CN102847496B - Preparation method of calcium ion crosslinked poly(tert-butyl acrylate) microcapsules - Google Patents
Preparation method of calcium ion crosslinked poly(tert-butyl acrylate) microcapsules Download PDFInfo
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- CN102847496B CN102847496B CN201110185436.9A CN201110185436A CN102847496B CN 102847496 B CN102847496 B CN 102847496B CN 201110185436 A CN201110185436 A CN 201110185436A CN 102847496 B CN102847496 B CN 102847496B
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- butyl ester
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Abstract
The invention relates to a preparation method of calcium ion crosslinked poly(tert-butyl acrylate) microcapsules, comprising the following steps of: preparing poly(tert-butyl acrylate) microcapsules by an emulsion polymerisation method; hydrolyzing the part of its superficial layer to obtain surface carboxylated poly(tert-butyl acrylate) microcapsules; crosslinking the surface carboxyl group by the use of calcium ion, and removing the core of the polymer to obtain the calcium ion crosslinked poly(tert-butyl acrylate) microcapsules. According to the invention, polymer microspheres are prepared by a self-templated method; an ionic bond is adopted to crosslink the superficial layer; and a template is etched to obtain the polymer microcapsules which are controllable to disintegrate in an acidic medium. The preparation technology is simple. The prepared polymer microcapsules have a certain application prospect in the fields of drug controlled release and slow release.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of preparation method of polymer microcapsule, specifically a kind of preparation method of polyacrylic acid tert-butyl ester micro-capsule of calcium ion crosslinking.
Background technology
Polymer microcapsule is a kind of micro-, nanoscale material with hollow-core construction, the polymer that the shell of micro-capsule is normally natural or synthetic.Polymer microcapsule, with its superior characteristic, can be widely used in controlled release, the slowly-releasing of medicine, thereby improves curative effect and reduce toxic and side effect, also can be used for dyestuff, the sending of enzyme and gene, the aspect such as protection and catalysis of photosensitive component.
Preparing in the method for functional polymer micro-capsule, emulsion polymerization, template and Self-Assembling of Block Copolymer method are in the news.Aspect the preparation of functional polymer microcapsule, developing easy preparation method is also one of research emphasis of researcher.In the preparation method of functional polymer microcapsule, because, polymer shell layer component controlled at template size can be selected and the advantage of the aspect such as pattern control, template is to have the most a preparation method of application prospect.But, in the matrix polymerization method of having reported, polymerisable or have and cause the group of function and all will first be introduced in and sacrifice the growing point of template surface as polymer shell, also be cross-linked by grafted polymer or directly monomer and crosslinking agent copolymerization formed to cross-linked polymer shell, last etching is removed template.The selection of template in this process, functionalization, polymerization and crosslinked, the various complexity of etching process step, and the crosslinking agent and the etching agent that adopt have toxicity.Equally, template-self assembly layer by layer used polymer be necessary for polyelectrolyte and make its application limited.Based on template, the people such as Liu are at " nanometer technology " (Liu P., Liu G.F., Zhang W., Jiang F.Crosslinked polymeric nanocapsules with controllable structure via a " self-templating " approach.Nanotechnology 2010, 21:015603.), use self-template legal system for polyvinyl acetate ester microsphere, to there is the functional template of surperficial crosslinkable groups (hydroxyl) by glutaraldehyde covalent cross-linking, after removing kernel, obtain polymer nanocomposite capsule, crosslinking agent glutaraldehyde used has toxicity.The present invention on this basis, utilizes ionomer to prepare by self-template technology and has selective disintegration properties polymer microcapsule in acid medium.
Summary of the invention
In view of above-mentioned, the object of this invention is to provide a kind of preparation method of polyacrylic acid tert-butyl ester micro-capsule of calcium ion crosslinking.Prepare polyacrylic acid tert-butyl ester microballoon by emulsion polymerisation process, and adopt ionic crosslinking, the polyacrylic acid tert-butyl ester (PtBA) micro-capsule of controlled disintegration in synthetic acidic medium.
The present invention includes following steps:
A. surfactant being dissolved in distilled water, adding tert-butyl acrylate, and carry out dispersed with stirring, then drip and account for the initator of tert-butyl acrylate molar content 0.64%, is polymerization 8h in the water-bath of 85 DEG C in temperature, must have the white emulsion of opalescence:
B. in the emulsion of step a gained, drip the hydrochloric acid solution of 0.12mol/L, rate of addition is that 5s/ drips, and makes the hydrolysis of polyacrylic acid tert-butyl ester superficial layer, is washed to neutrality;
C. the hydrolysate of step b is scattered in distilled water, adds 0.1% sodium hydroxide solution, regulate pH value to 10.0, the cross-linking agent solution that drips 0.001g/mL is cross-linked;
D. the polyacrylic acid tert-butyl ester microballoon through ionic crosslinking with the rotating speed release surface layer of 12000r/min, removes excessive calcium ion;
E. get polyacrylic acid tert-butyl ester microballoon crosslinked in steps d, add 15mL acetone to remove its inner linear polyacrylic acid tert-butyl ester kernel, obtain the polyacrylic acid tert-butyl ester (PtBA) micro-capsule of calcium ion crosslinking.
Mentioned emulsifier is for being neopelex (SDBS), lauryl sodium sulfate (SBS); Initator is ammonium persulfate (APS), potassium peroxydisulfate (KPS); Crosslinking agent is calcium chloride solution (CaCl
2).
The beneficial effect of advantage of the present invention and generation:
The present invention has successfully prepared polyacrylic acid tert-butyl ester micro-capsule calcium ion crosslinking, alternative disintegration in acid medium by ionic crosslinking technology.Compared with preparing polymer microcapsule with covalent cross-linking, in preparation process, do not use the poisonous crosslinking agent such as vulcabond, glutaraldehyde, in avoiding toxicity, adopt calcium ion cheap and easy to get to prepare polymer microcapsule by ionic crosslinking, be expected to like this realizing the maximum control release concentration of medicine carrying microcapsule to medicine and treating some acute illness in selective dielectric.This method of preparing polyacrylic acid tert-butyl ester micro-capsule has adaptability widely simultaneously, can expand to other polymer billet to prepare the environmental stimulus responsive polymer micro-capsule of various ionic crosslinkings.
In the example of conventional template synthesis cross-linked polymer micro-capsule, generally first can cause by surface modification chemical bonding or polymerisable function base in template, shell coated of realizing template surface cross-linked polymer under certain condition, etching is removed template and is obtained polymer microcapsule.The polymer billet surface that we directly make in emulsion polymerisation in the present invention obtains the polymer microballoon of carboxylated by partial hydrolysis, adopt ionomer technology to make the polyacrylic acid tert-butyl ester micro-capsule of selective disintegration in acid medium.By contrast, polyacrylic acid tert-butyl ester micro-capsule in the present invention has good dispersiveness and dimensional stability, has saved the modification of template and the process of glycerol polymerization thereof in conventional template, and preparation is simple for it, cost is low, and does not use poisonous chemical reagent.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of polyacrylic acid tert-butyl ester emulsion particle in the present invention.
Fig. 2 is the transmission electron microscope photo of the polyacrylic acid tert-butyl ester microballoon after surperficial partial hydrolysis in the present invention.
Fig. 3 is the transmission electron microscope photo of the crosslinked polyacrylic acid tert-butyl ester micro-capsule of intermediate ion key of the present invention.
Fig. 4 is the particle diameter distribution map of each intermediate product in the present invention.
Detailed description of the invention
Below, by reference to the accompanying drawings, technical scheme of the present invention is further described again:
Embodiment 1
A. taking 0.06g neopelex is dissolved in 145mL distilled water, then add 10mL tert-butyl acrylate, and carry out mechanical agitation and disperse 30min, mixing speed is that 300rpm is warming up to 85 DEG C, the speed of dripping with 5s/ drips ammonium persulfate solution (0.1g ammonium persulfate is dissolved in 5mL distilled water), polymerization 8h in water-bath, obtains having the white polypropylene tert-butyl acrylate nano particle (seeing Fig. 1) of opalescence.Can find out from transmission electron microscope Fig. 1, the particle size homogeneous of polyacrylic acid tert-butyl ester nano particle, is 50nm, is uniformly dispersed.The particle diameter of dynamic light scattering test distributes as Fig. 4;
The speed of b. hydrochloric acid solution of 0.12mol/L being dripped with 5s/ splashes in the emulsion of 25mL step a gained, reacts 6 hours.The nano particle centrifuge washing of surperficial partial hydrolysis, to neutral, is scattered in 100mL distilled water for subsequent use.The polyacrylic acid tert-butyl ester nano particle of surface partial hydrolysis is shown in Fig. 2.Can find out from transmission electron microscope Fig. 2: because the nano particle segment hydrolysis stretches, the particle diameter of nano particle increases to 150nm, is uniformly dispersed.The particle diameter of dynamic light scattering test distributes as Fig. 4;
C. get the nanoparticulate dispersed of surperficial partial hydrolysis in 12.5mL step b in 87.5mL distilled water, add 0.1% sodium hydroxide solution, regulator solution pH is 10.0.Under the mechanical agitation of room temperature and 300rpm, the calcium chloride solution that the speed of dripping with 5s/ splashes into 0.001g/mL is cross-linked, reaction 6h;
D. with the crosslinked polyacrylic acid tert-butyl ester microballoon of the rotating speed isolating ions key of 12000r/min, remove excessive calcium ion;
E. under room temperature and magnetic agitation, in crosslinked nano particle, add 15ml acetone in order to remove the linear polypropylene tert-butyl acrylate of the inner capsule of crosslinked shell, react 1 day.Repeat c step 3 time, obtain polyacrylic acid tert-butyl ester nano-microcapsule.Transmission electron microscope is referring to Fig. 3, and the shell of nano-microcapsule is thick is 40nm, and cavity size is 100nm, and is uniformly dispersed.The particle diameter of dynamic light scattering test distributes as Fig. 4.As shown in Figure 4, in the preparation process of polymer microcapsule, after can finding hydrolysis by the result of dynamic light scattering, because the hydrophily of microsphere surface carboxyl increases, polymer chain stretches and makes the particle diameter of microballoon after hydrolysis, become large; After calcium ion crosslinking, crosslinked polymer shell has limited polymer chain and has stretched and its particle diameter is reduced to some extent; After etching template, due to the swelling action in water of polymer microcapsule, it is large that the result of the corresponding transmission electron microscope of size ratio of dynamic light scattering resulting polymers micro-capsule is wanted.In whole preparation process, the nearly single dispersion of distribution of sizes.
Embodiment 2
A. taking 0.06g lauryl sodium sulfate is dissolved in 145mL distilled water, then add 10mL tert-butyl acrylate, and carry out mechanical agitation and disperse 30min, mixing speed is that 300rpm is warming up to 85 DEG C, the speed of dripping with 5s/ drips ammonium persulfate solution (0.1g ammonium persulfate is dissolved in 5mL distilled water), polymerization 8h in water-bath, obtains having the white polypropylene tert-butyl acrylate nano particle of opalescence.Can find out from transmission electron microscope picture, the particle diameter of polyacrylic acid tert-butyl ester nano particle is about 40nm, more difficult resolution spherical morphology, and between particle, bonding phenomenon is serious.
The speed of b. hydrochloric acid solution of 0.12mol/L being dripped with 5s/ splashes in the emulsion of 25mL step a gained, reacts 6 hours.The nano particle centrifuge washing of surface partial hydrolysis, to neutral, is scattered in 100mL distilled water for subsequent use.The polyacrylic acid tert-butyl ester nano particle of surface partial hydrolysis.Can find out from transmission electron microscope picture, the particle diameter of nano particle increases, and bonding phenomenon is serious, particle diameter indistinguishable.
C. get the nanoparticulate dispersed of surperficial partial hydrolysis in 12.5mL step b in 87.5mL distilled water, add 0.1% sodium hydroxide solution, regulator solution pH is 10.0.Under the mechanical agitation of room temperature and 300rpm, the calcium chloride solution that the speed of dripping with 5s/ splashes into 0.001g/mL is cross-linked, reaction 6h.
D. with the crosslinked polyacrylic acid tert-butyl ester microballoon of the rotating speed isolating ions key of 12000r/min, remove excessive calcium ion.
E. under room temperature and magnetic agitation, in crosslinked nano particle, add 15ml acetone in order to remove the linear polypropylene tert-butyl acrylate of the inner capsule of crosslinked shell, react 1 day.Repeat c step 3 time, obtain product and in transmission electron microscope analysis, substantially do not observe hollow-core construction.
Embodiment 3
A. taking 0.06g neopelex is dissolved in 145mL distilled water, then add 10mL tert-butyl acrylate, and carry out mechanical agitation and disperse 30min, mixing speed is that 300rpm is warming up to 85 DEG C, the speed of dripping with 5s/ drips ammonium persulfate solution (0.1g ammonium persulfate is dissolved in 5mL distilled water), polymerization 8h in water-bath, obtains having the white polypropylene tert-butyl acrylate nano particle of opalescence.Can find out from transmission electron microscope picture, the particle diameter of polyacrylic acid tert-butyl ester nano particle is 60nm, has certain agglomeration.
The speed of b. hydrochloric acid solution of 0.12mol/L being dripped with 5s/ splashes in the emulsion of 25mL step a gained, reacts 6 hours.The nano particle centrifuge washing of surperficial partial hydrolysis, to neutral, is scattered in 100mL distilled water for subsequent use.The polyacrylic acid tert-butyl ester nano particle of surface partial hydrolysis.Can find out from transmission electron microscope picture, the particle diameter of nano particle increases to 170nm, and can observe reunion.
C. get the nanoparticulate dispersed of surperficial partial hydrolysis in 12.5mL step b in 87.5mL distilled water, add 0.1% sodium hydroxide solution, regulator solution pH is 10.0.Under the mechanical agitation of room temperature and 300rpm, the calcium chloride solution that the speed of dripping with 5s/ splashes into 0.001g/mL is cross-linked, reaction 6h.
D. with the crosslinked polyacrylic acid tert-butyl ester microballoon of the rotating speed isolating ions key of 12000r/min, remove excessive calcium ion.
E. under room temperature and magnetic agitation, in crosslinked nano particle, add 15ml acetone in order to remove the linear polypropylene tert-butyl acrylate of the inner capsule of crosslinked shell, react 1 day.Repeat c step 3 time, obtain polyacrylic acid tert-butyl ester nano-microcapsule.Can find out from transmission electron microscope picture, the shell of nano-microcapsule is thick is 30nm, and cavity size is 120nm, reunite serious, and nano-microcapsule negligible amounts.
Claims (2)
1. a preparation method for the polyacrylic acid tert-butyl ester micro-capsule of calcium ion crosslinking, comprises the following steps:
A. surfactant being dissolved in distilled water, adding tert-butyl acrylate, and carry out dispersed with stirring, then drip and account for the initator of tert-butyl acrylate molar content 0.64%, is polymerization 8h in the water-bath of 85 DEG C in temperature, must have the white emulsion of opalescence;
B. in the emulsion of step a gained, drip the hydrochloric acid solution of 0.12mol/L, rate of addition is that 5s/ drips, and makes the hydrolysis of polyacrylic acid tert-butyl ester superficial layer, is washed to neutrality;
C. the hydrolysate of step b is scattered in distilled water, adds 0.1% sodium hydroxide solution, regulate pH value to 10.0, the calcium chloride solution that drips 0.001g/mL is cross-linked;
D. the polyacrylic acid tert-butyl ester microballoon through ionic crosslinking with the rotating speed release surface layer of 12000r/min, removes excessive calcium ion;
E. get polyacrylic acid tert-butyl ester microballoon crosslinked in steps d, add 15mL acetone to remove its inner linear polyacrylic acid tert-butyl ester kernel, obtain the polyacrylic acid tert-butyl ester micro-capsule of calcium ion crosslinking.
2. a kind of preparation method of polyacrylic acid tert-butyl ester micro-capsule of calcium ion crosslinking according to claim 1, is characterized in that above-mentioned emulsifying agent is neopelex or is lauryl sodium sulfate; Initator is ammonium persulfate or is potassium peroxydisulfate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1618824A (en) * | 2004-01-16 | 2005-05-25 | 清华大学 | Crosslinked core-shell structure nano-polymer microsphere and its preparation method |
| CN1816389A (en) * | 2003-07-03 | 2006-08-09 | Lg化学株式会社 | Method for preparing microcapsule by miniemulsion polymerization |
| EP1707260A1 (en) * | 2005-03-31 | 2006-10-04 | Ethicon, Inc. | Method of preparing crosslinked collagen microspheres |
| CN1933903A (en) * | 2004-02-23 | 2007-03-21 | 视觉股份公司 | Process for production of ionically crosslinked polysaccharide microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1816389A (en) * | 2003-07-03 | 2006-08-09 | Lg化学株式会社 | Method for preparing microcapsule by miniemulsion polymerization |
| CN1618824A (en) * | 2004-01-16 | 2005-05-25 | 清华大学 | Crosslinked core-shell structure nano-polymer microsphere and its preparation method |
| CN1933903A (en) * | 2004-02-23 | 2007-03-21 | 视觉股份公司 | Process for production of ionically crosslinked polysaccharide microspheres |
| EP1707260A1 (en) * | 2005-03-31 | 2006-10-04 | Ethicon, Inc. | Method of preparing crosslinked collagen microspheres |
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