CN102816274A - Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method - Google Patents
Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method Download PDFInfo
- Publication number
- CN102816274A CN102816274A CN2012102344669A CN201210234466A CN102816274A CN 102816274 A CN102816274 A CN 102816274A CN 2012102344669 A CN2012102344669 A CN 2012102344669A CN 201210234466 A CN201210234466 A CN 201210234466A CN 102816274 A CN102816274 A CN 102816274A
- Authority
- CN
- China
- Prior art keywords
- teb
- vinylbenzene
- weight
- silicon
- aqueous polyurethane
- 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
Images
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention discloses a silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method. According to the preparation method, self-made aqueous polyurethane is used as a surfactant, a double in situ miniemulsion method is adopted, in-situ hydrolysis of ethyl orthosilicate and in-situ polymerization of methyl methacrylate are utilized, and a second monomer styrene is subsequently added drop by drop so as to prepare the silica/poly(methyl methacrylate-styrene) double-layered composite microsphere. The method provided by the invention has a simple technology, is easy to operate, requires a mild reaction condition and is easy to control. Particles obtained are uniform in size. In addition, the mononuclear double-layered composite microsphere can be obtained by changing the additive amount of aqueous polyurethane and contents of monomer methyl methacrylate and styrene.
Description
Technical field
The invention belongs to the Nano capsule field, relate in particular to silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere and preparation method thereof.
Background technology
At present, the small molecules tensio-active agent that generally uses in the letex polymerization exists a lot of weak points; For example; Though such tensio-active agent has certain emulsifying effectiveness, during letex polymerization, play a role in the stage that needs tensio-active agent; And when inessential stage in later stage performance not effect; And residual surfactant may cause environmental problem, the free surfactant that contains in the finished product even possibly produce some negative impacts to performance of products, and this has limited the range of application of the finished product.Aqueous polyurethane is as a kind of novel polymerisable surfactant; More and more gain great popularity; It is the condensation reaction that utilizes between isocyano and the hydroxyl, generates low-molecular-weight base polyurethane prepolymer for use as, introduces hydrophilic radical then; And it is carried out end-blocking with C=C, realized the radical polymerization between itself and the monomer.Therefore; It ideally combines polymerizability and traditional small-molecular emulsifier surfactivity; Make its emulsifying effectiveness that not only has small molecules tensio-active agent hydrophilic and oleophilic, and the introducing of two keys in the molecular chain, make its in emulsion through radical polymerization; With the effect of emulsifying agent through chemical bond, permanent being keyed on the emulsion particle.So aqueous polyurethane is as polymerisable surfactant, have that the molecular structure designability is strong, reaction back noresidue, do not influence even advantage such as improved products performance, in letex polymerization, micro-emulsion polymerization and mini-emulsion polymerization, obtained very big application.
Nano capsule with nucleocapsid structure has obtained extensive concern, has very strong application prospect in fields such as electrochemistry, plastics, biological activity, photochemical catalysis and medical science.The more important thing is that they have the ability of encapsulated drug, be applicable to that medicine sends.But medicine discharges in advance, is a major challenge that limits its application always.For addressing this problem, it is crosslinked that the someone attempts utilizing linking agent that the shell polymkeric substance is carried out, and increases the density of shell, slows down the release rate of medicine, in the hope of solving the difficult problem that medicine discharges in advance.But effect is very unobvious, and most of linking agents are homemade, and the preparation process is loaded down with trivial details, complex process, and the capsule entrapped drug releasing effect of preparing is bad.
Summary of the invention
The purpose of this invention is to provide a kind of silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere and preparation method thereof.
The present invention adopts following technical scheme to achieve these goals:
Silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere is characterized in that: it is to be that nuclear, vinylbenzene are that outer shell, TEB 3K are the bivalve layer complex microsphere of inner layer case with the silicon dioxide microsphere; It is to be processed by the raw material of following weight parts:
TEB 3K 12-16
γ-methacryloxypropyl trimethoxy silane 1.2
Tetraethoxy 5-7
N-Hexadecane 0.6-1
Diisopropyl azodicarboxylate 0.15-0.25
Aqueous polyurethane 0.18-1.76
Vinylbenzene 6-12
Water 75-85
Concentration is ammoniacal liquor 1-3 part of 28%
Described aqueous polyurethane is to be processed by the raw material of following weight parts:
Vulcabond 8.88-10.61
Oligopolymer divalent alcohol 18-22
Chainextender 1.34-2.39
Rocryl 400 2-4
Triethylamine 0.8-1.2.
Described silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere; It is characterized in that: described vulcabond is one or more the mixture in isophorone diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, the dicyclohexyl methane diisocyanate.
Described silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere; It is characterized in that: described oligopolymer divalent alcohol is W 166, THF homopolymer, polyoxytrimethylene, polyoxyethylene glycol, poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, gathers adipate glycol-propylene glycol ester glycol, poly adipate succinic acid ester glycol, gathers one or more the mixture in the carbonic acid pinakon esterdiol.
Described silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere; It is characterized in that: described chainextender is a hydrophilic chain extender; It is dimethylol propionic acid (DMPA), dihydroxyl half ester, 1, the mixture of one or more in 4-butyleneglycol-2-sodium sulfonate.
The preparation method of described silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere is characterized in that: may further comprise the steps:
(1) gets vulcabond and oligopolymer divalent alcohol by weight, in atmosphere of inert gases, in 60-100 ℃ of reaction 2-3 hour; Add chainextender by weight,, be cooled to 50-65 ℃ in 60-100 ℃ of reaction 3-4 hour; Add Rocryl 400 more by weight, reaction 3-4h, in the product that obtains, add by weight in the triethylamine with after; Under violent stirring, add entry and carry out the emulsification dispersion, obtain aqueous polyurethane;
(2) fully dissolve mixing TEB 3K, n-Hexadecane, Diisopropyl azodicarboxylate, γ-methacryloxypropyl trimethoxy silane and tetraethoxy by weight as oil phase, it is soluble in water as water to get step (1) gained aqueous polyurethane more by weight, and oil phase is slowly added aqueous phase; Emulsification 0.5-1h utilizes the thin emulsification 2-5min of high-speed shearing equipment, and is transferred in the there-necked flask immediately under the ice-water bath in advance; Logical nitrogen 0.5-1h is to get rid of the system air under the whipped state; Behind 70-80 ℃ of following water-bath 0.5-1h, dropping ammonia by weight again, continue reaction 2-3h after; Drip an amount of vinylbenzene; Continue reaction 5-8h, centrifugal, purification promptly gets.
Principle of the present invention is: the present invention utilizes homemade aqueous polyurethane as tensio-active agent, adopts the miniemulsion method to prepare a kind of Nano capsule with bivalve layer structure.
Beneficial effect of the present invention:
(1) homemade aqueous polyurethane narrow molecular weight distribution, the molecular weight size is regulated easily, and the wetting ability size can be passed through the control of adjustment prescription, and stability is better;
(2) with the end capped aqueous polyurethane of two keys as tensio-active agent, have polymerizability, can not only play better emulsifying effectiveness, and have active pair of key, can participate in the polymerization between the monomer, and play crosslinked to a certain extent effect.And, can be through the aqueous polyurethane selecting synthesis material, prepare to have biological degradability as tensio-active agent;
(3) the used tensio-active agent aqueous polyurethane synthesis material of this method is originated extensively, cheaply is easy to get, and technology is simple, is easy to suitability for industrialized production;
(4) adopt the particle of two original position miniemulsion methods preparations, it is little to have an average particle size, and reaction conditions is gentle, and technology is simple, is easy to control, characteristics such as operation Yi Hang;
(5) preparation of bivalve layer structure complex microsphere for nuclear shell structure nano capsule coating medicine provides template, can effectively solve the problem that medicine coats the early release of process medicine, and the Nano capsule coating medicine, can better realize discharging and result of treatment.
Description of drawings
Fig. 1 is silicon-dioxide/the gather transmission electron microscope picture of (TEB 3K-vinylbenzene) bivalve layer complex microsphere.
Embodiment
Below in conjunction with embodiment the present invention is done explanation further.
Embodiment 1
The preparation aqueous polyurethane comprises following raw materials according:
8.88 parts of isophorone diisocyanate IPDI
20 parts of W 166 PPG
1.34 parts of dimethylol propionic acid DMPA
2.86 parts of Rocryl 400 HEMA
1.01 parts of triethylamine TEA
Concrete preparation method is following:
Take by weighing IPDI and PPG (relative molecular mass 1000), feed nitrogen, the air in the eliminating system was in 85 ℃ of reactions 3 hours; Add DMPA, in 85 ℃ of reactions 3 hours; Be cooled to 70 ℃, add HEMA and carried out end capping 3 hours; Be cooled to 50 ℃, in system, add the TEA neutralization, stir fast and add water-dispersion, obtain aqueous polyurethane.
Preparation silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere comprises following raw materials according:
14 parts of TEB 3K MMA
1.2 parts of γ-methacryloxypropyl trimethoxy silane MPS
6 parts of tetraethoxy TEOS
0.8 part of n-Hexadecane HD
0.2 part of Diisopropyl azodicarboxylate AIBN
0.88 part of aqueous polyurethane WPU
7 parts of vinylbenzene St
80 parts in water
Concentration is 28% NH
3H
21.5 parts of O
Concrete preparation method is following:
Take by weighing WPU and be dissolved in zero(ppm) water as water; MMA, TEOS, MPS, HD and AIBN are as oil phase; Treat that oil phase mixes the back and slowly adds aqueous phase, the room temperature lower magnetic force stirs preparatory emulsification 30min, homogenizing emulsifying 2min under frozen water cryostat then, the high speed shear; Mixture is transferred in the 250mL four-hole round-bottomed flask that TM, whisking appliance and reflux condensing tube are housed the down logical N of whipped state
230min, 70 ℃ of reactions of water-bath 1.5h drips NH then
3H
2O continues reaction 3 hours, drips St, continues reaction 5-8 hour, cooling discharge, and separating purifies obtains bivalve layer complex microsphere.
Embodiment 2
The raw material and the concrete preparation method of preparation aqueous polyurethane are following:
(with embodiment 1)
Preparation silicon-dioxide/P (MMA-St) bivalve layer structure complex microsphere comprises following raw materials according:
14 parts of TEB 3K MMA
1.2 parts of γ-methacryloxypropyl trimethoxy silane MPS
6 parts of tetraethoxy TEOS
0.8 part of n-Hexadecane HD
0.2 part of Diisopropyl azodicarboxylate AIBN
1.76 parts of aqueous polyurethane WPU
7 parts of vinylbenzene St
80 parts in water
Concentration is 28% NH
3H
21.5 parts of O
Concrete preparation method is following:
(with embodiment 1)
Embodiment 3
The raw material and the concrete preparation method of preparation aqueous polyurethane are following:
(with embodiment 1)
Preparation silicon-dioxide/P (MMA-St) bivalve layer structure complex microsphere comprises following raw materials according:
12 parts of TEB 3K MMA
1.2 parts of γ-methacryloxypropyl trimethoxy silane MPS
6 parts of tetraethoxy TEOS
0.8 part of n-Hexadecane HD
0.2 part of Diisopropyl azodicarboxylate AIBN
0.88 part of aqueous polyurethane WPU
12 parts of vinylbenzene St
80 parts in water
Concentration is 28% NH
3H
21.5 parts of O
Concrete preparation method is following:
(with embodiment 1)
Embodiment 4
The raw material and the concrete preparation method of preparation aqueous polyurethane are following:
(with embodiment 1)
Preparation silicon-dioxide/P (MMA-St) bivalve layer structure complex microsphere comprises following raw materials according:
12 parts of TEB 3K MMA
1.2 parts of γ-methacryloxypropyl trimethoxy silane MPS
6 parts of tetraethoxy TEOS
0.8 part of n-Hexadecane HD
0.2 part of Diisopropyl azodicarboxylate AIBN
1.76 parts of aqueous polyurethane WPU
12 parts of vinylbenzene St
80 parts in water
Concentration is 28% NH
3H
21.5 parts of O
Concrete preparation method is following:
(with embodiment 1).
Claims (5)
1. silicon-dioxide/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere, it is characterized in that: it is to be that nuclear, vinylbenzene are that outer shell, TEB 3K are the bivalve layer complex microsphere of inner layer case with the silicon dioxide microsphere; It is to be processed by the raw material of following weight parts:
TEB 3K 12-16
γ-methacryloxypropyl trimethoxy silane 1.2
Tetraethoxy 5-7
N-Hexadecane 0.6-1
Diisopropyl azodicarboxylate 0.15-0.25
Aqueous polyurethane 0.18-1.76
Vinylbenzene 6-12
Water 75-85
Concentration is ammoniacal liquor 1-3 part of 28%
Described aqueous polyurethane is to be processed by the raw material of following weight parts:
Vulcabond 8.88-10.61
Oligopolymer divalent alcohol 18-22
Chainextender 1.34-2.39
Rocryl 400 2-4
Triethylamine 0.8-1.2.
2. silicon-dioxide according to claim 1/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere; It is characterized in that: described vulcabond is one or more the mixture in isophorone diisocyanate, tolylene diisocyanate, '-diphenylmethane diisocyanate, hexamethylene diisocyanate, the dicyclohexyl methane diisocyanate.
3. silicon-dioxide according to claim 1/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere; It is characterized in that: described oligopolymer divalent alcohol is W 166, THF homopolymer, polyoxytrimethylene, polyoxyethylene glycol, poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, gathers adipate glycol-propylene glycol ester glycol, poly adipate succinic acid ester glycol, gathers one or more the mixture in the carbonic acid pinakon esterdiol.
4. silicon-dioxide according to claim 1/gather (TEB 3K-vinylbenzene) bivalve layer complex microsphere; It is characterized in that: described chainextender is a hydrophilic chain extender; It is dimethylol propionic acid (DMPA), dihydroxyl half ester, 1, the mixture of one or more in 4-butyleneglycol-2-sodium sulfonate.
5. a silicon-dioxide as claimed in claim 1/gather the preparation method of (TEB 3K-vinylbenzene) bivalve layer complex microsphere is characterized in that: may further comprise the steps:
(1) gets vulcabond and oligopolymer divalent alcohol by weight, in atmosphere of inert gases, in 60-100 ℃ of reaction 2-3 hour; Add chainextender by weight,, be cooled to 50-65 ℃ in 60-100 ℃ of reaction 3-4 hour; Add Rocryl 400 more by weight, reaction 3-4h, in the product that obtains, add by weight in the triethylamine with after; Under violent stirring, add entry and carry out the emulsification dispersion, obtain aqueous polyurethane;
(2) fully dissolve mixing TEB 3K, n-Hexadecane, Diisopropyl azodicarboxylate, γ-methacryloxypropyl trimethoxy silane and tetraethoxy by weight as oil phase, it is soluble in water as water to get step (1) gained aqueous polyurethane more by weight, and oil phase is slowly added aqueous phase; Emulsification 0.5-1h utilizes the thin emulsification 2-5min of high-speed shearing equipment, and is transferred in the there-necked flask immediately under the ice-water bath in advance; Logical nitrogen 0.5-1h is to get rid of the system air under the whipped state; Behind 70-80 ℃ of following water-bath 0.5-1h, dropping ammonia by weight again, continue reaction 2-3h after; Drip an amount of vinylbenzene; Continue reaction 5-8h, centrifugal, purification promptly gets.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210234466.9A CN102816274B (en) | 2012-07-06 | 2012-07-06 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210234466.9A CN102816274B (en) | 2012-07-06 | 2012-07-06 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102816274A true CN102816274A (en) | 2012-12-12 |
| CN102816274B CN102816274B (en) | 2014-07-02 |
Family
ID=47300749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210234466.9A Expired - Fee Related CN102816274B (en) | 2012-07-06 | 2012-07-06 | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102816274B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017143A (en) * | 2014-04-29 | 2014-09-03 | 安徽大学 | Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof |
| CN104892833A (en) * | 2015-05-21 | 2015-09-09 | 安徽大学 | Preparation method of polyacrylic acid hollow microgel |
| CN105622891A (en) * | 2015-12-21 | 2016-06-01 | 江南大学 | Preparation method for polysiloxane emulsion modified waterborne polyurethane emulsion |
| CN109266266A (en) * | 2018-08-30 | 2019-01-25 | 浙江理工大学 | A kind of water polyacrylic acid/polyurethane/SiO2The preparation method of nano combined binder |
| CN109575223A (en) * | 2018-12-28 | 2019-04-05 | 南京高正农用化工有限公司 | A kind of temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation method thereof |
| CN109943226A (en) * | 2019-03-20 | 2019-06-28 | 深圳市航天新材科技有限公司 | A kind of high class glass masking liquid composition resistant to bending and preparation method thereof |
| CN114560468A (en) * | 2022-02-25 | 2022-05-31 | 金三江(肇庆)硅材料股份有限公司 | Silicon dioxide for chemical mechanical polishing and preparation method and application thereof |
| CN114917847A (en) * | 2022-05-23 | 2022-08-19 | 华南理工大学 | Silicon dioxide microsphere and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446827A (en) * | 2003-04-09 | 2003-10-08 | 吉林大学 | Method for synthesizing nano microsphere of inorganic/polymer huds with narrow decentralization |
| CN1631906A (en) * | 2003-12-23 | 2005-06-29 | 中国科学院理化技术研究所 | Process for preparing monodispersity shell/core composite granular emulsion by using nano silicon dioxide microsphere coated by polystyrene |
| CN1631951A (en) * | 2004-12-02 | 2005-06-29 | 同济大学 | Hollow polymer microsphere and method for preparing same |
| WO2009075652A1 (en) * | 2007-12-11 | 2009-06-18 | Nanyang Technological University | Hollow multi-layered microspheres for delivery of hydrophilic active compounds |
| US20110291057A1 (en) * | 2003-03-13 | 2011-12-01 | Eugenia Kumacheva | Method of producing hybrid polymer-inorganic materials |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
-
2012
- 2012-07-06 CN CN201210234466.9A patent/CN102816274B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110291057A1 (en) * | 2003-03-13 | 2011-12-01 | Eugenia Kumacheva | Method of producing hybrid polymer-inorganic materials |
| CN1446827A (en) * | 2003-04-09 | 2003-10-08 | 吉林大学 | Method for synthesizing nano microsphere of inorganic/polymer huds with narrow decentralization |
| CN1631906A (en) * | 2003-12-23 | 2005-06-29 | 中国科学院理化技术研究所 | Process for preparing monodispersity shell/core composite granular emulsion by using nano silicon dioxide microsphere coated by polystyrene |
| CN1631951A (en) * | 2004-12-02 | 2005-06-29 | 同济大学 | Hollow polymer microsphere and method for preparing same |
| WO2009075652A1 (en) * | 2007-12-11 | 2009-06-18 | Nanyang Technological University | Hollow multi-layered microspheres for delivery of hydrophilic active compounds |
| CN102417552A (en) * | 2011-09-22 | 2012-04-18 | 中国科学院过程工程研究所 | Polymer nanomicrosphere product with uniform and controllable size and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017143A (en) * | 2014-04-29 | 2014-09-03 | 安徽大学 | Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof |
| CN104892833A (en) * | 2015-05-21 | 2015-09-09 | 安徽大学 | Preparation method of polyacrylic acid hollow microgel |
| CN105622891A (en) * | 2015-12-21 | 2016-06-01 | 江南大学 | Preparation method for polysiloxane emulsion modified waterborne polyurethane emulsion |
| CN105622891B (en) * | 2015-12-21 | 2018-04-17 | 江南大学 | A kind of preparation method of polysiloxane emulsion modified aqueous polyurethane emulsion |
| CN109266266A (en) * | 2018-08-30 | 2019-01-25 | 浙江理工大学 | A kind of water polyacrylic acid/polyurethane/SiO2The preparation method of nano combined binder |
| CN109266266B (en) * | 2018-08-30 | 2020-06-19 | 浙江理工大学 | Water-based polyacrylate/polyurethane/SiO2Preparation method of nano composite adhesive |
| CN109575223A (en) * | 2018-12-28 | 2019-04-05 | 南京高正农用化工有限公司 | A kind of temperature and pH stimuli-responsive intelligent polymer microcapsule and preparation method thereof |
| CN109943226A (en) * | 2019-03-20 | 2019-06-28 | 深圳市航天新材科技有限公司 | A kind of high class glass masking liquid composition resistant to bending and preparation method thereof |
| CN109943226B (en) * | 2019-03-20 | 2021-04-13 | 深圳市航天新材科技有限公司 | High-bending-resistance glass coating liquid composition and preparation method thereof |
| CN114560468A (en) * | 2022-02-25 | 2022-05-31 | 金三江(肇庆)硅材料股份有限公司 | Silicon dioxide for chemical mechanical polishing and preparation method and application thereof |
| CN114917847A (en) * | 2022-05-23 | 2022-08-19 | 华南理工大学 | Silicon dioxide microsphere and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102816274B (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102816274B (en) | Silica/poly(methyl methacrylate-styrene) double-layered composite microsphere and its preparation method | |
| Shim et al. | Size control of polystyrene beads by multistage seeded emulsion polymerization | |
| CN103394314B (en) | A kind of preparation method of microcapsules of polyurethane parcel essential oil | |
| CN100422076C (en) | Silicon/charcoal core-shell structure nanometer composite material and its preparation method and uses | |
| CN101775093B (en) | Method for preparing copolymer miniemulsion by stabilizing and modifying reactive co-stabilizer | |
| CN103910832A (en) | Polycarboxylate pesticide dispersing agent and preparation method thereof | |
| CN103387691B (en) | A kind of hollow polystyrene plastic pellet and its preparation method and application | |
| Okubo et al. | Water absorption behavior of polystyrene particles prepared by emulsion polymerization with nonionic emulsifiers and innovative easy synthesis of hollow particles | |
| CN105061689A (en) | Preparation method of powdery polycarboxylic acid high-performance water reducing agent | |
| CN103289099A (en) | Amphiphilic acid-sensitive ternary molecular brush polymer constructed acid-sensitive nanocapsule | |
| CN104017143A (en) | Silicon dioxide/poly(styrene-methyl methacrylate) nonspherical composite microspheres and preparation method thereof | |
| CN103172788B (en) | Preparation method of dispersing agent | |
| CN104273122B (en) | The preparation method of long-acting polyurethane pesticide micro capsule | |
| CN105085939B (en) | Three-dimensional structure and the preparation with electro photoluminescence and the pH polypyrrole/alginate responded and double control insoluble drug release | |
| CN102477220A (en) | Magnetic nylon microspheres with controllable particle size and preparation method thereof | |
| CN104262554A (en) | Self-crosslinking temperature-sensitive organic/inorganic hybrid block copolymer and preparation method thereof | |
| CN104356309A (en) | Preparation method of unsaturated polyester resin low shrinking agent | |
| Liu et al. | Single-Hole Janus Hollow Sphere | |
| Rodríguez et al. | Particle nucleation in high solids miniemulsion polymerization | |
| CN104437284A (en) | Preparation method of phase change microcapsule | |
| CN103772598A (en) | Method for regulating and controlling surface roughness of monodisperse functional polymeric microsphere | |
| CN105905913A (en) | Preparation of silicon dioxide microsphere with nonionic/anionic-combined-type surfactant as soft template | |
| CN102702470B (en) | Method for preparing micro-sized monodisperse polyurea microsphere in static condition | |
| CN102174145B (en) | Temperature-sensitive core-shell acrylate functional microspheres and preparation method thereof | |
| CN107955092A (en) | A kind of gas hydrate nanometer accelerating agent of size tunable and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140702 Termination date: 20150706 |
|
| EXPY | Termination of patent right or utility model |