at 60 ℃ and keeps steady surely, keeps stable after centrifugal 30 minutes with 3000rpm at whizzer, and place at-30 ℃ and recovered normal temperature (25 ℃) in one day and keep stable, but thin up during use.
Embodiment 11:
Aqueous siliconiting polymer emulsion prescription 11 (method C)
Form consumption (gram)
The end capped polydimethylsiloxane 45.1 of vinyl-dimethyl TMOS
Rhodia?CO436 1.0
Rhodia?CA897 1.0
Fumed nano silicon-dioxide 4.2
Ethylene glycol 1.1
Cetomacrogol 1000 0 1.0
Union carbide A-162 4.3
Deionized water 40.2
In the 250ml beaker, take by weighing deionized water 40.2g, add fumed nano silicon-dioxide (Cabot H-5 does not carry out surface treatment, 300 ± 25 meters of specific surface areas 2/ gram, Shanghai good fortune Xiang chemical industry company limited) 4.2g, be uniformly dispersed in 15 minutes at 40-50 ℃ of ultra-sonic dispersion, it is stand-by to put into minim pipette.In the 250ml beaker, add the end capped polydimethylsiloxane of 45.1g vinyl-dimethyl oxygen base, (weight-average molecular weight 60000, Henkel Kommanditgesellschaft Auf Aktien, the Dusseldorf, Germany), 1.0 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company) and 1.0 gram Rhodia CA897 (nonionogenic tensides, polyoxyethylene (40) nonyl phenolic ether, Rhodia company), 1.1 gram ethylene glycol (AR, Shanghai Ling Feng chemical reagent company limited), with 1.0g cetomacrogol 1000 0 (China (medicine) Shanghai chemical reagent company limited), at room temperature the 1500rpm rotating speed stirs down and mixed in 10-20 minute; Under the 3000rpm rotating speed, controlled temperature is not higher than 90 ℃, drips the good dispersion liquid of above-mentioned ultra-sonic dispersion in 30 minutes to 1 hour; After dripping off, keep temperature not to be higher than 90 ℃, under the 3000rpm rotating speed, continue to stir 0.5 hour; Add 4.3 gram Union carbide A-162s (Zhangjiagang Cathay China flourish new chemical materials company limited), stir instrument Speedmixer with high speed shear TM(Flacktek Inc) stirs three times at 3000rpm * 10s, can obtain aqueous siliconiting polymer emulsion.
The gained emulsion solid content is 57 weight %, Silanization polymer content 45 weight %, silane compound addition 4 weight %, nanometer titanium dioxide silicone content 4 weight %.Emulsion is at room temperature placed more than 3 months and to be kept stable, places 5 Tian Bao at 60 ℃ and keeps steady surely, keeps stable at whizzer in centrifugal 30 minutes with 3000rpm, and room temperature is placed and recorded median size after 14 days is 927nm, but thin up during use.
Embodiment 12:
Aqueous siliconiting polymer emulsion prescription 12 (method A)
Form consumption (gram)
The end capped polydimethylsiloxane 41.0 of vinyl-dimethyl TMOS
Rhodia?CO436 1.0
Rhodia?CA897 1.0
γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane 4.1
Tetraethoxysilane 1.1
Deionized water 50.0
In the 250ml beaker, take by weighing deionized water 50.0g, add γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane (Nanjing dawn chemistry company limited) 4.1g and tetraethoxysilane (WD-932, Wuhan University) 1.1 grams stir instrument Speedmixer with high speed shear TM(Flacktek Inc) stirs at 3000rpm * 30s and is uniformly dispersed for three times, and it is stand-by to put into minim pipette.In the 250ml beaker, add the end capped polydimethylsiloxane of 41.0g vinyl-dimethyl TMOS (weight-average molecular weight 12000, Henkel Co., Ltd), 1.0 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company) and 1.0 gram Rhodia CA897 (nonionogenic tenside, polyoxyethylene (40) nonyl phenolic ethers, Rhodia company), at room temperature following stirring of 1500rpm rotating speed mixed in 10-20 minute; Under the 3000rpm rotating speed, controlled temperature is not higher than 90 ℃, drips above-mentioned γ-(β-aminoethyl)-aminopropyl methyl dimethoxysilane/tetraethoxysilane aqueous solution in 30 minutes to 1 hour; After dripping off, keep temperature not to be higher than 90 ℃, under the 3000rpm rotating speed, continue to stir 0.5 hour; Can obtain aqueous siliconiting polymer emulsion.
The gained emulsion solid content is 48 weight %, Silanization polymer content 40 weight %, silane compound addition 5 weight %.Emulsion is at room temperature placed and is kept stable more than 3 months, and it is fixed to keep steady in 60 ℃ of placement 5 Tian Bao.
Embodiment 13
Aqueous siliconiting polymer emulsion prescription 13 (method C)
Form consumption (gram)
Hydroxy-end capped polydimethylsiloxane 39.5
Rhodia?CO436 0.4
Rhodia?CA897 0.4
Fumed nano silicon-dioxide 5.8
Cetomacrogol 1000 0 1.0
Union carbide A-162 10.0
Deionized water 65.6
In the 250ml beaker, take by weighing deionized water 65.6g, add fumed nano silicon-dioxide (Cabot
Figure A20071000722800361
H-5 does not carry out surface treatment, 300 ± 25 meters of specific surface areas 2/ gram, Shanghai good fortune Xiang chemical industry company limited) 5.8g, be uniformly dispersed in 15 minutes at 40-50 ℃ of ultra-sonic dispersion, it is stand-by to put into minim pipette.In the 250ml beaker, add hydroxy-end capped polydimethylsiloxane (the dynamic viscosity 2000cst under 25 ℃ of temperature of 39.5g, DC3-0136, Dow Corning Corporation), 0.4 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company), 0.4 gram Rhodia CA897 (nonionogenic tenside, polyoxyethylene (40) nonyl phenolic ether, Rhodia company), 1.0 gram cetomacrogol 1000s, 0 (AR, China (medicine) Shanghai chemical reagent company limited), at room temperature stirring mixed in 10-20 minute under the 1500rpm rotating speed; Under the 3000rpm rotating speed, controlled temperature is not higher than 90 ℃, drips the good dispersion liquid of above-mentioned ultra-sonic dispersion in 30 minutes to 1 hour; After dripping off, keep temperature not to be higher than 90 ℃, under the 3000rpm rotating speed, continue to stir 0.5 hour; Add 10.0 gram Union carbide A-162s (Zhangjiagang Cathay China flourish new chemical materials company limited), stir instrument Speedmixer with high speed shear TM(Flacktek Inc) stirs three times at 3000rpm * 10s, can obtain aqueous siliconiting polymer emulsion.
The gained emulsion solid content is 43 weight %, Silanization polymer content 32 weight %, silane compound addition 8 weight %, nanometer titanium dioxide silicone content 5 weight %.Emulsion is at room temperature placed more than 3 months and to be kept stable, 60 ℃ place 5 Tian Bao keep steady fixed, but thin up during use.
Embodiment 14
Aqueous siliconiting polymer emulsion prescription 14 (method B)
Form consumption (gram)
The end capped polydimethylsiloxane 10.1 of vinyl-dimethyl TMOS
Rhodia?CO436 1.0
Rhodia?CA897 1.1
Ethylene glycol 2.0
Methyltrimethoxy silane 6.0
Deionized water 80.4
Take by weighing deionized water 80.4g in the 250ml beaker, it is stand-by to put into minim pipette.In the 250ml beaker, add the end capped polydimethylsiloxane of 10.1 gram vinyl-dimethyl TMOSs (weight-average molecular weight 12000, Henkel Co., Ltd), 1.0 gram Rhodia CO436 (anion surfactant, polyoxyethylene (4) alkyl phend ether sulfate, Rhodia company), 1.1 gram Rhodia CA897 (nonionogenic tenside, polyoxyethylene (40) nonyl phenolic ether, Rhodia company), 2.0 gram ethylene glycol (AR, Chemical Reagent Co., Ltd., Sinopharm Group) and 6.0 gram methyltrimethoxy silanes (Hangzhou silicon treasured chemical industry company limited) at room temperature 1500rpm rotating speed stir down and mixed in 10-20 minute; Under the 3000rpm rotating speed, controlled temperature is not higher than 90 ℃, at the uniform velocity drips above-mentioned deionized water in 30 minutes to 1 hour; After dripping off, keep temperature not to be higher than 90 ℃, under the 3000rpm rotating speed, continue to stir 0.5 hour, can obtain aqueous siliconiting polymer emulsion.
The gained emulsion solid content is 18 weight %, Silanization polymer content 10 weight %, silane compound addition 6 weight %.Emulsion is at room temperature placed more than 3 months and to be kept stable, but thin up during use.

Claims (26)

1. aqueous siliconiting polymer emulsion, it comprises:
1) Silanization polymer;
2) water;
3) hydrolyzable silane compound;
4) nonessential nano silicon; With
5) nonessential emulsifying agent.
2. the emulsion of claim 1, wherein said Silanization polymer is for the functionalized polymkeric substance of at least one silicon-oxyl.
3. the emulsion of claim 2, wherein said Silanization polymer is selected from: silicon-oxyl polyethers, silicon-oxyl polyester, silicon-oxyl polyacrylic ester, silicon-oxyl polycarbonate, silicon-oxyl urethane, silicon-oxyl polymeric amide, silicon-oxyl polyimide, silicon-oxyl polyolefine, silicon-oxyl polysiloxane and arbitrary combination thereof.
4. the emulsion of claim 1, the viscosity of wherein said polymkeric substance is 0.01-10000Pa.s at 25 ℃.
5. the emulsion of claim 1, the weight-average molecular weight of wherein said polymkeric substance is 1000-200000, molecular weight distributing index is 1-3, is recorded by the gel permeation chromatography method.
6. the emulsion of claim 1, the content of wherein said Silanization polymer is the 20-84 weight % of emulsion total amount, and wherein said Silanization polymer when being the silanization polysiloxane its content be the 20-74 weight % of emulsion total amount.
7. the emulsion of claim 1, the wherein said water yield is the 15-78 weight % of emulsion total amount, and wherein said Silanization polymer is when being the silanization polysiloxane, the described water yield is the 25-78 weight % of emulsion total amount.
8. the emulsion of claim 1, the molecular formula of wherein said hydrolyzable silane compound is Y nSiX 4-nOr
Figure A2007100072280002C1
R wherein, R ' is identical or different, alkyl for hydrogen or C1-C10, m is the integer of 3-10, wherein X is selected from C1-C16-oxyl, C1-C16 acyloxy, C3-C16 ketoxime base and arbitrary combination thereof, Y is selected from hydrogen, hydroxyl, C1-C16 alkyl, amino, C1-C16 hydroxylamine base, C1-C16 brine alkyl, C1-C16 mercapto alkyl, C1-C16 hydroxyl alkyl, C1-C16 ammonia alkyl, C3-C16 epoxy alkyl, C4-C16 acryloyl-oxy alkyl, C3-C16 (alkyl) phosphoric acid ester alkyl and arbitrary combination thereof, n is the integer of 0-3.
9. the emulsion of claim 8, wherein said hydrolyzable silane compound is selected from: silicol, alkyl-oxyl silane, amino-oxyl silane, brine alkyl-oxyl silane, mercapto alkyl-oxyl silane, hydroxyl alkyl-oxyl silane, ammonia alkyl-oxyl silane, epoxy alkyl-oxyl silane, (methyl) acryloyl-oxy alkyl-oxyl silane, alkyl acyloxy silane, alkyl ketoximinosilanes, alkyl phosphate hydrocarbyl si lanes, alkyl cyclosiloxane and arbitrary combination thereof.
10. the emulsion of claim 8, the consumption of wherein said hydrolyzable silane compound is the 1-20 weight % of emulsion total amount.
11. the emulsion of claim 1, wherein said emulsifying agent is selected from anion surfactant, nonionogenic tenside and arbitrary combination thereof.
12. being selected from the HLB value, the emulsion of claim 11, wherein said emulsifying agent be the anion surfactant of 3-50, nonionogenic tenside and the combination arbitrarily thereof that the HLB value is 3-50.
13. the emulsion of claim 11, wherein said emulsifying agent be selected from C8-C22 alkylsulfonate, C8-C22 alkylbenzene sulfonate, C8-C22 alkyl-sulphate, phosphate ester salt, polyether surfactant, C8-C22 fatty amide-polyoxyethylene, contain emulsified Silanization polymer segmental wetting ability block polymer and arbitrary combination thereof.
14. the emulsion of claim 1, the consumption of wherein said emulsifying agent are the 0-4 weight % of emulsion total amount.
15. the emulsion of claim 1, the particle diameter of wherein said nano silicon are 10-300nm.
16. the emulsion of claim 1, the BET specific surface area of wherein said nano silicon is 30m 2/ g to 400m 2/ g.
17. the emulsion of claim 1, the consumption of wherein said nano silicon are the 0-20 weight % of emulsion total amount.
18. the emulsion of claim 1, the pH value of wherein said emulsion is 4-10.
19. the emulsion of claim 1, wherein said emulsion solid content are 20-85 weight %, and wherein said Silanization polymer is when being the silanization polysiloxane, emulsion solid content is 20-75 weight %.
20. the emulsion of claim 1, the average latex particle size of wherein said emulsion is less than 3 microns.
21. each emulsion of claim 1 to 20, wherein said emulsion is an emulsion oil-in-water.
22. each emulsion of claim 1 to 20, wherein said emulsion is a water-in-oil emulsion.
23. each the preparation method of Silanization polymer emulsion of claim 1 to 22, it comprises following steps:
1) Silanization polymer, nonessential emulsifying agent and nonessential emulsion adjuvant are carried out blend, form component AI;
2) not necessarily,, form component AII with silane compound, water and nonessential nano silicon blend;
3) under agitation condition, in the component AI that step (1) obtains, add the component AII that step (2) obtains, or add silane compound, water and nonessential nano silicon synchronously respectively, carry out back emulsification; With
4) not necessarily, after emulsification was finished, the adjusting ph value of emulsion was 4-10.
24. each the preparation method of Silanization polymer emulsion of claim 1 to 22, it comprises following steps:
1) Silanization polymer, silane compound, nonessential emulsifying agent and nonessential emulsion adjuvant blend are formed B component I;
2), form B component II with water and nonessential nano silicon blend;
3) under agitation condition, in the miscellany BI that step (1) obtains, add the B component II that obtains in the step (2), to carry out back emulsification; With
4) not necessarily, after emulsification was finished, the adjusting ph value of emulsion was 4-10.
25. each the preparation method of Silanization polymer emulsion of claim 1 to 22, it comprises following steps:
1) Silanization polymer, nonessential emulsifying agent and nonessential emulsion adjuvant are carried out blend, form component CI;
2) under agitation condition, add water and nonessential nano silicon among the component CI that in step (1), obtains, form component CII;
3) under agitation condition, add silane compound among the component CII that in step (2), obtains to carry out back emulsification; With
4) not necessarily, after emulsification was finished, the adjusting ph value of emulsion was 4-10.
26. each Silanization polymer emulsion of claim 1 to 22 is as the application of the raw material of coating, tackiness agent, seal gum, printing ink, releasing agent, skin care product, clean-out system.
CNA2007100072283A 2007-01-25 2007-01-25 Aqueous siliconiting polymer emulsion as well as preparation method and use thereof Pending CN101230138A (en)

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