CN102816274B - 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
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- CN102816274B CN102816274B CN201210234466.9A CN201210234466A CN102816274B CN 102816274 B CN102816274 B CN 102816274B CN 201210234466 A CN201210234466 A CN 201210234466A CN 102816274 B CN102816274 B CN 102816274B
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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 Nano capsule field, relate in particular to silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere and preparation method thereof.
Background technology
At present, the small molecules tensio-active agent generally using in letex polymerization, exist a lot of weak points, for example, although such tensio-active agent has certain emulsifying effectiveness, when letex polymerization, play a role in the stage that needs tensio-active agent, and in the time of the inessential stage in later stage, do not bring into play effect, and residual tensio-active agent may cause environmental problem, the free surfactant containing in the finished product even may produce some negative impacts to the performance of product, 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 utilizing between isocyano and hydroxyl, generate low-molecular-weight base polyurethane prepolymer for use as, then introduce hydrophilic radical, and with C=C, it is carried out to end-blocking, realize the radical polymerization between itself and monomer.Therefore, it ideally combines polymerizability and traditional small-molecular emulsifier surfactivity, make it not only there is the emulsifying effectiveness of small molecules tensio-active agent hydrophilic and oleophilic, and the introducing of two keys in molecular chain, make its in emulsion by radical polymerization, by emulsifying agent by the effect of chemical bond, permanent being keyed on emulsion particle.So aqueous polyurethane is as polymerisable surfactant, have that molecular structure designability is strong, noresidue after reaction, do not affect even the advantages such as improved products performance, in letex polymerization, micro-emulsion polymerization and mini-emulsion polymerization, obtain very large application.
The 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, they have the ability of encapsulated drug, are applicable to drug delivery.But medicine discharges in advance, it is a major challenge that limits its application always.For addressing this problem, someone attempts utilizing linking agent to be cross-linked shell polymkeric substance, increases the density of shell, slows down the release rate of medicine, the difficult problem discharging in advance to solving medicine.But effect is very unobvious, most of linking agents are homemade, and preparation process is loaded down with trivial details, complex process, and the encapsulated drug release effect of preparing is bad.
Summary of the invention
The object of this invention is to provide a kind of silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere and preparation method thereof.
The present invention adopts following technical scheme to achieve these goals:
Silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, is characterized in that: its be take silicon dioxide microsphere as core, the bivalve layer complex microsphere of vinylbenzene as outer shell, methyl methacrylate as inner layer case; It is to be made up of the raw material of following weight parts:
Methyl methacrylate 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 made up of the raw material of following weight parts:
Vulcabond 8.88-10.61
Oligopolymer dibasic alcohol 18-22
Chainextender 1.34-2.39
Hydroxyethyl methylacrylate 2-4
Triethylamine 0.8-1.2.
Described silicon-dioxide/poly-(Methyl Methacrylate-Styrene) 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, dicyclohexyl methane diisocyanate.
Described silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, it is characterized in that: described oligopolymer dibasic alcohol is polypropylene glycol, polytetrahydrofuran, polyoxytrimethylene, polyoxyethylene glycol the mixture of one or more in poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, polybutylene glyool adipate, poly-carbonic acid hexylene glycol esterdiol.
Described silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, it is characterized in that: described chainextender is hydrophilic chain extender, it is one or more the mixture in dimethylol propionic acid (DMPA), dihydroxyl half ester, BDO-2-sodium sulfonate.
The preparation method of described silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, is characterized in that: comprise the following steps:
(1) get by weight vulcabond and oligopolymer dibasic alcohol, in atmosphere of inert gases, in 60-100 ℃ of reaction 2-3 hour, add by weight chainextender, in 60-100 ℃ of reaction 3-4 hour, be cooled to 50-65 ℃, add by weight again hydroxyethyl methylacrylate, reaction 3-4h, in the product obtaining, add triethylamine by weight in and after, under violent stirring, add water to carry out emulsion dispersion, obtain aqueous polyurethane;
(2) fully dissolve and mix methyl methacrylate by weight, n-Hexadecane, Diisopropyl azodicarboxylate, γ-methacryloxypropyl trimethoxy silane and tetraethoxy are as oil phase, get by weight again step (1) gained aqueous polyurethane soluble in water as water, oil phase is slowly added in water, pre-emulsification 0.5-1h, under ice-water bath, utilize the thin emulsification 2-5min of high-speed shearing equipment, and be transferred to immediately in there-necked flask, under whipped state, logical nitrogen 0.5-1h is to get rid of system air, at 70-80 ℃ after water-bath 0.5-1h, drip by weight again ammoniacal liquor, continue after reaction 2-3h, drip appropriate vinylbenzene, continue reaction 5-8h, centrifugal, purify, obtain.
Principle of the present invention is: the present invention utilizes homemade aqueous polyurethane as tensio-active agent, adopts miniemulsion legal system for a kind of Nano capsule with two shell structures.
Beneficial effect of the present invention:
(1) homemade aqueous polyurethane narrow molecular weight distribution, molecular size range easily regulates, and wetting ability size can be by the adjustment control of filling a prescription, and stability is better;
(2) using the aqueous polyurethane of two key end-blockings as tensio-active agent, there is polymerizability, can not only play better emulsifying effectiveness, and activated pair of key of tool, can participate in the polymerization between monomer, and play crosslinked to a certain extent effect.And, can, by selecting synthesis material, prepare the aqueous polyurethane with biological degradability as tensio-active agent;
(3) this method tensio-active agent aqueous polyurethane synthesis material used is originated extensively, is cheaply easy to get, and technique is simple, is easy to suitability for industrialized production;
(4) adopt two standby particles of original position miniemulsion legal system, there is average particle size little, reaction conditions gentleness, technique is simple, is easy to control the features such as operation Yi Hang;
(5) preparation of bivalve layer structure composite microballoon, for nuclear shell structure nano capsule coating medicine provides template, can effectively solve pharmaceutical pack and cover the problem of process medicine early release, and Nano capsule coating medicine, can better realize and discharging and result for the treatment of.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
Prepare aqueous polyurethane and comprise following raw materials according:
8.88 parts of isophorone diisocyanate IPDI
20 parts of polypropylene glycol PPG
1.34 parts of dimethylol propionic acid DMPA
2.86 parts of hydroxyethyl methylacrylate HEMA
1.01 parts of triethylamine TEA
Concrete preparation method is as follows:
Take IPDI and PPG (relative molecular mass 1000), pass into nitrogen, the air in eliminating system, in 85 ℃ of reactions 3 hours; Add DMPA, in 85 ℃ of reactions 3 hours; Be cooled to 70 ℃, add HEMA to carry out end capping 3 hours; Be cooled to 50 ℃, in system, add TEA neutralization, rapid stirring also adds water-dispersion, obtains aqueous polyurethane.
Prepare silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere and comprise following raw materials according:
14 parts of methyl methacrylate 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, water
Concentration is 28% NH
3h
21.5 parts of O
Concrete preparation method is as follows:
Take WPU and be dissolved in distilled water as water, MMA, TEOS, MPS, HD and AIBN are as oil phase, after being uniformly mixed, oil phase slowly adds in water, room temperature lower magnetic force stirs pre-emulsification 30min, then homogenizing emulsifying 2min under frozen water cryostat, high speed shear, mixture is transferred in the 250mL four-hole round-bottomed flask that thermometer, agitator and reflux condensing tube are housed to logical N under whipped state
230min, then 70 ℃ of reaction 1.5h of water-bath, drip NH
3h
2o continues reaction 3 hours, drips St, continues reaction 5-8 hour, cooling discharge, and separating-purifying obtains bivalve layer complex microsphere.
Embodiment 2
The raw material and the concrete preparation method that prepare aqueous polyurethane are as follows:
(with embodiment 1)
Prepare silicon-dioxide/P (MMA-St) bivalve layer structure composite microballoon and comprise following raw materials according:
14 parts of methyl methacrylate 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, water
Concentration is 28% NH
3h
21.5 parts of O
Concrete preparation method is as follows:
(with embodiment 1)
Embodiment 3
The raw material and the concrete preparation method that prepare aqueous polyurethane are as follows:
(with embodiment 1)
Prepare silicon-dioxide/P (MMA-St) bivalve layer structure composite microballoon and comprise following raw materials according:
12 parts of methyl methacrylate 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, water
Concentration is 28% NH
3h
21.5 parts of O
Concrete preparation method is as follows:
(with embodiment 1)
Embodiment 4
The raw material and the concrete preparation method that prepare aqueous polyurethane are as follows:
(with embodiment 1)
Prepare silicon-dioxide/P (MMA-St) bivalve layer structure composite microballoon and comprise following raw materials according:
12 parts of methyl methacrylate 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, water
Concentration is 28% NH
3h
21.5 parts of O
Concrete preparation method is as follows:
(with embodiment 1).
Claims (4)
1. silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, is characterized in that: its be take silicon dioxide microsphere as core, the bivalve layer complex microsphere of vinylbenzene as outer shell, methyl methacrylate as inner layer case; It is to be made up of the raw material of following weight parts:
Methyl methacrylate 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 made up of the raw material of following weight parts:
Vulcabond 8.88-10.61
Oligopolymer dibasic alcohol 18-22
Chainextender 1.34-2.39
Hydroxyethyl methylacrylate 2-4
Triethylamine 0.8-1.2;
The preparation method of described silicon-dioxide/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, comprises the following steps:
(1) get by weight vulcabond and oligopolymer dibasic alcohol, in atmosphere of inert gases, in 60-100 ℃ of reaction 2-3 hour, add by weight chainextender, in 60-100 ℃ of reaction 3-4 hour, be cooled to 50-65 ℃, add by weight again hydroxyethyl methylacrylate, reaction 3-4h, in the product obtaining, add triethylamine by weight in and after, under violent stirring, add water to carry out emulsion dispersion, obtain aqueous polyurethane;
(2) fully dissolve and mix methyl methacrylate by weight, n-Hexadecane, Diisopropyl azodicarboxylate, γ-methacryloxypropyl trimethoxy silane and tetraethoxy are as oil phase, get by weight again step (1) gained aqueous polyurethane soluble in water as water, oil phase is slowly added in water, pre-emulsification 0.5-1h, under ice-water bath, utilize the thin emulsification 2-5min of high-speed shearing equipment, and be transferred to immediately in there-necked flask, under whipped state, logical nitrogen 0.5-1h is to get rid of system air, at 70-80 ℃ after water-bath 0.5-1h, drip by weight again ammoniacal liquor, continue after reaction 2-3h, drip appropriate vinylbenzene, continue reaction 5-8h, centrifugal, purify, obtain.
2. silicon-dioxide according to claim 1/poly-(Methyl Methacrylate-Styrene) 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, dicyclohexyl methane diisocyanate.
3. silicon-dioxide according to claim 1/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, it is characterized in that: described oligopolymer dibasic alcohol is polypropylene glycol, polytetrahydrofuran, polyoxytrimethylene, polyoxyethylene glycol the mixture of one or more in poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, polybutylene glyool adipate, poly-carbonic acid hexylene glycol esterdiol.
4. silicon-dioxide according to claim 1/poly-(Methyl Methacrylate-Styrene) bivalve layer complex microsphere, it is characterized in that: described chainextender is hydrophilic chain extender, it is one or more the mixture in dimethylol propionic acid (DMPA), dihydroxyl half ester, BDO-2-sodium sulfonate.
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| 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 |
| CN104892833B (en) * | 2015-05-21 | 2017-03-29 | 安徽大学 | A kind of preparation method of the hollow microgel of polyacrylic acid |
| CN105622891B (en) * | 2015-12-21 | 2018-04-17 | 江南大学 | A kind of preparation method of polysiloxane emulsion modified aqueous polyurethane emulsion |
| 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 |
| 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 |
| CN114560468B (en) * | 2022-02-25 | 2022-09-16 | 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 |
| CN114917847B (en) * | 2022-05-23 | 2023-06-30 | 华南理工大学 | Silica microsphere and preparation method and application thereof |
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