CN105859955A - Polyacrylate/nanometer SiO2 composite leather finishing agent prepared through miniemulsion polymerization method and preparation method thereof - Google Patents
Polyacrylate/nanometer SiO2 composite leather finishing agent prepared through miniemulsion polymerization method and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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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
- C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention relates to a polyacrylate/nanometer SiO2 composite leather finishing agent prepared through a miniemulsion polymerization method and a preparation method thereof. Research on the miniemulsion polymerization method is rarely reported. The preparation method includes the steps that nanometer SiO2, normal butanol and lauryl sodium sulfate are added to water and subjected to even ultrasonic dispersion, and a water phase is formed; butyl acrylate and methyl methacrylate are mixed to form an oil phase, the water phase and the oil phase are mixed and subjected to ultrasonic emulsification, and miniemulsion is obtained; 1/3 of a initiator water solution is subjected to bottoming, the other 2/3 of the initiator water solution and the miniemulsion are subjected to polymerization dropwise, and the leather finishing agent high in solid content is obtained. After the polyacrylate/nanometer SiO2 composite leather finishing agent is used for leather finishing, compared with performance of leather coated with a similar finishing agent sold on the market, tensile strength, dry and wet rubbing fastness and moisture permeability of the leather are obviously improved.
Description
Technical field
The present invention relates to a kind of leather finishing agent, be specifically related to polyacrylate/Nano-meter SiO_2 prepared by a kind of fine emulsion polymerization2Composite leather coating agent and preparation method thereof.
Background technology
Leather finishing agent, as the top finishing material of leather, has vital impact to external perception, sanitation performance and the physical and mechanical properties of leatherware.Acrylic ester monomer raw material sources are extensive, easily prepare, and have the cementability of excellence, light resistance, weatherability etc., and normal temperature solidified, and therefore polyacrylate emulsion is to apply a most common class coating material for leather at present.But, common acrylic acid ester emulsion film also exists the shortcomings such as " hot sticky cold crisp ", not solvent resistant, and use is restricted.It is improved, such as by the most many researcheres in different ways: introduce functional monomer and other finishing agents are compounding, introduce nanoparticle etc..Wherein Nano-meter SiO_22The introducing of particle has been demonstrated, increases the various aspects of performance of final finishing agent, but the introducing method of routine has many defects, such as: introduction volume is few, poor dispersion, and the performance boost to final finishing agent is limited.
Along with going deep into of development in science and technology research, fine emulsion polymerization is a kind of development New Emulsion polymerization quickly.Ni Shibao et al. (Ni Shibao, Wang Zheng, Nie Wangyan. acrylate/Nano-meter SiO_22The preparation of hybrid miniemulsion and sign [J]. material engineering, 2012(9), 66-73.) and it is prepared for acrylate/Nano-meter SiO_2 by fine emulsion polymerization2Complex emulsions.Use infrared spectrometry, transmission electron microscope, tensile testing machine and thermal analyzer etc. that complex emulsions and the structure of glued membrane, pattern, thermostability and mechanical property are characterized.Have studied Nano-meter SiO_22Consumption on complex emulsions and the impact of glue film performance thereof.Result shows: acrylate/Nano-meter SiO_22Complex emulsions particle has nucleocapsid structure；Nano-meter SiO_22The addition of particle, improves heat stability and the mechanical property of latex film；Work as SiO2Consumption is 5%(mass fraction) time, the light transmission of glued membrane is preferable.But relevant fine emulsion polymerization prepares polyacrylate/Nano-meter SiO_22The research of composite leather coating agent is also rarely reported.
Summary of the invention
It is an object of the invention to provide polyacrylate/Nano-meter SiO_2 prepared by a kind of fine emulsion polymerization2Composite leather coating agent and preparation method thereof, utilizes the feature of fine emulsion polymerization droplet nucleation to realize regular pattern polyacrylate/Nano-meter SiO_22The preparation of composite leather coating agent, improves and removes from office sample combination property after covering with paint, lacquer, colour wash, etc..
The technical solution adopted in the present invention is:
Fine emulsion polymerization prepares polyacrylate/Nano-meter SiO_22The preparation method of composite leather coating agent, it is characterised in that:
Realized by following steps:
Step one: pre-emulsification:
By 0.5-2 weight portion sodium lauryl sulphate, 1-5 weight portion Nano-meter SiO_22Be dissolved in 30-40 parts by weight of deionized water with 2-4 part by weight of n-butanol, ultrasonic uniformly, formed aqueous phase；
By 20-40 weight parts monomers mix and blend, form oil phase；
Step 2: fine crankshaft:
The aqueous phase that step one is obtained and oil phase mixing, first with high shear homogeneous emulsifying machine emulsifying 10min, then ultrasonic emulsification 10-25min, obtain milky, stable fine crankshaft liquid；
Step 3: polymerization:
2-3 weight portion Ammonium persulfate. is dissolved in 40-50 parts by weight of deionized water, obtains initiator solution, be classified as two parts of initiator solutions that weight ratio is A:B=1:2；
Water-bath is warmed up to 75 DEG C-80 DEG C, there-necked flask adds initiator solution A, is incubated 10min, after insulation, being simultaneously added dropwise the fine crankshaft liquid obtained by step 2 and initiator solution B, 3h dropping is complete, it is incubated two hours, is cooled to room temperature, filter discharging.
In step one, mix monomer is made up of weight ratio butyl acrylate between 6:4 to 5:5 and methyl methacrylate.
In step 2, the rotating speed of high shear homogeneous emulsifying machine emulsifying is 3000r/min.
Fine emulsion polymerization prepares polyacrylate/Nano-meter SiO_2 as mentioned2The finishing agent that the preparation method of composite leather coating agent prepares.
The invention have the advantages that
The present invention is with Nano-meter SiO_22, butyl acrylate, methyl methacrylate and n-butyl alcohol etc. be raw material, prepare polyacrylate/Nano-meter SiO_2 by fine emulsion polymerization2Composite leather coating agent, it is possible to reduce the consumption of surfactant, after being applied to leather finish, leather sample tensile strength, Bearable dry and wet wipe, water vapor permeability are all significantly improved, and wherein Bearable dry and wet wipe promotes effect more significantly, all improves one-level.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be described in detail.
The fine emulsion polymerization that the present invention relates to prepares polyacrylate/Nano-meter SiO_22The preparation method of composite leather coating agent, with Nano-meter SiO_22, butyl acrylate, methyl methacrylate and n-butyl alcohol etc. be raw material, prepare polyacrylate/Nano-meter SiO_2 by fine emulsion polymerization2Composite leather coating agent, is applied in leather finish, intends utilizing the feature of mini-emulsion polymerization to introduce Nano-meter SiO_22, specifically realized by following steps:
Step one: pre-emulsification:
By 0.5-2 weight portion sodium lauryl sulphate, 1-5 weight portion Nano-meter SiO_22Be dissolved in 30-40 parts by weight of deionized water with 2-4 part by weight of n-butanol, ultrasonic uniformly, formed aqueous phase；
By 20-40 weight parts monomers mix and blend, form oil phase；
Step 2: fine crankshaft:
The aqueous phase that step one is obtained and oil phase mixing, first with high shear homogeneous emulsifying machine emulsifying 10min, then ultrasonic emulsification 10-25min, obtain milky, stable fine crankshaft liquid；
Step 3: polymerization:
2-3 weight portion Ammonium persulfate. is dissolved in 40-50 parts by weight of deionized water, obtains initiator solution, be classified as two parts of initiator solutions that weight ratio is A:B=1:2；
Water-bath is warmed up to 75 DEG C-80 DEG C, there-necked flask adds initiator solution A, is incubated 10min, after insulation, being simultaneously added dropwise the fine crankshaft liquid obtained by step 2 and initiator solution B, 3h dropping is complete, it is incubated two hours, is cooled to room temperature, filter discharging.
In step one, mix monomer is made up of weight ratio butyl acrylate between 6:4 to 5:5 and methyl methacrylate.
In step 2, the rotating speed of high shear homogeneous emulsifying machine emulsifying is 3000r/min.
Embodiment 1:
Step one: pre-emulsification:
By 1.5 weight portion sodium lauryl sulphates, 5 weight portion Nano-meter SiO_22It is dissolved in 34 parts by weight of deionized water with 2 part by weight of n-butanol, ultrasonic uniformly forms aqueous phase, by 36 weight parts monomers mix and blends, form oil phase；
Wherein mix monomer is 6:4 butyl acrylate by weight ratio and methyl methacrylate forms；
Step 2: fine crankshaft:
Aqueous phase step one obtained and oil phase mixing, first with high shear homogeneous emulsifying machine emulsifying 10min(3000r/min), then ultrasonic emulsification 15min, obtain milky, stable fine crankshaft liquid.
Step 3: polymerization:
Being dissolved in 50 parts by weight of deionized water by 2 weight portion Ammonium persulfate .s, obtain initiator solution, being classified as weight ratio is 1:2(A:B=1:2) two parts of initiator solutions；
Water-bath being warmed up to 75 DEG C, adds initiator A aqueous solution, be incubated 10min in there-necked flask, after insulation, be simultaneously added dropwise the fine crankshaft liquid obtained by step 2 and initiator B aqueous solution, 3h dropping is complete, is incubated two hours, is cooled to room temperature, filters discharging.
Embodiment 2:
Step one: pre-emulsification:
By 2 weight portion sodium lauryl sulphates, 4 weight portion Nano-meter SiO_22It is dissolved in 34 parts by weight of deionized water with 2 part by weight of n-butanol, ultrasonic uniformly forms aqueous phase, by 36 weight parts monomers mix and blends, form oil phase；
Wherein mix monomer is 6:4 butyl acrylate by weight ratio and methyl methacrylate forms；
Step 2: fine crankshaft:
Aqueous phase step one obtained and oil phase mixing, first with high shear homogeneous emulsifying machine emulsifying 10min(3000r/min), then ultrasonic emulsification 10min, obtain milky, stable fine crankshaft liquid.
Step 3: polymerization:
Being dissolved in 50 parts by weight of deionized water by 2 weight portion Ammonium persulfate .s, obtain initiator solution, being classified as weight ratio is 1:2(A:B=1:2) two parts of initiator solutions；
Water-bath being warmed up to 75 DEG C, adds initiator A aqueous solution, be incubated 10min in there-necked flask, after insulation, be simultaneously added dropwise the fine crankshaft liquid obtained by step 2 and initiator B aqueous solution, 3h dropping is complete, is incubated two hours, is cooled to room temperature, filters discharging.
Embodiment 3:
Step one: pre-emulsification:
By 0.5 weight portion sodium lauryl sulphate, 4 weight portion Nano-meter SiO_22It is dissolved in 34 parts by weight of deionized water with 2 part by weight of n-butanol, ultrasonic uniformly forms aqueous phase, by 36 weight parts monomers mix and blends, form oil phase；
Wherein mix monomer is 5:5 butyl acrylate by weight ratio and methyl methacrylate forms；
Step 2: fine crankshaft:
Aqueous phase step one obtained and oil phase mixing, first with high shear homogeneous emulsifying machine emulsifying 10min(3000r/min), then ultrasonic emulsification 15min, obtain milky, stable fine crankshaft liquid.
Step 3: polymerization:
Being dissolved in 50 parts by weight of deionized water by 2 weight portion Ammonium persulfate .s, obtain initiator solution, being classified as weight ratio is 1:2(A:B=1:2) two parts of initiator solutions；
Water-bath being warmed up to 75 DEG C, adds initiator A aqueous solution, be incubated 10min in there-necked flask, after insulation, be simultaneously added dropwise the fine crankshaft liquid obtained by step 2 and initiator B aqueous solution, 3h dropping is complete, is incubated two hours, is cooled to room temperature, filters discharging.
Utilize said method can obtain polyacrylate/Nano-meter SiO_22Composite leather coating agent.The consumption of surfactant can be reduced, after being applied to leather finish, leather sample tensile strength, Bearable dry and wet wipe, water vapor permeability are all significantly improved, wherein Bearable dry and wet wipe lifting effect is the most notable, all improving one-level, leather sample tensile strength promotes 25%, and breathability promotes 66%, it is more notable that Bearable dry and wet wipe promotes effect, all improves one-level.
Present disclosure is not limited to cited by embodiment, and the conversion of any equivalence that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the invention, the claim being the present invention is contained.
Claims (4)
1. fine emulsion polymerization prepares polyacrylate/Nano-meter SiO_22The preparation method of composite leather coating agent, it is characterised in that:
Realized by following steps:
Step one: pre-emulsification:
By 0.5-2 weight portion sodium lauryl sulphate, 1-5 weight portion Nano-meter SiO_22Be dissolved in 30-40 parts by weight of deionized water with 2-4 part by weight of n-butanol, ultrasonic uniformly, formed aqueous phase；
By 20-40 weight parts monomers mix and blend, form oil phase；
Step 2: fine crankshaft:
The aqueous phase that step one is obtained and oil phase mixing, first with high shear homogeneous emulsifying machine emulsifying 10min, then ultrasonic emulsification 10-25min, obtain milky, stable fine crankshaft liquid；
Step 3: polymerization:
2-3 weight portion Ammonium persulfate. is dissolved in 40-50 parts by weight of deionized water, obtains initiator solution, be classified as two parts of initiator solutions that weight ratio is A:B=1:2；
Water-bath is warmed up to 75 DEG C-80 DEG C, there-necked flask adds initiator solution A, is incubated 10min, after insulation, being simultaneously added dropwise the fine crankshaft liquid obtained by step 2 and initiator solution B, 3h dropping is complete, it is incubated two hours, is cooled to room temperature, filter discharging.
Fine emulsion polymerization the most according to claim 1 prepares polyacrylate/Nano-meter SiO_22The preparation method of composite leather coating agent, it is characterised in that:
In step one, mix monomer is made up of weight ratio butyl acrylate between 6:4 to 5:5 and methyl methacrylate.
Fine emulsion polymerization the most according to claim 1 prepares polyacrylate/Nano-meter SiO_22The preparation method of composite leather coating agent, it is characterised in that:
In step 2, the rotating speed of high shear homogeneous emulsifying machine emulsifying is 3000r/min.
4. fine emulsion polymerization as claimed in claim 1 prepares polyacrylate/Nano-meter SiO_22The finishing agent that the preparation method of composite leather coating agent prepares.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317294A (en) * | 2016-09-13 | 2017-01-11 | 陕西科技大学 | Soap-free polyacrylate leather finishing agent prepared on basis of Pickering miniemulsion polymerization method and method for preparing soap-free polyacrylate leather finishing agent on basis of Pickering miniemulsion polymerization method |
| CN108424489A (en) * | 2018-04-10 | 2018-08-21 | 陕西科技大学 | Rodlike SiO2/ polyacrylate hybridized nanometer complex emulsions and preparation method thereof |
| CN109265599A (en) * | 2018-09-28 | 2019-01-25 | 陕西科技大学 | A kind of self-repair type polyacrylate dispersion and preparation method thereof |
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| CN102604003A (en) * | 2012-03-14 | 2012-07-25 | 大连工业大学 | Self-layering organic-inorganic nano composite emulsion and method for preparing same |
| CN102816275A (en) * | 2012-08-24 | 2012-12-12 | 浙江理工大学 | Textile deepening agent and preparation method thereof |
| CN105037614A (en) * | 2015-09-08 | 2015-11-11 | 陕西科技大学 | High-solid-content leather finishing agent prepared on basis of miniemulsion polymerization method and method thereof |
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2016
- 2016-06-17 CN CN201610429956.2A patent/CN105859955A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102604003A (en) * | 2012-03-14 | 2012-07-25 | 大连工业大学 | Self-layering organic-inorganic nano composite emulsion and method for preparing same |
| CN102816275A (en) * | 2012-08-24 | 2012-12-12 | 浙江理工大学 | Textile deepening agent and preparation method thereof |
| CN105037614A (en) * | 2015-09-08 | 2015-11-11 | 陕西科技大学 | High-solid-content leather finishing agent prepared on basis of miniemulsion polymerization method and method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317294A (en) * | 2016-09-13 | 2017-01-11 | 陕西科技大学 | Soap-free polyacrylate leather finishing agent prepared on basis of Pickering miniemulsion polymerization method and method for preparing soap-free polyacrylate leather finishing agent on basis of Pickering miniemulsion polymerization method |
| CN108424489A (en) * | 2018-04-10 | 2018-08-21 | 陕西科技大学 | Rodlike SiO2/ polyacrylate hybridized nanometer complex emulsions and preparation method thereof |
| CN108424489B (en) * | 2018-04-10 | 2020-07-14 | 陕西科技大学 | Rodlike SiO 2/polyacrylate hybrid nano composite emulsion and preparation method thereof |
| CN109265599A (en) * | 2018-09-28 | 2019-01-25 | 陕西科技大学 | A kind of self-repair type polyacrylate dispersion and preparation method thereof |
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