CN110066367A - Soap-free polymerization and the styrene-acrylic emulsion and preparation method thereof with core-shell structure - Google Patents
Soap-free polymerization and the styrene-acrylic emulsion and preparation method thereof with core-shell structure Download PDFInfo
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- CN110066367A CN110066367A CN201910387754.XA CN201910387754A CN110066367A CN 110066367 A CN110066367 A CN 110066367A CN 201910387754 A CN201910387754 A CN 201910387754A CN 110066367 A CN110066367 A CN 110066367A
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- 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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- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- 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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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- 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
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a kind of soap-free polymerization and with the styrene-acrylic emulsion of core-shell structure, it is collectively constituted by pre-emulsion, shell monomers, backing material and remaining small powder, and raw material includes water, reactive emulsifier, styrene, C4~C13Alkyl acrylate monomer, functional monomer, silane crosslinker, silica solution, sodium bicarbonate and initiator.The invention also discloses soap-free polymerization and with the styrene-acrylic emulsion preparation method of core-shell structure, this method and semi-continuous seed emulsion polymerization method, using silica solution as seed, mixing soft monomer is core, hard monomer and organosilane monomers are shell, emulsifier whole and reactive emulsifier, and manufactured styrene-acrylic emulsion rate of drying is fast, hardness is high, grinability is good, and high glaze, wet film permeability are excellent, and such water-based emulsion is particularly suitable for wood furniture incrustation.
Description
Technical field
The invention belongs to synthesis of polymer material technical fields, in particular it relates to a kind of manufacture aqueous wooden ware
Paint lotion, especially a kind of soap-free polymerization and the styrene-acrylic emulsion and preparation method thereof with core-shell structure.
Background technique
Lotion used in current aqueous woodware paint available on the market is mainly acrylic acid ester emulsion, such lotion has production
The advantages that at low cost, good weatherability, gloss are high and environmentally friendly, therefore be used widely.Research and development through many years, industry production third
The technology and technique of olefin(e) acid ester lotion are very mature, especially a seed nucleus disclosed in Chinese Patent Application No. 201710102922.7
The preparation method of shell structure hydroxyl acrylic emulsion is relatively advanced, it is organically by acrylic monomers pre-emulsification technology, seed gas
Emulsion polymerization technology, core-shell emulsion polymerization technology, self-crossing emulsion polymerization technique, emulsion polymerization technology combine.Along with adopting
With the monomer pre-emulsification of seeded emulsion polymerization part, the monomer of core emulsion polymerization part is directly added dropwise and shell emulsion polymerization part
The pre-emulsified technique of monomer, and select different initiator and rate of addition respectively during core-shell emulsion polymerization.Due to core
Shell selects the anion emulsifier and nonionic emulsifier compounding of different performance, has efficiently controlled emulsion particle diameter and distribution.Separately
Outside, glue solidification is not generated or only seldom generated in the synthesis process.Since the distribution of this technology groups is set, reasonable, technique is advanced,
The emulsifier being added in supernatant liquid synthesis accounts for the 6% or less of acrylic monomers total amount.But after the emulsion film forming of this technology production
Not high, glossiness that there are hardness and the imperfect problem of richness, the expectation with user still have certain gap.
Summary of the invention
Present invention is generally directed to problems of the existing technology, propose a kind of soap-free polymerization and the phenylpropyl alcohol with core-shell structure
Lotion, emulsion components collocation rationally, are easy to prepare, and the paint film richness obtained after coating is good, glossiness is sufficient, hardness is high, and
And water-whitening resistance is significantly improved.The invention also includes the preparation methods to match.
The present invention is achieved through the following technical solutions technical goal.
Soap-free polymerization and the styrene-acrylic emulsion with core-shell structure, the improvement is that: it is by a, pre-emulsion, b, shell
Monomer, c, backing material, d, remaining small powder collectively constitute, and the sum of four composition by weight amounts are 1000 parts, and each component accounting is as follows:
A, pre-emulsion
180~260 parts of water
1~5 part of reactive emulsifier
150~250 parts of styrene
C4~C13150~250 parts of alkyl acrylate monomer
1~5 part of functional monomer；
B, shell monomers
80~120 parts of styrene
1~5 part of silane crosslinker；
C, backing material
180~280 parts of water
2~20 parts of silica solution
1~5 part of reactive emulsifier
1~3 part of sodium bicarbonate；
D, remaining small powder
1~3 part of initiator
20~80 parts of water.
As the scheme of further improvement, the reactive emulsifier is allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy nonyl
One or two kinds of mixtures in base phenol polyethenoxy ether ammonium sulfate.
As the scheme of further improvement, the C4~C13Alkyl acrylate monomer be methyl acrylate, acrylic acid second
The mixture that ester, butyl acrylate, acrylic acid-2-ethyl caproite, decyl acrylate one or more of are worked as.
As the scheme of further improvement, the functional monomer is acrylic acid, trimethylolpropane trimethacrylate, methyl
The mixture that hydroxy-ethyl acrylate one or more of is worked as.
As the scheme of further improvement, the silane crosslinker is the mixing that A-171, A-174 one or both of work as
Object.
Soap-free polymerization and the styrene-acrylic emulsion preparation method with core-shell structure, it is characterised in that follow these steps to carry out:
1. measuring raw material respectively by each component accounting；
2. prepared by pre-emulsion material, by water, reactive emulsifier, styrene, the C in the component4~C13Acrylic acid alkyl
Ester monomer, functional monomer are sequentially added into respectively in the container with agitating function, and with 200~1000r/min revolving speed point
It dissipates and obtains pre-emulsion material；
3. prepared by backing material, water, reactive emulsifier, silica solution and the sodium bicarbonate in the component, which are added to, has stirring function
Can reaction vessel in, 10~15min is stirred with 20~120r/min revolving speed to be heated to 80~90 DEG C；
4. shell monomers prepare, by the component styrene and silane crosslinker be uniformly mixed；
5. prepared by remaining small powder, the initiator in the component is added to the water and is stirred evenly, the water containing initiator is made
Solution；
6. the aqueous solution containing initiator made of will be rigid is divided into 3 parts, takes out a copy of it and pours into the backing material prepared,
Another that the pre-emulsion prepared and another aqueous solution for containing initiator are added using dropwise addition mode, dropping temperature is 80~90
DEG C, 1.5~2h of process duration is added dropwise, at least 15min is kept the temperature after being added dropwise to complete；
7. continuing to add shell monomers into the material that previous process is completed using dropwise addition mode and remaining portion containing initiator
Aqueous solution, dropping temperature is maintained at 80~90 DEG C, 0.5~1h of process duration is added dropwise, and 1~2h is kept the temperature after being added dropwise to complete；
8. the material that previous process is completed is when being naturally cooled to 40 ± 2 DEG C, discharge when adjusting pH value to 7~9 with ammonium hydroxide.
Compared with prior art, the present invention having the positive effect that:
1, instant component configuration is simple, reasonable, and raw material is easy to get, matched preparation method special-less process requirement, working specification,
Therefore product quality is guaranteed, is particularly suitable for batch production；
2, the present invention has rationally synthesized the styrene-acrylic emulsion with core-shell structure using soap-free polymerization mode, and stratum nucleare is mixed in polymerization process
It closes monomer and shell mix monomer is added stage by stage, the milk particle of formation is in soft core monocoque.Along with being added in shell
Silane crosslinker is remarkably improved lotion water resistance.In addition newly-increased silica solution also significantly improves the water-whitening resistance of lotion, resistance toization
The property learned and heat resistance, hardness, richness and rub resistance achieve the desired results after the film curing obtained after lotion applicator.
Specific embodiment
The present invention is further illustrated below by embodiment, each embodiment each component amount of being by weight adds up to
1000g。
Embodiment 1
1. measuring raw material respectively by component accounting first；
2. prepared by pre-emulsion, 180g water, the 1g allyloxy nonyl phenol polyethenoxy ether ammonium sulfate, 150g benzene second measured by component
Alkene, 250g butyl acrylate, 1g acrylic acid are added separately to have in the container of agitating function in order, and are turned with 200r/min
Speed dispersion obtains pre-emulsion；
3. prepared by backing material, 5g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 2g silicon solution, 1g sodium bicarbonate and the 280g measured by component
Water is added in the reaction vessel with agitating function, stirs 15min with 50r/min revolving speed to be heated to 82 ± 2 DEG C；
4. prepared by shell monomers, the 80 g styrene and 1gA-171 measured by component are uniformly mixed；
5. prepared by remaining small powder, the 2g initiator and 47g water measured by component is mixed into the aqueous solution containing initiator；
6. the aqueous solution containing initiator made of will be rigid is divided into 3 parts, takes out a copy of it and pours into manufactured backing material,
Another that manufactured pre-emulsion and another aqueous solution for containing initiator is added using dropwise addition mode, dropping temperature is maintained at 80
~84 DEG C, process duration 1.5h is added dropwise, at least 15min is kept the temperature after being added dropwise to complete；
7. continuing to add shell monomers into the material that previous process is completed using dropwise addition mode and remaining portion containing initiator
Aqueous solution, dropping temperature is maintained at 80~84 DEG C, process duration 1h is added dropwise, keeps the temperature 1h after being added dropwise to complete；
8. the material that previous process is completed discharges when being naturally cooled to 40 ± 2 DEG C.
Embodiment 2
1. measuring raw material respectively by component accounting first；
2. prepared by pre-emulsion, 260g water, the 5g allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, 250g benzene measured by component
Ethylene, 150g butyl acrylate, 5g acrylic acid are added separately to have in the container of agitating function in order, and with 600r/min
Revolving speed disperses to obtain pre-emulsion；
3. backing material prepare, by component measure 1g allyloxy hydroxypropyl azochlorosulfonate acid sodium, 20g silicon solution, 3g sodium bicarbonate and
180g water is added in the reaction vessel with agitating function, stirs 15min with 20r/min revolving speed to be heated to 86 ± 2 DEG C；
4. prepared by shell monomers, the 100 g styrene and 5gA-171 measured by component are uniformly mixed；
5. prepared by remaining small powder, the 1g initiator and 20g water measured by component is mixed into the aqueous solution containing initiator；
6. the aqueous solution containing initiator made of will be rigid is divided into 3 parts, takes out a copy of it and pours into manufactured backing material,
Another that manufactured pre-emulsion and another aqueous solution for containing initiator is added using dropwise addition mode, dropping temperature is maintained at 84
~88 DEG C, process duration 1h is added dropwise, at least 25min is kept the temperature after being added dropwise to complete；
7. continuing to add shell monomers into the material that previous process is completed using dropwise addition mode and remaining portion containing initiator
Aqueous solution, dropping temperature is maintained at 84~88 DEG C, process duration 0.5h is added dropwise, keeps the temperature 2h after being added dropwise to complete；
8. the material that previous process is completed discharges when being naturally cooled to 40 ± 2 DEG C.
Embodiment 3
1. measuring raw material respectively by component accounting first；
2. prepared by pre-emulsion, 200g water, the 5g allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, 174g benzene measured by component
Ethylene, 200g ethyl acrylate, 4g acrylic acid are sequentially added into the container with agitating function, and are turned with 1000r/min
Speed dispersion obtains pre-emulsion；
3. prepared by backing material, 3g allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, the 1g allyloxy hydroxypropyl measured by component
Base sodium sulfonate, 10g silicon solution, 1.0g sodium bicarbonate and 218g water are added in the reaction vessel with agitating function, to be heated
15min is stirred with 120r/min revolving speed when to 88 ± 2 DEG C；
4. prepared by shell monomers, the 100 g styrene and 2gA-171 measured by component are uniformly mixed；
5. prepared by remaining small powder, the 3g initiator and 80g water measured by component is mixed into the aqueous solution containing initiator；
6. the aqueous solution containing initiator made of will be rigid is divided into 3 parts, takes out a copy of it and pours into manufactured backing material,
Another that manufactured pre-emulsion and another aqueous solution for containing initiator is added using dropwise addition mode, dropping temperature is maintained at 86
~90 DEG C, process duration 2h is added dropwise, keeps the temperature 30min after being added dropwise to complete；
7. continuing to add shell monomers into the material that previous process is completed using dropwise addition mode and remaining portion containing initiator
Aqueous solution, dropping temperature is maintained at 86~90 DEG C, process duration 0.8h is added dropwise, keeps the temperature 1.5h after being added dropwise to complete；
8. the material that previous process is completed discharges when being naturally cooled to 40 ± 2 DEG C.
The present invention rationally uses soap-free polymerization mode to synthesize the styrene-acrylic emulsion with core-shell structure, stratum nucleare in polymerization process
Mix monomer and shell mix monomer are added stage by stage, and the milk particle of formation is in soft core monocoque.Emulsifier used in component
All using reactive emulsifier, the benzene that rate of drying is fast, grinability is good, high rigidity, high glaze, wet film permeability are good has been obtained
Acrylic emulsion.Along with silane crosslinker is added in shell, it is remarkably improved lotion water resistance.In addition newly-increased silica solution
Water-whitening resistance, chemical resistance and the heat resistance of lotion are further increased, it is hardness after the film curing obtained after lotion applicator, plentiful
Degree and rub resistance achieve the desired results.Styrene-acrylic emulsion made of above-mentioned three embodiments is taken to be respectively coated in three blocks of glass
On plate, coating thickness is 50 microns, the super 2H of the sample hardness of three embodiments, grinability than one times of the prior art with
On.The water-fast 96h of embodiment 1 does not whiten, and the water-fast 102h of embodiment 2 does not whiten, and the water-fast 93h of embodiment 3 does not whiten.In 60 degree of gloss
Reach 95.
Above-described embodiment is only illustrated the purpose of the present invention, technical scheme and beneficial effects, it should be understood that institute
It states bright only to the explanation of invention, and does not have to the limitation present invention, all within the spirits and principles of the present invention, that is done any repairs
Change, equivalent replacement, improvement etc., should all include within protection scope of the present invention.
Claims (6)
1. a kind of soap-free polymerization and the styrene-acrylic emulsion with core-shell structure, it is characterised in that: it is by a, pre-emulsion, b, shell list
Body, c, backing material, d, remaining small powder collectively constitute, and the sum of four composition by weight amounts are 1000 parts, and each component accounting is as follows:
A, pre-emulsion
180~260 parts of water
1~5 part of reactive emulsifier
150~250 parts of styrene
C4~C13150~250 parts of alkyl acrylate monomer
1~5 part of functional monomer；
B, shell monomers
80~120 parts of styrene
1~5 part of silane crosslinker；
C, backing material
180~280 parts of water
220 parts of silica solution
1~5 part of reactive emulsifier
1~3 part of sodium bicarbonate；
D, remaining small powder
1~3 part of initiator
20~80 parts of water.
2. soap-free polymerization according to claim 1 and the styrene-acrylic emulsion with core-shell structure, it is characterised in that: the reaction
Type emulsifier is that allyloxy hydroxypropyl azochlorosulfonate acid sodium, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate one or both of are worked as
Mixture.
3. soap-free polymerization according to claim 1 and the styrene-acrylic emulsion with core-shell structure, it is characterised in that: the C4~
C13Alkyl acrylate monomer be methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid-2-ethyl caproite, propylene
The mixture that sour last of the ten Heavenly stems ester one or more of is worked as.
4. soap-free polymerization according to claim 1 and the styrene-acrylic emulsion with core-shell structure, it is characterised in that: the function
Property monomer be mixing that acrylic acid, trimethylolpropane trimethacrylate, hydroxyethyl methacrylate one or more of are worked as
Object.
5. soap-free polymerization according to claim 1 and the styrene-acrylic emulsion with core-shell structure, it is characterised in that: the silane
Crosslinking agent is the mixture that A-171, A-174 one or both of work as.
6. a kind of soap-free polymerization and the styrene-acrylic emulsion preparation method with core-shell structure, it is characterised in that follow these steps to carry out:
1. measuring raw material respectively by each component accounting；
2. prepared by pre-emulsion material, by water, reactive emulsifier, styrene, the C in the component4~C13Acrylic acid alkyl
Ester monomer, functional monomer are sequentially added into respectively in the emulsification container with agitating function, and are turned with 200~1000r/min
Speed dispersion obtains pre-emulsion material；
3. prepared by backing material, water, reactive emulsifier, silica solution and the sodium bicarbonate in the component, which are added to, has stirring function
Can reaction vessel in, 10~15min is stirred with 20~120r/min revolving speed to be heated to 80~90 DEG C；
4. shell monomers prepare, by the component styrene and silane crosslinker be uniformly mixed；
5. prepared by remaining small powder, the initiator in the component is added to the water and is stirred evenly, the water containing initiator is made
Solution；
6. the aqueous solution containing initiator made of will be rigid is divided into 3 parts, takes out a copy of it and pours into the backing material prepared,
Another that the pre-emulsion prepared and another aqueous solution for containing initiator are added using dropwise addition mode, dropping temperature is 80~90
DEG C, 1.5~2h of process duration is added dropwise, at least 15min is kept the temperature after being added dropwise to complete；
7. continuing to add shell monomers into the material that previous process is completed using dropwise addition mode and remaining portion containing initiator
Aqueous solution, dropping temperature is maintained at 80~90 DEG C, 0.5~1h of process duration is added dropwise, and 1~2h is kept the temperature after being added dropwise to complete；
8. the material that previous process is completed is when being naturally cooled to 40 ± 2 DEG C, discharge when adjusting pH value to 7~9 with ammonium hydroxide.
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| CN201910387754.XA CN110066367A (en) | 2019-05-10 | 2019-05-10 | Soap-free polymerization and the styrene-acrylic emulsion and preparation method thereof with core-shell structure |
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| CN201910387754.XA CN110066367A (en) | 2019-05-10 | 2019-05-10 | Soap-free polymerization and the styrene-acrylic emulsion and preparation method thereof with core-shell structure |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138595A (en) * | 2019-12-25 | 2020-05-12 | 广东银洋环保新材料有限公司 | Water-based glazing oil emulsion with heat resistance, preparation method thereof and water-based glazing oil |
-
2019
- 2019-05-10 CN CN201910387754.XA patent/CN110066367A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138595A (en) * | 2019-12-25 | 2020-05-12 | 广东银洋环保新材料有限公司 | Water-based glazing oil emulsion with heat resistance, preparation method thereof and water-based glazing oil |
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