CN107880207A - Novel aqueous acroleic acid resin/lithium soap soil composite leather coating agent prepared by a kind of Pickering emulsion polymerization technologies - Google Patents
Novel aqueous acroleic acid resin/lithium soap soil composite leather coating agent prepared by a kind of Pickering emulsion polymerization technologies Download PDFInfo
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- CN107880207A CN107880207A CN201711167541.3A CN201711167541A CN107880207A CN 107880207 A CN107880207 A CN 107880207A CN 201711167541 A CN201711167541 A CN 201711167541A CN 107880207 A CN107880207 A CN 107880207A
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- lithium soap
- emulsion polymerization
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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
-
- 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
-
- 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
-
- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
-
- 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
-
- 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
- C08K7/00—Use of ingredients characterised by shape
Abstract
The invention provides a kind of aqueous acroleic acid resin/lithium soap soil organo-mineral complexing leather finishing agent prepared based on Pickering emulsion polymerization technologies, it is that traditional organic surface active agent is replaced for emulsion stabilizer with nontoxic solid nanoparticles lithium soap soil, the aqueous acroleic acid resin/lithium soap soil composite leather coating agent using acrylate polymer as core, using nanoclay as shell for using Pickering emulsion polymerization technologies to prepare.The present invention solves acrylic resin in emulsion polymerization production technology because of environmental hazard that the use of organic emulsifier is brought and its film forming water resistance caused by being migrated during emulsion film forming and adhesive force reduce the problems such as, and the stabilizer lithium soap soil used is a kind of nanoclay with Nano lamellite structure, modification strengthening agent that can simultaneously as acrylic resin, the wear-resisting, water-fast of material, weatherability and mechanical property are effectively improved, and assigns film anti-ultraviolet ageing performance.
Description
Technical field
The present invention relates to water-based acrylic resin and leather finish field, and in particular to one kind is gathered based on Pickering emulsions
Novel aqueous acroleic acid resin/lithium soap soil Organic-inorganic composite leather finishing agent prepared by conjunction technology.
Background technology
Covering with paint is the critical process for making crust leather have performance, " Golden Touch " being described as in process hides, because it is determined
Sense organ, performance and the value of resultant Leather；Particularly current traditional leather industry is faced with the immense pressure of industrial transformation upgrading,
Therefore to the Functional Requirement more and more higher of coating material, but also must be environment-friendly.The exploitation of new material is from solvent
Section bar material is converted to the water-based material of environmental protection.Water polyacrylic acid emulsion have excellent film forming, cementability, weatherability,
Light colour retention is protected, and it is inexpensive, safe and environment-friendly, it has also become a kind of film forming matter being most widely used in coating material for leather.But
It is that not ideal enough acrylic acid ester emulsion water resistance, cold resistance, heat resistance are poor, is easy to the change of plasticity type, normal temperature is not easy to be crosslinked, it is difficult to
Three-dimensional netted crosslinking film is formed, heat can be produced and stick cold short phenomenon, generally required composite modified to its.In its numerous modification side
In method, the inorganic nano material modified latest development for modification of acrylic resin research.
The preparation method of polyacrylate includes a variety of methods such as solution, emulsion, suspension, polymerisation in bulk, and emulsion is gathered at present
Close and solution polymerization process is the most commonly used.Emulsion polymerization technology has obtained significant progress since the twenties in last century occurs, because
It is a kind of polymerization using water as reaction medium for it, avoids the harm of organic solvent in traditional solution method, and it is poly-
Easily transfer is sudden and violent poly- so as to avoid for heat during conjunction, and polymerization rate is higher, and cost is relatively low, safe, to body
Nonhazardous, environmentally safe, polymerization technique is simple, is to prepare the very important method of acrylate polymer at present.But pass
Emulsifying agent will be added in the emulsion polymerization of system, so that stable system and nucleation, but the free emulsifying agent remained in product can be right
Electrical property, optical property, surface nature and water resistance of emulsion polymer etc. cause necessarily to influence.What is more important, emulsification
Agent is generally expensive, and product cost can be increased by adding emulsifying agent, and surfactant during emulsion film forming easily to film-
Air and film-ground enrichment migration, so as to cause the water resistance of film, adhesive force and adhesion strength to decline.To solve emulsifying agent
Problem, occurs the emulsifier-free emulsion polymerization method without using emulsifying agent in succession.But due to being not present in emulsifier-free emulsion polymerization system
The protective effect of emulsifying agent, emulsion intercalation method are to be improved.Common solution is in emulsifier-free emulsion polymerization reaction system
It is middle to add excessive initiator, by the way that initiator to be connected to the end of polymer so as to play emulsification, so as to compensate for
In system emulsifier content it is few or without the problem of, but still to hardly result in stability preferably newborn for this polymerization system
Liquid, and it is relatively low generally to polymerize obtained emulsion solid content, mostly 10% or so.Therefore need to find suitable emulsion polymerization side
Method and technology, development environment is friendly and the water-and acrylate coating material of excellent performance, promotes the upgrading and further of material
Commercial Application.
In recent years, the stable emulsion of solids, namely Pickering emulsions, because which obviating the poison of surfactant
Property and negative effect (such as foaming, toxicity, influence material property) and exclusive interface particle self assembly effect, developed recently
It is rapid and cause the extensive concern of scientific circles.The A of patent CN 106317294 select SiO2, water, n-butanol and comonomer are
Primary raw material is prepared for no soap polyacrylate leather finishing agent, with reference to pickering emulsion polymerizations and mini-emulsion polymerization side
Method, prepare no soap polyacrylate leather finishing agent.Although organic surfactant in conventional emulsion polymerizations is avoided in the method
The use of agent, but still used organic solvent n-butanol.It was noted that lithium soap soil is a kind of stronger artificial synthesized of hydrophily
The phyllosilicate with Nano lamellite structure, its particle diameter concentrates on 25 ~ 30 nm, and lamellae thickness is ~ 1 nm.Size is controllable
And hydrophily is stronger, lamellar structure can be peeled off into water, ultimately forms the colloidal dispersion of water white transparency, therefore be used as and add
Add agent and rheological agent be widely used in industry and the consumer goods such as coating lacquer, printing, toothpaste, and its colloid property make its
The advantage of uniqueness is shown in terms of stable emulsion or latex particle.In fact, by nano clay modified polyacrylate it is existing compared with
More research report, such as patent CN200610035511.2《The preparation method of organic silicon acrylic ester/nano clay composite emulsion
And its application》Deng.But there is the problem of compatibility is bad in inorganic nano clay always with organic polymer.Current research finds to adopt
Can solve this problem, and the solids breast of stable Pickering emulsions well with the Pickering methods polymerizeing
Agent has the advantages that inexpensive, nontoxic, pollution-free, and the polymer emulsion of preparation needs not move through the post processing of complexity.The application with
Nontoxic nanoclay lithium soap soil stablizes the emulsion polymerization of acrylate for stabilizer, is gathered by Pickering emulsions
Low-dimensional nano-particle lithium soap soil with lamellar structure is incorporated into acroleic acid resin by conjunction technology, prepare using lithium soap soil as shell, with
Polyacrylate polymers are the organic and inorganic coating material for leather of core.It is relevant that water is prepared by pickering emulsion polymerizations
Research in terms of property acroleic acid resin/nanoclay Organic-inorganic composite leather finishing agent yet there are no document report.
The content of the invention
A kind of aqueous acroleic acid resin/lithium soap soil Organic-inorganic composite prepared based on Pickering emulsion polymerization technologies
Leather finishing agent, it is characterised in that it replaces traditional organic surface to live with nontoxic inorganic nano-particle lithium soap soil for stabilizer
Property agent, use pickering emulsion polymerization technologies prepare using acrylate polymer as core, using inorganic nano-particle as shell
Aqueous acroleic acid resin/lithium soap soil composite leather coating agent, its synthesis step are as follows：
（1）A certain amount of lithium soap soil and deionized water are added into reaction bulb, 8 h, mixing speed 600 are dispersed with stirring under normal temperature
~ 1500 rpm, obtain lithium soap soil dispersion liquid；Then acrylate co-monomers, comonomer and water quality ratio are added（0.4~
1）:1, the min of high speed emulsion dispersion 10 ~ 30, mixing speed are 4000 ~ 10000 rpm；Obtain the Pickering of lithium soap soil stabilization
Emulsion；
（2）Above-mentioned Pickering emulsions are added in the reactor with condensation and agitating device, temperature is 60 ~ 80 DEG C,
A certain amount of initiator solution is added dropwise thereto, control rate of addition causes time for adding control to be used in 0.5 ~ 1 h, initiator
0.4 ~ 1 wt% for comonomer total amount is measured, the mass ratio of comonomer and water is in whole reaction system（0.2~0.5）:1；
75~100 DEG C are warming up to, the rpm of mixing speed 500~2000, the h of stirring reaction 2~5, obtains aqueous acroleic acid resin/lithium soap
Native Organic-inorganic composite leather finishing agent.
Described acrylate co-monomers include three components of soft monomer and hard monomer and functional monomer；Soft monomer is
One kind in ethyl acrylate, n-propyl and n-butyl acrylate；Hard monomer is methyl acrylate, methyl methacrylate
It is a kind of in ester, EMA；Functional monomer is α-methacrylic acid beta-hydroxy ethyl ester, acrylamide and metering system
Acid -2, one kind in 3 polyglycidyls, functional monomer dosage are 4 ~ 12 wt% of comonomer gross mass
Described lithium soap soil is a kind of stronger artificial synthesized nanoclay with lamellar structure of hydrophily, and its particle diameter is concentrated
In 25 ~ 30 nm, lamellae thickness is ~ 1 nm, and its dosage is 2 ~ 8 wt% of comonomer total amount.
Described initiator is one kind in ammonium persulfate, potassium peroxydisulfate.
The invention provides a kind of aqueous acroleic acid resin/lithium soap soil prepared based on Pickering emulsion polymerization technologies
Organic-inorganic composite leather finishing agent, it is characterised in that it replaces passing with nontoxic solid nanoparticles lithium soap soil for stabilizer
The organic surface active agent of system, use Pickering emulsion polymerization technologies prepare using acrylate polymer as core, with inorganic
Nano-particle be shell aqueous acroleic acid resin/lithium soap soil composite leather coating agent, used Pickering emulsion polymerizations skill
Art not only avoid the use of organic surface active agent in conventional emulsion polymerizations method, solve the toxicity problem of organic emulsifier
And its negative effect to emulsion later stage filming performance, and the stabilizer lithium soap soil nano-particle used is that one kind has lamella
The nanoclay of structure, reinforced modifier that can simultaneously as acrylic resin, significantly improve the mechanical property, wear-resisting of finishing agent
Performance and heat endurance, and assign film good anti-ultraviolet ageing performance.
Applicating example 1
0.5 g nano-particles lithium soap soil and 25 g deionized waters are added into reactor, 4 h, stirring speed are dispersed with stirring under normal temperature
Spend for 600 rpm, obtain lithium soap soil dispersion liquid；Then acrylate co-monomers mixture is added：The g of methyl acrylate 4.2,
The g of butyl acrylate 12.85, the g of acrylamide 1, the min of high speed emulsion dispersion 10 ~ 30, emulsion dispersion speed are 8000 rpm；
To the Pickering emulsions of lithium soap soil stabilization；
Above-mentioned Pickering emulsions are added in the 250 ml three-necked flasks equipped with agitator and condensing unit, temperature preserves
At 70 DEG C, the rpm of mixing speed 1000,0.15g initiator ammonium sulfate is dissolved in 20 g water, ammonium sulfate solution.To reaction bulb
In be progressively added dropwise ammonium sulfate solution, control rate of addition so that be added dropwise in 0.5h.85 DEG C are warming up to, reacts 3h；Cooling
To normal temperature, filtering, water polyacrylic acid/lithium soap soil Organic-inorganic composite leather finishing agent is produced.
Applicating example 2
1g nano-particles lithium soap soil and 60 g deionized waters are added into reactor, are dispersed with stirring 4 h under normal temperature, mixing speed is
600 rpm, obtain lithium soap soil dispersion liquid；Then acrylate co-monomers mixture is added：The g of methyl methacrylate 8.4,
The g of ethyl acrylate 25, the g of methacrylic acid -2,3 polyglycidyl 3, the min of high speed emulsion dispersion 10 ~ 30, emulsion dispersion speed are
8000 rpm；Obtain the Pickering emulsions of lithium soap soil stabilization；
Above-mentioned Pickering emulsions are added in the 250 ml three-necked flasks equipped with agitator and condensing unit, temperature preserves
At 70 DEG C, the rpm of mixing speed 1000,0.3 g initiator ammonium sulfate is dissolved in 40 g water, ammonium sulfate solution.To reaction bulb
In be progressively added dropwise ammonium sulfate solution, control rate of addition so that be added dropwise in 0.5 h.85 DEG C are warming up to, reacts 4 h；It is cold
But to normal temperature, filtering, water polyacrylic acid/lithium soap soil Organic-inorganic composite leather finishing agent is produced.
Applicating example 3
1.5 g nano-particles lithium soaps soil and 75 g deionized waters are added into reactor, 4 h, stirring speed are dispersed with stirring under normal temperature
Spend for 600 rpm, obtain lithium soap soil dispersion liquid；Then acrylate co-monomers mixture is added：The g of n-propyl 10,
The g of EMA 20, the g of α-methacrylic acid beta-hydroxy ethyl ester 3, the min of high speed emulsion dispersion 10 ~ 30, emulsion dispersion speed
For 8000 rpm；Obtain the Pickering emulsions of lithium soap soil stabilization；
Above-mentioned Pickering emulsions are added in the 250ml three-necked flasks equipped with agitator and condensing unit, temperature preserves
At 70 DEG C, the rpm of mixing speed 1000,0.3 g initiator ammonium sulfate is dissolved in 40g water, ammonium sulfate solution.To reaction bulb
In be progressively added dropwise ammonium sulfate solution, control rate of addition so that be added dropwise in 0.5h.80 DEG C are warming up to, reacts 5 h；It is cold
But to normal temperature, filtering, water polyacrylic acid/lithium soap soil Organic-inorganic composite leather finishing agent is produced.
Claims (4)
1. a kind of novel aqueous acroleic acid resin/lithium soap soil organic and inorganic prepared based on Pickering emulsion polymerization technologies is answered
Close leather finishing agent, it is characterised in that preparation method be replaced with nontoxic nanoclay lithium soap soil for stabilizer it is traditional organic
Surfactant, use pickering emulsion polymerization technologies prepare using acrylate polymer as core, with inorganic nano-particle
It is as follows for aqueous acroleic acid resin/lithium soap soil composite leather coating agent of shell, its synthesis step：
（1）A certain amount of lithium soap soil and deionized water are added into reactor, 8 h, mixing speed 600 are dispersed with stirring under normal temperature
~ 1500 rpm, obtain lithium soap soil dispersion liquid；Then acrylate co-monomers, comonomer and water quality ratio are added（0.4~
1）:1, the min of high speed emulsion dispersion 10 ~ 30, mixing speed are 4000 ~ 10000 rpm；Obtain the Pickering of lithium soap soil stabilization
Emulsion；
（2）Above-mentioned Pickering emulsions are added in the reactor with condensation and agitating device, temperature is 60 ~ 80 DEG C,
A certain amount of initiator solution is added dropwise thereto, control rate of addition causes time for adding control to be used in 0.5 ~ 1 h, initiator
0.4 ~ 1 wt% for comonomer total amount is measured, the mass ratio of comonomer and water is in whole reaction system（0.2~0.5）:1；
75~100 DEG C are warming up to, the rpm of mixing speed 500~2000, the h of stirring reaction 2~5, obtains aqueous acroleic acid resin/lithium soap
Native Organic-inorganic composite leather finishing agent.
A kind of 2. aqueous acroleic acid resin/lithium prepared based on Pickering emulsion polymerization technologies according to claim 1
Bentonite Organic-inorganic composite leather finishing agent, it is characterised in that described acrylate co-monomers include soft monomer and hard list
Three components of body and functional monomer；Soft monomer is one kind in ethyl acrylate, n-propyl and n-butyl acrylate；
Hard monomer is a kind of in methyl acrylate, methyl methacrylate, EMA；Functional monomer is Alpha-Methyl propylene
One kind in sour beta-hydroxy ethyl ester, acrylamide and methacrylic acid -2,3 polyglycidyl, the quality of soft monomer and rigid monomer
Than for（1~1.3）:1, functional monomer dosage is 4 ~ 12 wt% of comonomer gross mass.
A kind of 3. aqueous acroleic acid resin/lithium prepared based on Pickering emulsion polymerization technologies according to claim 1
Bentonite Organic-inorganic composite leather finishing agent, it is characterised in that described lithium soap soil is a kind of stronger artificial synthesized of hydrophily
The phyllosilicate nano clay with lamellar structure, its particle diameter concentrates on 25 ~ 30 nm, and lamellae thickness is ~ 1 nm, and it is used
Measure 2 ~ 8 wt% for comonomer total amount.
A kind of 4. aqueous acroleic acid resin/lithium prepared based on Pickering emulsion polymerization technologies according to claim 1
Bentonite Organic-inorganic composite leather finishing agent, it is characterised in that described initiator is one in ammonium persulfate, potassium peroxydisulfate
Kind.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401599A (en) * | 2018-09-12 | 2019-03-01 | 安徽康瑞高科新材料技术工程有限公司 | A kind of UV coating and preparation method thereof suitable for BMC |
| CN109943220A (en) * | 2019-03-28 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of aqueous leather coating of wear-resisting scratch resistance and preparation method thereof |
| CN109943301A (en) * | 2019-03-28 | 2019-06-28 | 中国石油大学(华东) | Resin emulsion sealing agent composition and preparation method thereof and the application in fracture formation |
| CN111234060A (en) * | 2020-03-19 | 2020-06-05 | 长春工业大学 | Soap-free emulsion polymerization method of high polymer resin |
| CN111303320A (en) * | 2020-03-13 | 2020-06-19 | 华南理工大学 | Polymer/inorganic nano particle composite material and preparation method thereof |
| CN115612120A (en) * | 2022-10-10 | 2023-01-17 | 四川大学 | Method for preparing novel waterborne polyurethane based on Pickering emulsion method |
| CN115612120B (en) * | 2022-10-10 | 2024-04-19 | 四川大学 | Method for preparing novel aqueous polyurethane based on Pickering emulsion method |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109401599A (en) * | 2018-09-12 | 2019-03-01 | 安徽康瑞高科新材料技术工程有限公司 | A kind of UV coating and preparation method thereof suitable for BMC |
| CN109943220A (en) * | 2019-03-28 | 2019-06-28 | 中国科学院长春应用化学研究所 | A kind of aqueous leather coating of wear-resisting scratch resistance and preparation method thereof |
| CN109943301A (en) * | 2019-03-28 | 2019-06-28 | 中国石油大学(华东) | Resin emulsion sealing agent composition and preparation method thereof and the application in fracture formation |
| CN111303320A (en) * | 2020-03-13 | 2020-06-19 | 华南理工大学 | Polymer/inorganic nano particle composite material and preparation method thereof |
| CN111303320B (en) * | 2020-03-13 | 2022-06-14 | 华南理工大学 | Polymer/inorganic nano particle composite material and preparation method thereof |
| CN111234060A (en) * | 2020-03-19 | 2020-06-05 | 长春工业大学 | Soap-free emulsion polymerization method of high polymer resin |
| CN111234060B (en) * | 2020-03-19 | 2022-11-18 | 长春工业大学 | Soap-free emulsion polymerization method of high polymer resin |
| CN115612120A (en) * | 2022-10-10 | 2023-01-17 | 四川大学 | Method for preparing novel waterborne polyurethane based on Pickering emulsion method |
| CN115612120B (en) * | 2022-10-10 | 2024-04-19 | 四川大学 | Method for preparing novel aqueous polyurethane based on Pickering emulsion method |
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Application publication date: 20180406 |