CN106519092A - Method for preparing polymer nanometer composite by using Pickering emulsion with organic modified magadiite as emulsifying agent - Google Patents
Method for preparing polymer nanometer composite by using Pickering emulsion with organic modified magadiite as emulsifying agent Download PDFInfo
- Publication number
- CN106519092A CN106519092A CN201611019424.8A CN201611019424A CN106519092A CN 106519092 A CN106519092 A CN 106519092A CN 201611019424 A CN201611019424 A CN 201611019424A CN 106519092 A CN106519092 A CN 106519092A
- Authority
- CN
- China
- Prior art keywords
- organically
- emulsifying agent
- magadiite
- modified magadiite
- pickering emulsions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08F120/00—Homopolymers 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
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a method for preparing a polymer nanometer composite by using a Pickering emulsion with organic modified magadiite as an emulsifying agent. According to the method, the organic modified magadiite is used as the emulsifying agent, a polymerizing monomer is used as an oil phase, and the stable Pickering emulsion is prepared; and then, a water-soluble free radical polymerizing initiator is added, and emulsion polymerization is carried out so as to prepare the polymer nanometer composite. By adopting organic modified magadiite solid particles to replace a traditional surfactant to perform an emulsifying function, the usage of the emulsifying agent is greatly reduced, and the emulsifying agent is nontoxic and harmless and has the advantages of being green and environment-friendly. The preparing method is simple in technology and simple to operate, and polymerizing products do not need to be post-treated.
Description
Technical field
The present invention relates to emulsion polymerizing preparation compound technical field of nano material, and in particular to one kind is with organically-modified wheat
Hydroxyl silicon sodium stone is the method that the Pickering emulsions of emulsifying agent prepare polymer nanocomposites.
Background technology
Emulsion polymerization is a kind of monomer polymerization high molecular conventional polymerization of synthesis, it using water as solvent, to ring
Border is highly beneficial.Emulsion polymerization be monomer by emulsifying agent and mechanical agitation, make monomer dispersion that emulsion is formed in water, add
Initiator trigger monomer is polymerized.The beginning of the thirties, emulsion polymerisation process have been come across in industrial production.Include in many polymer
In the production of synthetic rubber, synthetic fibers, synthetic plastic, flocculant, adhesive, synthetic resin coating and impact copolymer,
Emulsion polymerization has become one of main method, and the polymer in the world by emulsion polymerisation process production is thousands of every year,
Vinyl emulsion polymers emulsion is fastest-rising type, and acrylic acid emulsion polymer emulsion is a maximum class.It is poly-
The manufacture of compound emulsion is notable in the expansion of five annual capacity of past, and the main application fields of polymer emulsion are transport, durable consumer goods
And building and construction industry, and market has very high annual compound growth rate.Emulsion polymerization technology has great to World Economics
Meaning.
Emulsifying agent belongs to surfactant, and it can be the class material to form micella, play important in emulsion polymerization
Effect.Also it is widely used in other each technical fields and daily life simultaneously.In general, emulsifying agent is in reaction
During do not participate in reaction, but it plays very important effect as one of the main component of emulsion polymerization.Traditional emulsion
The emulsifying agent that polymerization is used can be divided into the emulsification of cationic emulsifier, anionic emulsifier, amphoteric emulsifier and nonionic
Agent, and the emulsifying agent and its system of these types has studied more thorough.More importantly traditional emulsifying agent has necessarily
Toxicity, the stability of emulsion of formation is poor, and after polymerisation, emulsifying agent is remained in polymeric articles, affects the performance of product,
Polymerisation needs to post-process product after terminating, and post processing cost is high and can not eliminate completely.
Solid particle can make water phase and an oil phase form stable oil-in-water or water-in-oil emulsion, and use solid particle now
It is less that stable emulsion is polymerized.Magadiite（magadiite）Traditional emulsifying agent can be replaced to gather as emulsifying agent
Macromolecule is closed, and mixes to form polymer nanocomposites with macromolecule, and consumption is conventional emulsifier consumption
Percent zero point several can just reach good emulsifying effectiveness；Made as emulsifying agent with organically-modified magadiite
Pickering type emulsions, carry out emulsion polymerization, and the research for forming polymer nanocomposites does not have so far.
The content of the invention
It is an object of the invention to provide a kind of based on the Pickering emulsions that organically-modified magadiite is emulsifying agent
The method for preparing polymer nanocomposites.
Using organically-modified magadiite as emulsifying agent, polymerized monomer is prepared stable the inventive method as oil phase
Pickering emulsions, then add water-soluble radical polymerization initiator, carry out emulsion polymerization, prepare polymer nanocomposite
Composite.
The present invention is achieved through the following technical solutions.
Pickering emulsions with organically-modified magadiite as emulsifying agent prepare the side of polymer nanocomposites
Method, comprises the steps：
（1）Organically-modified magadiite is added in deionized water, is stirred and is heated up, make organically-modified magadiite uniform
Dispersion is in deionized water；Lower the temperature after being uniformly dispersed, add polymerized monomer, continue stirring, form uniform and stable Pickering
Emulsion；
（2）Heating Pickering emulsions, are added dropwise water-soluble radical polymerization initiator；Heat up after completion of dropping and reacted, instead
Should lower the temperature after terminating, stop stirring, discharging.
Further, step（1）In, 50wt%-90wt% of the deionized water for Pickering emulsions.
Further, step（1）In, 0.01wt%-1wt% of the organically-modified magadiite for polymerized monomer.
Further, step（1）In, the organically-modified magadiite is to change through quaternary ammonium salt, quaternary salt or silane
The magadiite of property.
Further, step（1）In, the polymerized monomer includes styrene, methyl methacrylate or vinylacetate.
Further, step（1）In, it is described to heat up to be warming up to 60-80 DEG C.
Further, step（1）In, the cooling is to be cooled to 40-60 DEG C.
Further, step（2）In, 0.1wt%- of the water-soluble radical polymerization initiator for polymerized monomer
0.5wt%。
Further, step（2）In, the water-soluble radical polymerization initiator includes that persulfate and redox are drawn
One kind in the system of sending out.
Further, step（2）In, the heating is heated to 70-90 DEG C.
Further, step（2）In, the reaction is to react 1-5h at 80-90 DEG C.
Further, step（2）In, the cooling is to be cooled to less than 50 DEG C.
Further, organically-modified magadiite particle constitutes the polymer in being retained in the polymeric material of synthesis
Nano composite material.
Further, the whole stirring of the preparation process.
Compared with prior art, the invention has the advantages that and beneficial effect：
（1）The present invention is good as the emulsifying effectiveness of Pickering emulsions made by emulsifying agent with organically-modified magadiite, has
The consumption of the modified magadiite of machine is compared the consumption of conventional emulsifier and is significantly reduced, and substantially reduces the usage amount of emulsifying agent, saves
About cost；
（2）Organically-modified magadiite is a kind of mineral clay, nontoxic, and environment will not also will not be endangered
Health of the evil to the mankind；
（3）The organically-modified magadiite particle reservation of the present invention may make up polymer nanocomposites in the material, be polymerized
Product need not be post-processed afterwards, and economic benefit is improved, environmentally friendly；
（4）The present invention is strong as Pickering stability of emulsion made by emulsifying agent with organically-modified magadiite, is difficult to receive
The impact of the external environments such as temperature, with long-time stability；
（5）The biocompatibility that organically-modified magadiite has been had with organism, does not affect polymer nanocomposites to exist
The daily lifes such as the industrial circles such as oil exploitation, cosmetics and food and the extensive application of field of medicaments；
（6）The inventive method process is simple, it is easy to operate.
Description of the drawings
Fig. 1 is the infrared spectrogram of obtained polymer nanocomposites in embodiment 1；
Fig. 2 is the infrared spectrogram of obtained polymer nanocomposites in embodiment 2；
Fig. 3 is the infrared spectrogram of obtained polymer nanocomposites in embodiment 3；
Fig. 4 is the X-ray diffractogram of obtained polymer nanocomposites in embodiment 3.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is described in further details, but the invention is not restricted to following enforcement
Example.
Embodiment 1
（1）Sequentially add toward there-necked flask and account for the deionized water of total emulsion quality 50%, account for the ten of polymerized monomer quality 0.01%
The modified magadiite of six alkyl triphenyl phosphonium quaternary salts, starts stirring, is warming up to 60 DEG C, make organically-modified magadiite uniform
After being dispersed in water, 40 DEG C are cooled to, methyl methacrylate monomer is subsequently adding, mixed solution are stirred continuously with oar propeller,
Mixed solution is made to form uniform and stable Pickering emulsions；Appropriate emulsion is taken to finger bottle, can be observed what is be layered before
Water-oil phase becomes uniform milky milk, and by standing observation, emulsion remains stable.
（2）Heating Pickering emulsions to 70 DEG C, accounting for the ammonium persulfate that methyl methacrylate monomer quality is 0.1%
It is added in there-necked flask by constant pressure funnel, the container of splendid attire is washed with deionized after completion of dropping, and is added to
In flask；It is warmed up to 80 DEG C and continues reaction 1h, starts cooling afterwards；When reaction mass temperature is down to below 50 DEG C, stop stirring
Mix, discharge.
The infrared spectrogram of the polymer nanocomposites for obtaining is as shown in figure 1, shown by Fig. 1,1734 cm-1For C=O
The stretching vibration characteristic peak of double bond, and the intensity at peak is big；1488 cm-1With 1448 cm-1It is-CH2- flexural vibrations characteristic absorption
Peak；1281 cm-1With 1244 cm-1It is the asymmetric stretching vibration characteristic peak of-C-O-C-；Understand, the polymer for obtaining is poly-
Methyl methacrylate；And prove that magadiite is stayed by testing.
Use gel permeation chromatography（GPC）Product to obtaining carries out the measure of molecular weight and its dispersiveness, the knot for obtaining
Fruit is as shown in table 1.
1 polymethyl methacrylate of table（PMMA）The molecular weight and its dispersiveness of nano composite material
| Mn | Mw | Mz | Mz+1 | Polydispersity |
| 165639 | 435675 | 903508 | 1349719 | 2.630267 |
As shown in Table 1, the polymethyl methacrylate of higher molecular weight is obtained by Pickering emulsion polymerizations, number is divided equally
Son amount is 165639, and the polydispersity of polymethyl methacrylate（Mw/Mn）About 2.63, molecular weight distribution width.
Embodiment 2
（1）The deionized water for accounting for emulsion gross mass 70% is sequentially added toward there-necked flask, account for that polymerized monomer quality is 0.5% ten
The quaternary ammonium salt-modified magadiite of six alkyl triphenyl phosphoniums, starts stirring, is warming up to 70 DEG C, makes organically-modified magadiite uniform
After being dispersed in water, 50 DEG C are cooled to, styrene monomer is subsequently adding, mixed solution are stirred continuously with oar propeller, make mixing molten
Liquid forms uniform and stable Pickering emulsions；
（2）Heating Pickering emulsions pass through perseverance the cumyl peroxide that styrene monomer quality is 0.3% is accounted for 80 DEG C
Pressure dropping funel is added in there-necked flask, is washed with deionized the container of splendid attire, and is added in flask after completion of dropping；
It is warmed up to 85 DEG C and continues reaction 3h, starts cooling afterwards；When reaction mass temperature is down to below 50 DEG C, stop stirring, discharging.
The infrared spectrogram of the polymer nanocomposites for obtaining as shown in Fig. 2 Fig. 2 shows, 3000-3100 cm-1It is
The stretching vibration characteristic peak of phenyl ring=CH；2924 cm-1With 2851 cm-1It is CH respectively2Asymmetric and symmetrical stretching vibration it is special
Levy peak；The polymer that confirmation is obtained is polystyrene；And prove that magadiite is stayed by testing
Nano composite material.
Embodiment 3
（1）The deionized water for accounting for that emulsion gross mass is 90% is sequentially added toward there-necked flask, it is 1% to account for polymerized monomer quality
The modified magadiite of gamma-aminopropyl-triethoxy-silane, starts stirring, is warming up to 80 DEG C, make organically-modified magadiite
After being dispersed in water, 60 DEG C are cooled to, vinyl acetate monomer is subsequently adding, mixed solution are stirred continuously with oar propeller,
Mixed solution is made to form uniform and stable Pickering emulsions；
（2）Heating Pickering emulsions subsequently pass through the hydrogen peroxide that vinyl acetate monomer quality is 0.5% is accounted for 90 DEG C
Constant pressure funnel is added in there-necked flask, is washed with deionized the container of splendid attire, and is added to flask after completion of dropping
In；90 DEG C of insulation continues reaction 5h, starts cooling afterwards；When reaction mass temperature is down to below 50 DEG C, stops stirring, go out
Material.
The infrared spectrogram of the polymer nanocomposites for obtaining is as shown in figure 3, in 2925 cm-1Place is that C-H is flexible to shake
Dynamic characteristic peak；1739 cm-1Place is the stretching vibration characteristic peak of C=O, and intensity is larger；1443 cm-1Place is CH2 Bending shake
Dynamic characteristic peak；Understand, the polymer for obtaining is polyvinyl acetate.
X-ray diffraction test is carried out to product, test result is as shown in Figure 4：Characteristic diffraction peak in 2 θ=4.34 ° is poly-
The characteristic diffraction peak of vinyl acetate, 24.76 ° -28.60 ° be magadiite characteristic peak region；Illustrate magadiite conducts
Emulsifying agent successfully prepares polymer, and magadiite is stayed.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.It is all the present invention
Any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (10)
1. the Pickering emulsions with organically-modified magadiite as emulsifying agent prepare the side of polymer nanocomposites
Method, it is characterised in that comprise the steps：
（1）Organically-modified magadiite is added in deionized water, is stirred and is heated up, make organically-modified magadiite uniform
Dispersion is in deionized water；Lower the temperature after being uniformly dispersed, add polymerized monomer, continue stirring, form uniform and stable Pickering
Emulsion；
（2）Heating Pickering emulsions, are added dropwise water-soluble radical polymerization initiator；Heat up after completion of dropping and reacted, instead
Should lower the temperature after terminating, stop stirring, discharging.
2. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（1）In, 50wt%- of the deionized water for Pickering emulsions
90wt%。
3. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（1）In, the organically-modified magadiite is polymerized monomer
0.01wt%-1wt%。
4. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（1）In, the organically-modified magadiite be through quaternary ammonium salt,
Quaternary salt or silane-modified magadiite.
5. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（1）In, the polymerized monomer includes styrene, methyl methacrylate
Ester or vinylacetate.
6. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（1）In, it is described to heat up to be warming up to 60-80 DEG C；The cooling is
It is cooled to 40-60 DEG C.
7. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（2）In, the water-soluble radical polymerization initiator is single for polymerization
The 0.1wt%-0.5wt% of body.
8. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（2）In, the water-soluble radical polymerization initiator includes over cure
One kind in hydrochlorate and redox initiation system.
9. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that step（2）In, the heating is heated to 70-90 DEG C；The reaction is
1-5h is reacted at 80-90 DEG C；The cooling is to be cooled to less than 50 DEG C.
10. the Pickering emulsions with organically-modified magadiite as emulsifying agent according to claim 1 prepare polymerization
The method of thing nano composite material, it is characterised in that organically-modified magadiite particle is retained in the polymeric material of synthesis
It is middle to constitute the polymer nanocomposites；The whole stirring of the preparation process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611019424.8A CN106519092B (en) | 2016-11-21 | 2016-11-21 | The method for preparing polymer nanocomposites as the Pickering lotion of emulsifier using organically-modified magadiite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611019424.8A CN106519092B (en) | 2016-11-21 | 2016-11-21 | The method for preparing polymer nanocomposites as the Pickering lotion of emulsifier using organically-modified magadiite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106519092A true CN106519092A (en) | 2017-03-22 |
| CN106519092B CN106519092B (en) | 2019-01-18 |
Family
ID=58352218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611019424.8A Active CN106519092B (en) | 2016-11-21 | 2016-11-21 | The method for preparing polymer nanocomposites as the Pickering lotion of emulsifier using organically-modified magadiite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106519092B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107412193A (en) * | 2017-03-29 | 2017-12-01 | 华南理工大学 | Nano hybridization pharmaceutical carrier and its preparation method prepared by the Pickering emulsion template methods using magadiite as emulsifying agent |
| CN108641024A (en) * | 2018-05-15 | 2018-10-12 | 华南理工大学 | The method of pH value regulation and control synthesis magadiite/PMMA composite nano-microspheres is utilized in Pickering lotions |
| CN111087538A (en) * | 2020-01-02 | 2020-05-01 | 中国科学院长春应用化学研究所 | W/O emulsion and preparation method thereof, polymer particles and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101691A2 (en) * | 2003-05-02 | 2004-11-25 | Dow Global Technologies Inc. | Coating and filler compositions comprising platy layered silicate pigments |
| CN104558356A (en) * | 2014-12-25 | 2015-04-29 | 常州大学 | Method for synthesizing Pickering-type emulsion through semi-continuous polymerization |
| CN105496799A (en) * | 2015-12-28 | 2016-04-20 | 西北工业大学 | Stable photo-responsive Pickering emulsion with photosensitive POSS hybrid particles as emulsifying agent and preparation method |
| CN105858678A (en) * | 2016-02-29 | 2016-08-17 | 华南理工大学 | Preparation method of hybrid type interpenetrating-network-structure material based on magadiite |
-
2016
- 2016-11-21 CN CN201611019424.8A patent/CN106519092B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004101691A2 (en) * | 2003-05-02 | 2004-11-25 | Dow Global Technologies Inc. | Coating and filler compositions comprising platy layered silicate pigments |
| CN104558356A (en) * | 2014-12-25 | 2015-04-29 | 常州大学 | Method for synthesizing Pickering-type emulsion through semi-continuous polymerization |
| CN105496799A (en) * | 2015-12-28 | 2016-04-20 | 西北工业大学 | Stable photo-responsive Pickering emulsion with photosensitive POSS hybrid particles as emulsifying agent and preparation method |
| CN105858678A (en) * | 2016-02-29 | 2016-08-17 | 华南理工大学 | Preparation method of hybrid type interpenetrating-network-structure material based on magadiite |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107412193A (en) * | 2017-03-29 | 2017-12-01 | 华南理工大学 | Nano hybridization pharmaceutical carrier and its preparation method prepared by the Pickering emulsion template methods using magadiite as emulsifying agent |
| WO2018176891A1 (en) * | 2017-03-29 | 2018-10-04 | 华南理工大学 | Hybrid medicament nanocarrier prepared per pickering emulsion template method with megadiite as emulsifier and preparation method for nanocarrier |
| CN108641024A (en) * | 2018-05-15 | 2018-10-12 | 华南理工大学 | The method of pH value regulation and control synthesis magadiite/PMMA composite nano-microspheres is utilized in Pickering lotions |
| WO2019218607A1 (en) * | 2018-05-15 | 2019-11-21 | 华南理工大学 | Method for synthesizing magadiite/pmma nano composite microspheres by using ph value regulation in pickering emulsion |
| CN111087538A (en) * | 2020-01-02 | 2020-05-01 | 中国科学院长春应用化学研究所 | W/O emulsion and preparation method thereof, polymer particles and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106519092B (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3804881A (en) | Polymerization using varying monomer concentration | |
| Landfester | Polyreactions in miniemulsions | |
| CN101955555B (en) | Implementation method of reversible addition fragmentation chain emulsion polymerization | |
| CN103289099B (en) | A kind of amphipathic acid sensitivity ternary molecular brush polymer constructs acid-sensitive type Nano capsule | |
| CN106519092A (en) | Method for preparing polymer nanometer composite by using Pickering emulsion with organic modified magadiite as emulsifying agent | |
| CN101016363A (en) | Poly(styrene-b-butyl acrylate-b-styrene)copolymer latex and preparing method thereof | |
| Wang et al. | Pickering emulsion of metal-free photoinduced electron transfer-ATRP stabilized by cellulose nanocrystals | |
| CN103254374A (en) | Toughed transparent plastic containing glass transition temperature-adjustable block and preparation method of plastic | |
| Hungenberg et al. | Trends in emulsion polymerization processes from an industrial perspective | |
| Ahamad Said et al. | Polymerization and applications of poly (methyl methacrylate)–graphene oxide nanocomposites: a review | |
| Lv et al. | Rod–coil block copolymer aggregates via polymerization-induced self-assembly | |
| CN103936948A (en) | Poly(methyl) crylic acid-b-styrene-b-styrene/acrylonitrile) segmented copolymer latex and preparation method thereof | |
| Xu et al. | Nanoparticle surface cross-linking: A universal strategy to enhance the mechanical properties of latex films | |
| CN107532065A (en) | Heat-expandable microsphere and application thereof | |
| CN104861107A (en) | Preparation method for silicone-acrylic miniemulsion | |
| CN114015000B (en) | Preparation method of block copolymer latex | |
| CN108699188B (en) | Vinyl chloride-vinyl acetate copolymer particles and automobile lower body coating agent | |
| CN105916893A (en) | Vinyl chloride-based polymer and method for producing same | |
| Wang et al. | Synthesis of a Cross-Linked Poly (vinyl chloride) Microsphere by Self-Stabilized Precipitation Polymerization and Its Contribution to Superior Enhancement in Toughness and Mechanical Strength of Rigid PVC | |
| FI76813C (en) | Stable and amphoteric latexes of copolymers based on conjugated dyes. | |
| Yang et al. | Ab initio emulsion RAFT polymerization of vinylidene chloride mediated by amphiphilic macro‐RAFT agents | |
| JP5992547B2 (en) | Method for producing microcapsule particles and method for producing hollow particles | |
| CN110402257A (en) | Lotion, the preparation method of lotion and the method for forming film using lotion | |
| Borisova et al. | Synthesis of amphiphilic block-gradient copolymers of styrene and acrylic acid by Nitroxide Mediated Polymerization | |
| CN105949370A (en) | High-strength rapid water absorption resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |