CN101289522B - Method for preparing hollow ball with temperature response or temperature and pH responses - Google Patents
Method for preparing hollow ball with temperature response or temperature and pH responses Download PDFInfo
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- CN101289522B CN101289522B CN2007100984585A CN200710098458A CN101289522B CN 101289522 B CN101289522 B CN 101289522B CN 2007100984585 A CN2007100984585 A CN 2007100984585A CN 200710098458 A CN200710098458 A CN 200710098458A CN 101289522 B CN101289522 B CN 101289522B
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Abstract
The invention belongs to the functional polymer material field, in particular to a method for making a hollow sphere which takes poly N-isopropyl acrylamide as the main raw material and has the temperature response or the temperature and pH responses. The method is based on the precipitation polymerization reaction of N-isopropyl acrylamide in a water solution and comprises the following steps that: when the temperature is higher than the lowest intersolubility critical temperature, PNIPAM is hydrophobic and the generated PNIPAM low polymer aggregates to a nucleus; in the stage of the nucleus growth, a cross-linking agent is added, a layer of cross-linking shell is formed on the periphery of the nucleus, thereby obtaining a nuclear shell structure. At the same time the cross-linking agent is added in the stage, a water-solubility functional monomer is added, the nucleus is made of PNIPAM, a shell layer consists of a multipolymer taking the PNIPAM as a main body and a water-solubility polymer as the auxiliary part. When the temperature is decreased below the lowest intersolubility critical temperature, the PNIPAM or a hollow structure which takes the PNIPAM as the main body and takes other water-solubility compounds as auxiliary parts is formed.
Description
Technical field
The invention belongs to functional high polymer material field, relate to the technology of preparing of environmental response hollow ball, specifically be a kind of be the preparation method of the hollow ball with temperature response or temperature response and pH response of main raw material with the poly N-isopropyl acrylamide.
Background technology
In recent years, polymeric hollow sphere is at catalytic field, the packing of slow releasing pharmaceutical, and the simulation of artificial cell, there is very big potential using value in fields such as macromolecular coating protection of active bio and pigment carrier.Tiny balloon with environmental response ability is owing to have huge potential use and practicability value, one of research focus of this area especially.Wherein, temperature response is important a kind of in the environmental response, and the hollow ball material that possesses the temperature response ability is at biology, medicine, and fields such as chemical industry have important use to be worth.At present, people research and to use maximum class environmental response macromolecular materials be poly N-isopropyl acrylamide (PNIPAM).PNIPAM has temperature sensitive property, takes place to change mutually about 32 ℃, and this temperature is exactly its minimum critical temperature of dissolving each other (LCST).Below LCST, PNIPAM is wetting ability, and macromolecular chain is unfolds state, and more than LCST, PNIPAM is hydrophobicity, and macromolecular chain is contraction schedule.Therefore, if temperature near its phase transition temperature subtle change takes place, will cause the contraction or the expansion of macromolecular chain, thereby cause the great variety of microsphere volume.
At present, the synthetic the most frequently used method of this PNIPAM hollow ball is a template, promptly uses a kind of specific particle as template, then the surface of this particle is modified, as is introduced two keys etc., carries out polymerization then, coats the last layer macromolecular material at template surface.At last, add etching reagent and template is removed (Liusheng Zha, Yan Zhang, Wuli Yang, Shoukuan Fu, Advanced Materials, 2002,14,1090.).This method can obtain hollow ball effectively, but this method steps is more, handle loaded down with trivial details, the tooling cost height.In addition, the affiliation that adds of final step etching reagent pollutes system, thereby influences its range of application.Simultaneously, on the control device of hollow ball size, template must be synthesized the template of different size in order to obtain the hollow ball of different size, and obviously, this means are subjected to the restriction of template synthetic technology, and core technology is a template particles size control technology.Simultaneously, in the application of reality,, often need the PNIPAM hollow ball to have to environment multiparameter responding ability according to the variation of institute's environment for use and purpose, as, have different LCST values, perhaps except possessing temperature sensitive property, also require to possess pH susceptibility.Yet, also do not have relevant report at present in the document at PNIPAM hollow ball functionalization.Therefore, the present invention is a kind of simple in order to find, synthetic easily, the scheme of size control and functionalization.
Summary of the invention
One of purpose of the present invention provides a kind of mould material of need not, simply, synthetic easily poly N-isopropyl acrylamide (PNIPAM) or based on poly N-isopropyl acrylamide (PNIPAM), other water-solubility function polymkeric substance are the method for the hollow ball of assisting.
Two of purpose of the present invention provides a kind of mould material that need not, simply to the poly N-isopropyl acrylamide (PNIPAM) that synthesizes or based on poly N-isopropyl acrylamide (PNIPAM), other water-solubility function polymkeric substance is the means of the hollow ball size control of assisting.
Three of purpose of the present invention provides a kind of mould material that need not, and is synthetic based on poly N-isopropyl acrylamide (PNIPAM), and possesses the preparation method of the hollow ball that temperature response or temperature response and pH respond.
The preparation poly N-isopropyl acrylamide (PNIPAM) that the present invention proposes or based on poly N-isopropyl acrylamide (PNIPAM), other water-solubility function polymkeric substance is the feature of the hollow ball scheme of assisting, be based on the precipitation polymerization reaction of N-N-isopropylacrylamide in the aqueous solution, this scheme is divided into three phases: first stage is the nucleation stage of PNIPAM, because when temperature is higher than the minimum critical temperature of dissolving each other (LCST), PNIPAM is hydrophobicity, and the PNIPAM oligopolymer of generation is assembled nucleation.Subordinate phase, promptly He build phase adds linking agent, along with the growth of nuclear, forms the crosslinked shell of one deck in the periphery of nuclear like this, can obtain a nucleocapsid structure thus.The nuclear and the shell of this nucleocapsid structure all are made up of PNIPAM, but nuclear is non-crosslinked, and shell is crosslinked.If in this stage, when adding linking agent, add the water-solubility function monomer, above-mentioned like this unreacted is N-N-isopropylacrylamide monomer and water-solubility function monomer copolymerization completely, under the effect of linking agent adding, is coated on above-mentioned nuclear surface simultaneously, the nucleocapsid structure that obtains, its nuclear is made up of PNIPAM, and shell is based on poly N-isopropyl acrylamide (PNIPAM), and water-soluble polymers is that the multipolymer of assisting is formed.In the phase III, temperature is reduced to below the LCST, PNIPAM will become wetting ability by hydrophobicity, noncrosslinking nuclear will be dismissed, and see through crosslinked shell to external diffusion, final form poly N-isopropyl acrylamide (PNIPAM) or based on poly N-isopropyl acrylamide (PNIPAM), other water-solubility function polymkeric substance is the hollow structure of assisting; This process does not need to add any etching reagent, can be regarded as the process of " removing certainly ".
The feature of the hollow ball size control means that the present invention proposes is: add the tensio-active agent that accounts for monomer content 0～2% (molar content) in N-N-isopropylacrylamide polymerization system.
The feature that the PNIPAM hollow ball is carried out temperature response or temperature and pH response characteristic control method that the present invention proposes is: after the fs finishes, after promptly the nucleation stage finishes, when adding linking agent, add the water-solubility function monomer.
Preparation method with hollow ball of temperature response or temperature response and pH response of the present invention may further comprise the steps:
(1). preparation N-N-isopropylacrylamide monomer (NIPAM) aqueous solution, concentration is 1～50g/L, is advisable with 10～20g/L, adds simultaneously that to account for N-N-isopropylacrylamide monomer molar percentage composition be 0～2% tensio-active agent;
(2). in the monomer solution of step (1) logical nitrogen with the oxygen in the system of removing after, add the initiator that accounts for N-N-isopropylacrylamide molar content 0.5～5%, with the system sealing, be 35～80 ℃ water-bath initiated polymerization in temperature;
(3). the polymerization-filling for the treatment of step (2) begins and nucleation (system by colourless become light blue) after, injection accounts for the water-solubility function monomer of N-N-isopropylacrylamide molar content 0～50%, simultaneously cross-linking agent solution is injected in the system, reaction continued 3～12 hours, wherein, to account for the per-cent of N-N-isopropylacrylamide and water-solubility function monomer molar total amount be 0.5～5% to linking agent;
(4). the system temperature of step (3) is reduced to the minimum critical temperature following (5～30 ℃) of dissolving each other of poly N-isopropyl acrylamide, stirs product;
(5). on whizzer, collect the poly N-isopropyl acrylamide (PNIPAM) of step (4) or based on poly N-isopropyl acrylamide (PNIPAM), other water-solubility function polymkeric substance is the hollow ball product of assisting with the rotating speed of 8000～12000r/min.
Described step (2) logical nitrogen in monomer solution is 10～40 minutes with time of the oxygen in the system of removing.
It is 24～48 hours that described step (5) stirs the product time.
The tensio-active agent that uses among the present invention is selected from sodium lauryl sulphate (SDS), succsinic acid two (2-ethylhexyl) ester sulfonic acid (AOT), cetyl trimethylammonium bromide (CTAB), a kind of in the octadecyl trimethyl ammonium chloride etc.
The initiator that uses among the present invention is selected from 2,2 '-Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide (BPO), ammonium persulphate (APS), or ammonium persulphate-N, N, N ', N '-methyl ethylenediamine (TMEA), a kind of in the redox initiation system that hydrogen peroxide-sodium bisulfite is formed etc.
The linking agent that uses among the present invention is selected from Vinylstyrene, N, N '-methylene-bisacrylamide, a kind of in the dimethyl diallyl ammonium chloride etc.
The water-solubility function monomer that uses among the present invention is selected from acrylamide (AM), Methacrylamide (MAM), N hydroxymethyl acrylamide (HAM), vinylformic acid (AA), methacrylic acid (MAA), N-vinyl imidazole (VI), N-vinyl pyrrolidone (VP), 2-acrylamido-2-methyl propane sulfonic acid (AMPS), the mixture of one or more in the methylacryoyloxyethyl trimethyl ammonium chloride (DMC) etc.
Among the present invention, the feature of step (3) nucleation stage be system by colourless become light blue.
Among the present invention, step (4) (removing process certainly) is characterised in that and cools the temperature to below the minimum critical temperature of dissolving each other of poly N-isopropyl acrylamide (LCST), is advisable with 20～25 ℃.
Among the present invention, add the size that tensio-active agent can be regulated the resulting hollow ball of the inventive method.Content by the reconciliation statement surface-active agent is between 0～2% (molar content), can control poly N-isopropyl acrylamide (PNIPAM) or based on poly N-isopropyl acrylamide (PNIPAM), other water-solubility function polymkeric substance be the outside dimension of the hollow ball of assisting at 100～1000nm, cavity diameter is 80～800nm.
Among the present invention, add the LCST that the water-solubility function monomer can be regulated hollow ball.By adding difference in functionality monomer and the mole percent level by adjusting function monomer at 0～50%, the LCST that can control hollow ball is at 30～70 ℃.
The present invention compares with traditional template, has following characteristics: 1. and adopt " one kettle way " synthetic, simple, convenient.2. provide a kind of simple, effectively controlled the method for hollow ball size, only need just can realize the control of hollow ball size by regulating the content of the tensio-active agent that adds.3. the present invention is by monomeric kind of water-solubility function and content that control adds, can realize the control of hollow ball LCST and gives hollow ball pH susceptibility.4. the particle diameter (external diameter) of the prepared hollow ball of the present invention is characterized as size at 100～1000nm, cavity diameter 80～800nm.5. the temperature response scope of the prepared hollow ball of the present invention is 30～70 ℃.6. the pH responding range of the prepared tiny balloon of the present invention is 2～10.
Description of drawings
Fig. 1. be the prepared PNIPAM hollow ball transmission electron microscope photo of the embodiment of the invention 1.
Fig. 2. be the prepared temperature sensitive curve of PNIPAM hollow ball of the embodiment of the invention 1.
Fig. 3. be the prepared PNIPAM-5%PAA hollow ball pH sensitivity curve of the embodiment of the invention 7.
Embodiment
Embodiment 1.
The N-N-isopropylacrylamide aqueous solution 200ml of preparation 13.6g/L.Logical nitrogen added the N of 24g/L AIBN, dinethylformamide (DMF) solution 2ml after 15 minutes in the N-N-isopropylacrylamide aqueous solution.After the reactor sealing, at 60 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L dimethyl diallyl ammonium chloride 4ml with syringe, continue reaction 8 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 8000r/min.The PNIPAM hollow ball that obtains has temperature sensitive property, and its LCST is about 32 ℃, and outside dimension is about 800～1000nm, and cavity diameter is 600～800nm.Its electromicroscopic photograph as shown in Figure 1, temperature sensitive curve is as shown in Figure 2.
Preparation 6.8g/L N-N-isopropylacrylamide aqueous solution 200ml.Logical nitrogen added the N of 35g/L benzoyl peroxide (BPO) after 15 minutes in above-mentioned solution, and dinethylformamide (DMF) solution 2ml is after the reactor sealing, at 60 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L N with syringe, N '-methylene-bisacrylamide 2ml adds the acrylamide soln 5ml of 8.6g/L simultaneously, continues reaction 12 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 10000r/min.The PNIPAM hollow ball that contains 5mol%PAM that obtains has temperature sensitive property, and its LCST is about 36 ℃, and outside dimension is about 800～1000nm, and cavity diameter is 600～800nm.
Preparation 6.8g/L N-N-isopropylacrylamide aqueous solution 200ml.Logical nitrogen added 2g/L superoxol 2ml, the sodium sulfite solution 2ml of 6g/L after 15 minutes in above-mentioned solution.After the reactor sealing, at 50 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L N with syringe, N '-methylene-bisacrylamide 2ml adds the acrylamide soln 5ml of 17.2g/L simultaneously.Continue reaction 4 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 10000r/min.The PNIPAM hollow ball that contains 10mol%PAM that obtains has temperature sensitive property, and its LCST is about 41 ℃, and outside dimension is about 800～1000nm, and cavity diameter is 600～800nm.
Preparation 6.8g/L N-N-isopropylacrylamide aqueous solution 200ml.Logical nitrogen added 2g/L superoxol 2ml, the sodium sulfite solution 2ml of 6g/L after 15 minutes in above-mentioned solution.After the reactor sealing, at 50 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L N with syringe, N '-methylene-bisacrylamide 2ml adds 2-acrylamido-2-methyl propane sulfonic acid (AMPS) solution 5ml of 13.4g/L simultaneously.Continue reaction 4 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 10000r/min.The PNIPAM hollow ball that contains 2mol%PAMPS that obtains has temperature sensitive property, and its LCST is about 37 ℃, and outside dimension is about 800～1000nm, and cavity diameter is 600～800nm.
Preparation 13.6g/L N-N-isopropylacrylamide aqueous solution 200ml, the SDS aqueous solution 4ml of adding 17.2g/L.Logical nitrogen added the N of 24g/L AIBN, dinethylformamide (DMF) solution 2ml after 15 minutes in above-mentioned solution.After the reactor sealing, at 60 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L dimethyl diallyl ammonium chloride solution 4ml with syringe, continue reaction 8 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 12000r/min.The PNIPAM hollow ball that obtains has temperature sensitive property, and its LCST is about 32 ℃, and outside dimension is about 150～200nm, and cavity diameter is 100～150nm.
Preparation 13.6g/L N-N-isopropylacrylamide aqueous solution 200ml, the SDS aqueous solution 2ml of adding 17.2g/L.Logical nitrogen added the N of 24g/L AIBN, dinethylformamide (DMF) solution 2ml after 15 minutes in above-mentioned solution.After the reactor sealing, at 60 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L dimethyl diallyl ammonium chloride solution 4ml with syringe, add the acrylamide soln 5ml of 8.6g/L simultaneously, continue reaction 8 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 12000r/min.The PNIPAM hollow ball that contains 5mol%PAM that obtains has temperature sensitive property, and its LCST is about 32 ℃, and outside dimension is about 250～300nm, and cavity diameter is 150～200nm.
Preparation 6.8g/L N-N-isopropylacrylamide aqueous solution 200ml.Logical nitrogen added the N of benzoyl peroxide (BPO), dinethylformamide (DMF) solution 2ml after 15 minutes in above-mentioned solution.After the reactor sealing, at 70 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L N with syringe, N '-methylene-bisacrylamide 2ml adds the acrylic acid solution 5ml of 8.6g/L simultaneously.Continue reaction 4 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 10000r/min.The PNIPAM hollow ball that contains 5mol%PAA that obtains has temperature sensitive property, and its LCST is about 34 ℃, and outside dimension is about 600～700nm, and cavity diameter is 600～800nm.This hollow ball has pH susceptibility simultaneously, pH responding range 2～10.The pH sensitivity curve as shown in Figure 3.
Embodiment 8.
Preparation 13.6g/L N-N-isopropylacrylamide aqueous solution 200ml.Logical nitrogen added the N of 24g/L AIBN, dinethylformamide (DMF) solution 2ml after 15 minutes in above-mentioned solution.After the reactor sealing, at 60 ℃ of water-bath initiated polymerizations.When system is become when light blue by transparent, add 9.2g/L dimethyl diallyl ammonium chloride solution 4ml with syringe, add vinyl imidazole (VI) aqueous solution 10ml of 12.4g/L simultaneously.Continue reaction 8 hours.Then system is cooled to room temperature (about 25 ℃), stirred 36 hours.Solution is collected on whizzer with the rotating speed of 10000r/min.The PNIPAM hollow ball that contains 10mol%PVI that obtains has temperature sensitive property, and its LCST is about 36 ℃, and outside dimension is about 600～700nm, and cavity diameter is 500～600nm.This hollow ball has pH susceptibility simultaneously, pH responding range 2～10.
Claims (9)
1. preparation method with hollow ball of temperature response or temperature response and pH response, it is characterized in that: described method may further comprise the steps:
(1). preparation N-N-isopropylacrylamide monomer solution, concentration is 1～50g/L, adds simultaneously that to account for N-N-isopropylacrylamide monomer molar percentage composition be 0～2% tensio-active agent;
(2). in the monomer solution of step (1) logical nitrogen with the oxygen in the system of removing after, add the initiator that accounts for N-N-isopropylacrylamide molar content 0.5～5%, with the system sealing, be 35～80 ℃ water-bath initiated polymerization in temperature;
(3). the polymerization-filling for the treatment of step (2) begin and nucleation after, injection accounts for the water-solubility function monomer of N-N-isopropylacrylamide molar content 0～50%, simultaneously cross-linking agent solution is injected in the system, reaction continued 3～12 hours, wherein, to account for the per-cent of N-N-isopropylacrylamide and water-solubility function monomer molar total amount be 0.5～5% to linking agent;
(4). the system temperature of step (3) is reduced to the minimum critical of poly N-isopropyl acrylamide dissolves each other below the temperature, stir product;
(5). on whizzer, collect the poly N-isopropyl acrylamide of step (4) or based on poly N-isopropyl acrylamide, other water-solubility function polymkeric substance is the hollow ball product of assisting with the rotating speed of 8000～12000r/min;
Described water-solubility function monomer is selected from acrylamide, Methacrylamide, N hydroxymethyl acrylamide, vinylformic acid, methacrylic acid, N-vinyl imidazole, N-vinyl pyrrolidone, 2-acrylamido-2-methyl propane sulfonic acid, the mixture of one or more in the methylacryoyloxyethyl trimethyl ammonium chloride.
2. method according to claim 1 is characterized in that: described tensio-active agent is selected from sodium lauryl sulphate, succsinic acid two (2-ethylhexyl) ester sulfonic acid, cetyl trimethylammonium bromide, a kind of in the octadecyl trimethyl ammonium chloride.
3. method according to claim 1 is characterized in that: described initiator is selected from 2,2 '-Diisopropyl azodicarboxylate, benzoyl peroxide, ammonium persulphate, or ammonium persulphate-N, N, N ', N '-methyl ethylenediamine, a kind of in the redox initiation system that hydrogen peroxide-sodium bisulfite is formed.
4. method according to claim 1 is characterized in that: described linking agent is selected from Vinylstyrene, N, N '-methylene-bisacrylamide, a kind of in the dimethyl diallyl ammonium chloride.
5. method according to claim 1 is characterized in that: the concentration of described step (1) preparation N-N-isopropylacrylamide monomer solution is 10～20g/L.
6. method according to claim 1 is characterized in that: described step (4) cools the temperature to minimum critical the dissolving each other below the temperature of poly N-isopropyl acrylamide, and temperature is 20～25 ℃.
7. method according to claim 1 is characterized in that: the temperature response scope of described hollow ball is 30～70 ℃.
8. method according to claim 1 is characterized in that: the pH responding range of described hollow ball is 2～10.
9. according to claim 1,7 or 8 described methods, it is characterized in that: the outside dimension of described hollow ball is at 100～1000nm, and cavity diameter is 80～800nm.
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| CN101724157B (en) * | 2008-10-16 | 2011-08-31 | 中国科学院理化技术研究所 | Synthesis method of macromolecular vesicles with pH response performance under alkaline conditions |
| GB0823400D0 (en) * | 2008-12-23 | 2009-01-28 | Eastman Kodak Co | Method of preparing stimuls-responsive polymeric particles |
| CN104662424A (en) * | 2012-07-31 | 2015-05-27 | 加利福尼亚大学董事会 | Selective capture and stimulated release of circulating cells on nanostructured devices |
| CN102964538B (en) * | 2012-12-03 | 2014-06-11 | 西北工业大学 | Method for preparing environmentally responsive monodisperse cyclodextrin polymer hollow microspheres |
| CN104928851B (en) * | 2015-06-24 | 2017-03-01 | 东华大学 | The preparation method of silver-carrying nano particle temperature stimulating responsive Hybrid nanofibers film |
| CN105294278B (en) * | 2015-11-19 | 2019-02-05 | 福建农林大学 | A kind of sugarcane charcoal base liquid manure double-cotrolled type composite slow release carrier and preparation method thereof |
| CN107602891B (en) * | 2017-09-08 | 2020-11-03 | 哈尔滨工业大学 | Preparation method of composite PNIPAM-based microgel PDMS (polydimethylsiloxane) film |
| CN107778417B (en) * | 2017-11-13 | 2020-06-02 | 深圳市中医院 | Preparation method of poly (isopropyl acrylamide) temperature-sensitive polyester gel |
| CN111004344B (en) * | 2019-12-20 | 2021-07-20 | 北京化工大学 | Method for regulating and controlling maximum critical miscible temperature of zwitterionic polymer through end group modification |
| CN113201316B (en) * | 2021-04-25 | 2022-08-26 | 西南石油大学 | temperature/CO 2 pH multi-responsive emulsifier and emulsion and application thereof |
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