CN107456996A - A kind of pH/ responsive to temperature type complex microsphere and its preparation method and application - Google Patents

A kind of pH/ responsive to temperature type complex microsphere and its preparation method and application Download PDF

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Publication number
CN107456996A
CN107456996A CN201710579249.6A CN201710579249A CN107456996A CN 107456996 A CN107456996 A CN 107456996A CN 201710579249 A CN201710579249 A CN 201710579249A CN 107456996 A CN107456996 A CN 107456996A
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styrene
methacrylic acid
complex microsphere
isopropylacrylamide
responsive
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CN107456996B (en
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徐祖顺
廖光福
李庆
赵文哲
庞秋虎
喻春函
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Hubei University
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Hubei University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/40—
    • B01J35/51—
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

The invention provides a kind of pH/ responsive to temperature type complex microsphere, polymer microballoon that the complex microsphere is polymerized by styrene, N-isopropylacrylamide, methacrylic acid these three monomers, then in the polymer microballoon adsorption Nano Silver.Further, the invention provides the preparation method of above-mentioned composite nano-microsphere, poly- (styrene N-isopropylacrylamide methacrylic acid) microballoon is prepared first by emulsifier-free emulsion polymerization, then as base material, in its area load Nano Silver, poly- (styrene N-isopropylacrylamide methacrylic acid)/silver nanoparticle complex microsphere is prepared.Composite nano-microsphere prepared by the present invention not only has good temperature-responsive and pH response performances, but also the performance with good catalytic degradation methylene blue, has very high application value in terms of sewage disposal.

Description

A kind of pH/ responsive to temperature type complex microsphere and its preparation method and application
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of pH/ responsive to temperature type complex microsphere and its system Preparation Method and application.
Background technology
In recent years, nano structural material causes the extensive concern of people because of its unique chemistry, physics, biological nature. Particularly metal nanoparticle and its metal oxide, such as Ag, Au, Cu, TiO2, ZnO.These nano structural materials are being catalyzed Agent field has been obtained for widely using.The Nano silver grain catalysis material very high as a kind of catalytic efficiency, in sewage Processing, photocatalytic degradation and photocatalysis hydrogen production etc. have very important application.However, single Nano Silver is as catalysis Material has a series of shortcomings such as easily oxidized, easy reunion and high cost.In order to solve these problems, many methods are tasted Examination, most important of which method is exactly to mix Ag to various substrate surfaces.Being typically prepared this kind of Ag nano composite materials needs two Step, first, base material is activated, and then, nanometer Ag is downloaded to substrate surface.Need to add many surface-actives in preparation process Agent, stabilizer and its reducing agent, these reagents typically all pollute the environment, therefore particularly heavy from a kind of environment-friendly method Will.Polyvinylpyrrolidone (PVP) is a kind of reducing agent and stabilizer well when Ag nano composite materials are prepared, and is subtracted The addition of many toxic reagents is lacked, has been a kind of environment-friendly method.Poly- (the styrene-nitrogen isopropyl third that the present invention uses Acrylamide-methacrylic acid) microballoon benefit, complex microsphere pH and temperature sensitivity energy can be mainly provided, pass through regulation Temperature and pH value；Catalytic performance is directly adjusted, there is good application value.
The content of the invention
In view of this, the invention provides a kind of pH/ responsive to temperature type complex microsphere and its preparation method and application, the system Preparation Method is simple, gentle and environmentally friendly, and any toxic reagent is not added in reaction system.
First aspect present invention provides a kind of preparation method of pH/ responsive to temperature type complex microsphere, and step includes：
S1, poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon preparation：By styrene, nitrogen isopropyl Acrylamide, methacrylic acid, initiator react 6-10h at 78-85 DEG C, centrifugation, washing, it is dry must poly- (styrene-nitrogen be different Propylacrylamide-methacrylic acid) microballoon；
S2, poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere preparation：To go from Poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon prepared by sub- water, polyvinylpyrrolidone and step S1 mixes Mixed liquor is closed to obtain, silver ammino solution is added in mixed liquor, being sufficiently stirred at 15~35 DEG C makes silver-colored ammonium ion be adsorbed onto poly- (benzene second Alkene-N-isopropylacrylamide-methacrylic acid) microsphere surface, 68-72 DEG C is warming up to, reacts 7-12h under nitrogen atmosphere, from The heart, washing, drying, obtain poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere.
Second aspect of the present invention provides a kind of pH/ responsive to temperature type complex microsphere, and the composite nano-microsphere is by benzene second The polymer microballoon that these three monomers of alkene, N-isopropylacrylamide, methacrylic acid are polymerized is then micro- in the polymer Ball surface adsorbs Nano Silver.
Third aspect present invention provides application of the above-mentioned pH/ responsive to temperature type complex microsphere in sewage disposal.
The beneficial effects of the invention are as follows：The preparation method of the present invention is simple, gentle and environmentally friendly, no in reaction system to add Enter any toxic reagent.Material prepared by the present invention not only has good temperature-responsive and pH response performances, but also has There is the performance of good catalytic degradation methylene blue, catalytic performance can be adjusted by adjusting pH value and temperature, at sewage There is very high application value in terms of reason.
Brief description of the drawings
Fig. 1 is poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon and poly- (styrene-nitrogen isopropyl third Acrylamide-methacrylic acid)/silver nanoparticle complex microsphere field emission scanning electron microscope (FESEM) picture；
Fig. 2 is poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere with temperature The curve for changing and changing；
Fig. 3 is poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere with pH change The curve changed and changed；
Fig. 4 is that poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere catalytic degradation is sub- Methyl blue result schematic diagram.
Embodiment
First aspect present invention provides a kind of preparation method of pH/ responsive to temperature type complex microsphere, and step includes：
S1, poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon preparation：By styrene, nitrogen isopropyl Acrylamide, methacrylic acid, initiator react 6-10h at 78-85 DEG C, centrifugation, washing, it is dry must poly- (styrene-nitrogen be different Propylacrylamide-methacrylic acid) microballoon；
S2, poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere preparation：To go from Poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon prepared by sub- water, polyvinylpyrrolidone and step S1 mixes Mixed liquor is closed to obtain, silver ammino solution is added in mixed liquor, being sufficiently stirred at 15~35 DEG C makes silver-colored ammonium ion be adsorbed onto poly- (benzene second Alkene-N-isopropylacrylamide-methacrylic acid) microsphere surface, 68-72 DEG C is warming up to, reacts 7-12h under nitrogen atmosphere, from The heart, washing, drying, obtain poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere.
General selected base material needs band strong electronegative, and the present invention selects poly- (styrene-nitrogen isopropyl acrylamide Amine-methacrylic acid) base material is used as, it can not only provide strong elecrtonegativity, and it is new to assign Ag nano composite materials Function, such as pH responses and temperature-responsive.
Preferably, styrene, N-isopropylacrylamide, methacrylic acid mass ratio are 5~7 described in step S1：0.5~ 0.6：0.25~0.5.
Preferably, styrene, the mass ratio of initiator are 5~7 described in step S1：0.1~0.2.
Preferably, initiator described in step S1 includes one or more of in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate.
Preferably, it is micro- per 4g poly- (styrene-N-isopropylacrylamide-methacrylic acid) in mixed liquor in step S2 The amount that ball adds silver-colored ammonium ion is 2~6mol.
Preferably, in step S2, deionized water, polyvinylpyrrolidone and it is poly- (styrene-N-isopropylacrylamide- Methacrylic acid) microballoon weight ratio be 25~35：0.8~1.2:4.
Second aspect of the present invention provides a kind of pH/ responsive to temperature type complex microsphere, and the composite nano-microsphere is by by benzene The polymer microballoon that these three monomers of ethene, N-isopropylacrylamide, methacrylic acid are polymerized, then in the polymer Microsphere surface adsorbs Nano Silver.
Preferably, the styrene, N-isopropylacrylamide, methacrylic acid polymer microballoon particle diameter be 280 ~310nm.
Preferably, the complex microsphere is prepared using aforementioned preparation process.
Third aspect present invention provides application of the above-mentioned poly- complex microsphere of pH/ responsive to temperature type in sewage disposal, institute Stating application process step includes, by poly- (styrene-N-isopropylacrylamide-methacrylic acid)/Yin Na of pH/ responsive to temperature type Rice complex microsphere is used for sewage disposal.Specifically, the application process can be that poly- (styrene-nitrogen is different by pH/ responsive to temperature type Propylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere be added to pending sewage in.
Below in conjunction with specific embodiment to a kind of pH/ responsive to temperature type complex microsphere provided by the invention and its preparation side Method and application are further described.The embodiments described below is exemplary, is only used for explaining the present invention, without being understood that For limitation of the present invention.
Experimental method in following embodiments, it is conventional method unless otherwise specified.Reality used in following embodiments Test material unless otherwise specified, be that market is commercially available.
Embodiment one
A kind of pH/ responsive to temperature type complex microsphere is present embodiments provided, the complex microsphere is by by styrene, nitrogen isopropyl The polymer microballoon that these three monomers of base acrylamide, methacrylic acid are polymerized, the polymer microballoon for it is poly- (styrene- N-isopropylacrylamide-methacrylic acid) complex microsphere, it is described poly- then in the polymer microballoon adsorption Nano Silver The particle diameter of (styrene-N-isopropylacrylamide-methacrylic acid) complex microsphere is 295nm.
Further, the preparation method of above-mentioned pH/ responsive to temperature type complex microsphere, specific steps bag are present embodiments provided Include：
Emulsifier-free emulsion polymerization prepares poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon：Styrene 6g, N-isopropylacrylamide 0.5g, methacrylic acid 0.3g) and initiator 0.1g, the initiator be ammonium persulfate, be added to In 250mL four-hole bottles, first ultrasonic 30min, then moves into 80 DEG C and reacts 8h, and product is made.Finally will obtain product by from Poly- (styrene-N-isopropylacrylamide-methacrylic acid) powder is made in the heart, washing and the method for drying.
Styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere preparation：By deionized water, Poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon prepared by polyvinylpyrrolidone and upper step is according to 30：1: 4 weight mixes to obtain mixed liquor than adding in reaction vessel, then adds freshly prepared silver ammino solution in mixed liquor, mixing Silver-colored ammonium ion and poly- (styrene-N-isopropylacrylamide-methacrylic acid) amount ratio are 4mmol in liquid：4g, fill at room temperature Divide stirring silver-colored ammonium ion is adsorbed onto microsphere surface, be warming up to 70 DEG C, 10h is reacted under nitrogen atmosphere, centrifugation, washing, dries, obtains Poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere.
Embodiment two
A kind of pH/ responsive to temperature type complex microsphere is present embodiments provided, the complex microsphere is by by styrene, nitrogen isopropyl The polymer microballoon that these three monomers of base acrylamide, methacrylic acid are polymerized, the polymer microballoon for it is poly- (styrene- N-isopropylacrylamide-methacrylic acid) complex microsphere, it is described poly- then in the polymer microballoon adsorption Nano Silver The particle diameter of (styrene-N-isopropylacrylamide-methacrylic acid) complex microsphere is 300nm.
Further, the preparation method of above-mentioned pH/ responsive to temperature type complex microsphere, specific steps bag are present embodiments provided Include：
Emulsifier-free emulsion polymerization prepares poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon：Styrene 7g, N-isopropylacrylamide 0.6g, methacrylic acid 0.5g and initiator 0.2g, the initiator are potassium peroxydisulfate, are added to In 250mL four-hole bottles, first ultrasonic 20min, then moves into 85 DEG C and reacts 6h, and product is made.Finally will obtain product by from Poly- (styrene-N-isopropylacrylamide-methacrylic acid) powder is made in the heart, washing and the method for drying.
Styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere preparation：By deionized water, Poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon prepared by polyvinylpyrrolidone and upper step is according to 35： 1.2:4 weight mixes to obtain mixed liquor than adding in reaction vessel, then adds freshly prepared silver ammino solution in mixed liquor, Silver-colored ammonium ion and poly- (styrene-N-isopropylacrylamide-methacrylic acid) amount ratio are 6mmol in mixed liquor：4g, room temperature Under be sufficiently stirred and silver-colored ammonium ion is adsorbed onto microsphere surface, be warming up to 72 DEG C, react 7h under nitrogen atmosphere, it is centrifugation, washing, dry It is dry, obtain poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere.
Embodiment three
A kind of pH/ responsive to temperature type complex microsphere is present embodiments provided, the complex microsphere is by by styrene, nitrogen isopropyl The polymer microballoon that these three monomers of base acrylamide, methacrylic acid are polymerized, the polymer microballoon for it is poly- (styrene- N-isopropylacrylamide-methacrylic acid) complex microsphere, it is described poly- then in the polymer microballoon adsorption Nano Silver The particle diameter of (styrene-N-isopropylacrylamide-methacrylic acid) complex microsphere is 290nm.
Further, the preparation method of above-mentioned pH/ responsive to temperature type complex microsphere, specific steps bag are present embodiments provided Include：
Emulsifier-free emulsion polymerization prepares poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon：Styrene 5g, N-isopropylacrylamide 0.5g, methacrylic acid 0.25g and initiator 0.1g, the initiator are sodium peroxydisulfate, are added to In 250mL four-hole bottles, first ultrasonic 25min, then moves into 78 DEG C and reacts 10h, and product is made.Finally will obtain product by from Poly- (styrene-N-isopropylacrylamide-methacrylic acid) powder is made in the heart, washing and the method for drying.
Styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere preparation：By deionized water, Poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon prepared by polyvinylpyrrolidone and upper step is according to 25： 0.8:4 weight mixes to obtain mixed liquor than adding in reaction vessel, then adds freshly prepared silver ammino solution in mixed liquor, Silver-colored ammonium ion and poly- (styrene-N-isopropylacrylamide-methacrylic acid) amount ratio are 2mmol in mixed liquor：4g, room temperature Under be sufficiently stirred and silver-colored ammonium ion is adsorbed onto microsphere surface, be warming up to 68 DEG C, react 12h under nitrogen atmosphere, it is centrifugation, washing, dry It is dry, obtain poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere.
Example IV
Pattern, temperature/pH response performances and the catalytic performance for the complex microsphere that embodiment one is prepared the present embodiment Tested, method of testing is the conventional method used in performance test, and gained concrete outcome is as follows：
Field emission scanning electron microscope (FESEM) test gives poly- (styrene-N-isopropylacrylamide-methyl Acrylic acid) microballoon and poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere shape appearance figure (figure 1).It can be seen that poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon is spherical structure from Fig. 1 (a), grain Footpath is about 295nm.Contrast a figures, it can be seen that nanometer Ag has loaded to poly- (styrene-nitrogen isopropyl acrylamide in b figures Amine-methacrylic acid) on microsphere surface.
By test poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere temperature and PH response performances test (Fig. 2, Fig. 3), we can see that its temperature and pH response performances have obtained preferable reservation, have Good temperature and pH response performances.
Poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere catalytic degradation methylene blue Performance as shown in figure 3, it can be seen that can just be degraded completely in 11min, illustrate that it has preferable catalytic Energy.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims (10)

1. a kind of preparation method of pH/ responsive to temperature type complex microsphere, step include：
S1, poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon preparation：By styrene, nitrogen isopropyl propylene Acid amides, methacrylic acid, initiator react 6-10h at 78-85 DEG C, centrifugation, washing, dry obtain poly- (styrene-nitrogen isopropyl Acrylamide-methacrylic acid) microballoon；
S2, poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere preparation：By deionization Poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon mixing prepared by water, polyvinylpyrrolidone and step S1 Mixed liquor, will silver ammino solution add mixed liquor in, be sufficiently stirred at 15~35 DEG C make silver-colored ammonium ion be adsorbed onto it is poly- (styrene- N-isopropylacrylamide-methacrylic acid) microsphere surface, 68-72 DEG C is warming up to, reacts 7-12h under atmosphere of inert gases, from The heart, washing, drying, obtain poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere.
2. the preparation method of pH/ responsive to temperature type complex microsphere as claimed in claim 1, it is characterised in that：Described in step S1 Styrene, N-isopropylacrylamide, methacrylic acid mass ratio are 5~7：0.5~0.6：0.25~0.5.
3. the preparation method of the pH/ responsive to temperature type complex microspheres described in claim 1, it is characterised in that：Benzene described in step S1 Ethene, the mass ratio of initiator are 5~7：0.1~0.2.
4. the preparation method of pH/ responsive to temperature type complex microsphere as claimed in claim 1, it is characterised in that：In step S2, institute Stating initiator includes one or more in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate.
5. the preparation method of pH/ responsive to temperature type complex microsphere as claimed in claim 1, it is characterised in that：In step S2, mix Close added in liquid per poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoons of 4g the amount of silver-colored ammonium ion for 2~ 6mol。
6. the preparation method of pH/ responsive to temperature type complex microsphere as claimed in claim 1, it is characterised in that：In step S2, go The weight ratio of ionized water, polyvinylpyrrolidone and poly- (styrene-N-isopropylacrylamide-methacrylic acid) microballoon is 25 ~35：0.8~1.2:4.
A kind of 7. pH/ responsive to temperature type complex microsphere, it is characterised in that：The complex microsphere is by styrene, nitrogen isopropyl third The polymer microballoon that these three monomers of acrylamide, methacrylic acid are polymerized, then received in the polymer microballoon adsorption Meter Yin.
8. pH/ responsive to temperature type complex microsphere as claimed in claim 7, it is characterised in that：The particle diameter of the polymer microballoon For 280~310nm.
9. pH/ responsive to temperature type complex microsphere as claimed in claim 8, it is characterised in that：The complex microsphere uses right It is required that 1 preparation method is prepared.
10. application of the pH/ responsive to temperature type complex microsphere in sewage disposal described in claim 7, it is characterised in that：By pH/ Poly- (styrene-N-isopropylacrylamide-methacrylic acid)/silver nanoparticle complex microsphere of responsive to temperature type is used for sewage disposal.
CN201710579249.6A 2017-07-17 2017-07-17 pH/temperature sensitive composite microsphere and preparation method and application thereof Active CN107456996B (en)

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Assignee: Wuhan Yuanzhong Technology Center

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Assignee: Wuhan jian'anhua science and Technology Center

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Assignee: Wuhan Chuangzhiwei science and Technology Center

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Denomination of invention: A pH/temperature sensitive composite microsphere and its preparation method and application

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Assignee: Wuhan Huizhuo Technology Center

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Denomination of invention: A pH/temperature sensitive composite microsphere and its preparation method and application

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Assignee: Wuhan Yucheng Technology Center

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Denomination of invention: A pH/temperature sensitive composite microsphere and its preparation method and application

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Assignee: Wuhan Boya Technology Center

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