CN105732919A - Preparation method of porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel - Google Patents
Preparation method of porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel Download PDFInfo
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Abstract
The invention relates to a preparation method of a porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel. The method comprises the following steps: preparing monohydroxy porphyrin from parahydroxyben-zaldehyde, benzaldehyde and pyrrole, carrying out chain extension with 6-chloro-1-hexanol, carrying out reaction with methacrylic chloride to synthesize a porphyrin-containing acrylate monomer, and carrying out copolymerization on the porphyrin-containing acrylate monomer and N-isopropyl acrylamide by soap-free emulsion polymerization to prepare the porphyrin-containing temperature/multi-metal-ion-responsive block copolymer gel. The two-block copolymer is uniformly distributed spheres in a normal-temperature water solution, and is used as a metal ion fluorescent sensor for trapping and identifying different metal ions in the water solution. After the ambient temperature rises from the room temperature to the low critical solution temperature of poly(N-isopropylacrylamide), the fluorescence emission intensity of the fluorescent sensor is obviously enhanced. Thus, the two-block copolymer has wide potential application range in the aspects of fluorescent probes, life science, chemical analysis and the like.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of temperature containing porphyrin and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel.
Background technology
Fluorescent optical sensor is an emerging efficient detection technology based on physics, Chemical recognition and fluoroscopic examination principle.The instrument underaction that traditional detection technique such as chromatograph, mass spectrum etc. are used, instrument operation and maintenance cost are higher, it is impossible to obtain popularity and use.Therefore, metal ion identification signal can be converted into fluorescence signal by high sensitivity and the selective fluorescent optical sensor of height neatly, has that quantum yield is big, stability is high and the advantage such as convenient and swift, enjoys the favor of people.From report small molecule fluorescent sensor in 1980 for Ca2+Since detection, various forms of metal ions such as Cr3+、Cu2+Deng and other some organic small molecule fluorescent sensors report the most in a large number, even to this day, the multifunction of polymer fluorescent sensor is modified and is imparted the more performance of polymer fluorescent sensor, it has also become the study hotspot of fluorescent optical sensor at present.Wherein, porphyrin/polymeric system is the most easily distinguished due to higher fluorescence quantum yield, stable system under multiple solution system, its absorbing wavelength and generation wavelength interval, is a kind of preferably fluorescent optical sensor type.This fluorescent optical sensor detects at trace metal ion, and cancer optical dynamic therapy and water pollutant adsorption cleaning aspect have wide application.And by emulsifier-free emulsion polymerization method, the metal ion in polymer fluorescent sensor is detected group and be fixed on nanogel surface, microphase-separated is formed with solution system, utilize the temperature-sensing property of poly-N-isopropyl acrylamide simultaneously, reach the purpose of microfacies hydrophobic environment, macroscopically realize the effect that fluorescent assay signal strengthens.
Porphyrin is a kind of small molecule fluorescent compound with macro ring skeleton, and it can be combined with the many kinds of metal ions in aqueous solution, forms metalloporphyrin, thus causes the change of fluorescent emission intensity and the skew of fluorescence emission wavelengths.By introducing different metal ions, the fluorescent emission intensity of metalloporphyrin and fluorescence emission wavelengths all can occur change in various degree, and the selectivity that therefore can realize different metal ion is distinguished, i.e. fluorescent probe.Polymer is obtained by copolymerization after porphyrin is prepared as acrylic ester monomer, the water solublity of porphyrin and the binding ability of metal ion can be increased, after the polymer containing porphyrin is prepared as nanogel, the highly sensitive fluorescent optical sensor of biocompatibility, composite multifunction can be developed into.The more important thing is, thermoinducible nanogel produces reversible hydrophobicity microcell, considerably improves the fluorescent yield of porphyrin group, thus further increases accuracy of detection.
Utilize the amphipathic of poly-N-isopropyl acrylamide, polymerization in conjunction with this advanced person of emulsifier-free emulsion polymerization, polyacrylate block introduces the porphyrin group of metal ion response, can prepare the temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel, this will have extensively utilization in terms of biochemistry, bionic catalysis and photometric analysis with sensor.
Summary of the invention
It is an object of the invention to provide a kind of temperature containing porphyrin and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel.
It is an object of the invention to the porphyrin group by metal ion responds be incorporated in block polymer, it is achieved the preparation of the block polymer of metal ion response.Present invention commercialization hydroxy benzaldehyde, benzaldehyde, pyrroles have synthesized monohydroxy porphyrin, then the potassium carbonate and 6-chloro-1-hexanol by commercialization reacts the monohydroxy porphyrin modified after obtaining chain extension.Then by reacting the preparation acrylic ester monomer containing porphyrin with methacrylic chloride.Finally agalactia emulsion polymerisation process is used to cause the acrylate monomer containing porphyrin and NIPA to prepare block polymer gel with business-like over cure acids initiator.
The present invention proposes a kind of temperature containing porphyrin and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, specifically comprises the following steps that
(1) hydroxy benzaldehyde and benzaldehyde being sequentially added in propanoic acid according to the mol ratio of 1:3, mix homogeneously, wherein the volume ratio of benzaldehyde and propanoic acid is 1:(30 ~ 50).Liquid after mix homogeneously is warming up to 120 ~ 150 DEG C, and mechanical agitation refluxes 1 ~ 5 hour.Then dose volume mark is the new steaming pyrrole propanoic acid solution of 10%, and volume used by it is 1:(3 ~ 1:4 with the ratio of benzaldehyde and the volume of hydroxy benzaldehyde propionic acid solution cumulative volume).The new pyrrole propanoic acid solution that steams is added drop-wise in the propionic acid solution of benzaldehyde and hydroxy benzaldehyde by constant pressure funnel, and time for adding is 30 minutes ~ 1 hour, and reaction temperature is 120 ~ 150 DEG C, and the response time is 4～8 hours.Reaction terminate after, dilute, cool down, purify, wash dry.
(2) being dissolved in appropriate solvent by products therefrom in potassium carbonate, 6-chloro-1-hexanol and step (1), system reaction temperature is 10 ~ 50 DEG C, and the response time is 12 ~ 24 hours.Wherein: in potassium carbonate, 6-chloro-1-hexanol and step (1), the mol ratio of products therefrom is 1:1.1 ~ 1.2:1.Reaction extracts after terminating, filters, purifies, is dried.
(3) products therefrom in step (2) and acid binding agent B being dissolved in appropriate anhydrous solvent according to certain mol ratio, the liquid ice bath after mix homogeneously is cooled to 0 DEG C.Then methacrylic chloride is dissolved in appropriate anhydrous solvent, it is added drop-wise in the mixing liquid after ice bath by constant pressure funnel, wherein in step (2), the mol ratio of products therefrom, acid binding agent B and methacrylic chloride is 1:(1.2 ~ 1.5): (1.2 ~ 1.5), system reaction temperature is 10 ~ 50 DEG C, and the response time is 12 ~ 24 hours.Reaction extracts, washs after terminating, column chromatography purifies, precipitates, is vacuum dried.
(4) by N after recrystallization, N-methylene-bisacrylamide, NIPA and surfactant D are dissolved in appropriate deionized water according to certain mol ratio, system gets rid of air-treatment 30 minutes ~ 1 hour by extraction argon or nitrogen, and under 400 ~ 600rpm rotating speed, mechanical agitation is heated to 70 ~ 90 DEG C and keeps constant temperature simultaneously.System adds initiator E subsequently and causes emulsion polymerization, obtain reactant liquor.Then weigh in the mixed solution that products therefrom monomer in step (3) is dissolved in dimethyl sulfoxide and acetone composition, mix homogeneously, dropped in reactant liquor by constant pressure funnel.Wherein: N, in N-methylene-bisacrylamide, NIPA, surfactant D, initiator E and step (3), the mol ratio of products therefrom monomer is 1:(30 ~ 50): (1.5 ~ 3): (1 ~ 5): (0.1 ~ 0.5), the volume ratio of deionized water, dimethyl sulfoxide and acetone is 1:(0.001 ~ 0.01): (0.1 ~ 1).System is reacted under argon or nitrogen are protected, and reaction temperature is 70 ~ 90 DEG C, and the response time is 7 ~ 10 hours.Reaction is cooled to room temperature after terminating, and filters, and dialysis is dried, i.e. obtained required product.
In the present invention, described in step (2), solvent is DMF, N, one or more in N-diethylformamide or N,N-dimethylacetamide.
In the present invention, described in step (3), acid binding agent B is one or more in triethylamine, ethylenediamine or propane diamine.
In the present invention, described in step (3), anhydrous solvent C is DMF, N, one or more in N-diethylformamide or N,N-dimethylacetamide.
In the present invention, described in step (4), surfactant D is one or more in dodecylbenzene sodium sulfonate or sodium lauryl sulphate.
In the present invention, initiator E described in step (4) is one or both in Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate.
The beneficial effects of the present invention is: raw materials used market all has been commercialized and wide material sources, 1-hexanol as chloro-in 6-, methacrylic chloride, N,N methylene bis acrylamide and solvent etc. all have been achieved with industrialized production, and design procedure orderliness is clear, simple synthetic method is easy to get, favorable repeatability.Temperature containing porphyrin and the many kinds of metal ions dual responsiveness block copolymer gel of experiment preparation utilize the amphipathic of poly-N-isopropyl acrylamide, polymerization in conjunction with this advanced person of emulsifier-free emulsion polymerization, introducing the porphyrin group of metal ion response on polyacrylate block, this will have extensively utilization in terms of biochemistry, bionic catalysis and photometric analysis with sensor.
Accompanying drawing explanation
Fig. 1 is the temperature containing porphyrin and the structural representation of many kinds of metal ions dual responsiveness block copolymer gel of embodiment 1 preparation.
Detailed description of the invention
Following example are to further illustrate the present invention rather than limit the scope of the present invention.
The molecular structure Fourier transform infrared spectrometer (FTIR) of this temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel and magnetic nuclear resonance analyzer (NMR) measure.Optical signals point source uviol lamp is launched.The microscopic appearance of copolymer gel transmission electron microscope (TEM) measures with atomic force microscope (AFM).Metal ion and the temperature dual response of copolymer gel are measured by fluorescence emission spectrum.
Embodiment 1
Benzaldehyde 5.47mL and hydroxy benzaldehyde 2.2735g is dissolved in 190mL propanoic acid, it is warming up to 135 DEG C reflux 1 hour, then 5mL pyrroles's (newly distillation) being pipetted with liquid-transfering gun and join in 20mL propanoic acid and dilute with 30mL propanoic acid, constant pressure funnel drips 30 minutes, and 135 DEG C are refluxed 4 hours.Dilution cool overnight in methanol, carry out twice column chromatography purification respectively and obtain product A.0.63g product A, 0.15mL 6-chloro-1-hexanol, 0.14g potassium carbonate is dissolved in 100mL DMF, reaction backflow 12 hours.Dissolving with dichloromethane after being spin-dried for DMF, and extract with water, dichloromethane extract is dried overnight with anhydrous magnesium sulfate after concentrating.Mother solution is collected through column chromatography and is obtained product B.0.365g product B, 0.06g triethylamine, 20mL oxolane is placed in 50mL round-bottomed flask.Under the conditions of ice bath 0 DEG C, being dissolved in 5mL anhydrous tetrahydro furan by 0.062g methacrylic chloride and dropwise dripping in round-bottomed flask under magnetic agitation, 20 DEG C are stirred overnight.Filtering, be spin-dried for after solution extracting with dchloromethane and with saline, add anhydrous magnesium sulfate and be dried overnight after extraction, crude product column chromatography purifies, and flushing liquor is dichloromethane, obtains product C.By N after 15g recrystallization, N-methylene-bisacrylamide, 0.5g NIPA and 4mg Surfactant SDS are dissolved in 50mL deionized water, system gets rid of air-treatment 30 minutes by extraction argon, and under 400rpm rotating speed, mechanical agitation is heated to 70 DEG C and keeps constant temperature simultaneously.System adds initiator ammonium persulfate subsequently and causes emulsion polymerization.Then weigh 3mg product C to be dissolved in 1mL dimethyl sulfoxide and 10mL acetone and mix homogeneously, dropped in reactant liquor by constant pressure funnel.System is reacted under argon shield, and reaction temperature is 70 DEG C, and the response time is 7 hours.Reaction is cooled to room temperature after terminating, and filters, and dialysis is dried, and i.e. obtains the required product temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel.
Embodiment 2
Benzaldehyde 5.47mL and hydroxy benzaldehyde 2.2735g is dissolved in 250mL propanoic acid, it is warming up to 150 DEG C reflux 2 hours, then pipetting in addition 30mL propanoic acid by 6mL pyrroles's (newly distillation) with liquid-transfering gun and dilute with 30mL propanoic acid, constant pressure funnel drips 45 minutes, and 150 DEG C are refluxed 6 hours.Dilution cool overnight in methanol, carry out twice column chromatography purification respectively and obtain product A.0.63g product A, 0.2mL 6-chloro-1-hexanol, 0.14g potassium carbonate is dissolved in 80mL DMF, reaction backflow 18 hours.Dissolving with dichloromethane after being spin-dried for DMF, and extract with water, dichloromethane extract is dried overnight with anhydrous magnesium sulfate after concentrating.Mother solution is collected through column chromatography and is obtained product B.0.73g product B, 0.15g triethylamine, 45mL oxolane is placed in 100mL round-bottomed flask.Under the conditions of ice bath 0 DEG C, being dissolved in 5mL anhydrous tetrahydro furan by 0.062g methacrylic chloride and dropwise dripping in round-bottomed flask under magnetic agitation, 10 DEG C are stirred overnight.Filtering, be spin-dried for after solution extracting with dchloromethane and with saline, add anhydrous magnesium sulfate and be dried overnight after extraction, crude product column chromatography purifies, and flushing liquor is dichloromethane, obtains product C.By N after 10g recrystallization, N-methylene-bisacrylamide, 0.3g NIPA and 4mg Surfactant SDS are dissolved in 60mL deionized water, system gets rid of air-treatment 30 minutes by extraction nitrogen, and under 600rpm rotating speed, mechanical agitation is heated to 90 DEG C and keeps constant temperature simultaneously.System adds initiator ammonium persulfate subsequently and causes emulsion polymerization.Then weigh 2mg product C to be dissolved in 0.6mL dimethyl sulfoxide and 7mL acetone and mix homogeneously, dropped in reactant liquor by constant pressure funnel.System is reacted under nitrogen protection, and reaction temperature is 90 DEG C, and the response time is 10 hours.Reaction is cooled to room temperature after terminating, and filters, and dialysis is dried, and i.e. obtains the required product temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel.
Embodiment 3
Benzaldehyde 2.74mL and hydroxy benzaldehyde 1.1368g is dissolved in 150mL propanoic acid, it is warming up to 120 DEG C reflux 5 hours, then pipetting in addition 20mL propanoic acid by 4mL pyrroles's (newly distillation) with liquid-transfering gun and dilute with 20mL propanoic acid, constant pressure funnel drips 1 hour, and 150 DEG C are refluxed 6 hours.Dilution cool overnight in methanol, carry out twice column chromatography purification respectively and obtain product A.0.37g product A, 0.1mL 6-chloro-1-hexanol, 0.07g potassium carbonate is dissolved in 50mL DMF, reaction backflow 24 hours.Dissolving with dichloromethane after being spin-dried for DMF, and extract with water, dichloromethane extract is dried overnight with anhydrous magnesium sulfate after concentrating.Mother solution is collected through column chromatography and is obtained product B.0.37g product B, 0.08g triethylamine, 25mL DMF is placed in 50mL round-bottomed flask.Under the conditions of ice bath 0 DEG C, being dissolved in 10mL DMF by 0.030g methacrylic chloride and dropwise dripping in round-bottomed flask under magnetic agitation, 20 DEG C are stirred overnight.Filtering, be spin-dried for after solution extracting with dchloromethane and with saline, add anhydrous magnesium sulfate and be dried overnight after extraction, crude product column chromatography purifies, and flushing liquor is dichloromethane, obtains product C.By N after 5g recrystallization, N-methylene-bisacrylamide, 0.15g NIPA and 2mg Surfactant SDS are dissolved in 30mL deionized water, system gets rid of air-treatment 1 hour by extraction argon, and under 500rpm rotating speed, mechanical agitation is heated to 80 DEG C and keeps constant temperature simultaneously.System adds initiator ammonium persulfate subsequently and causes emulsion polymerization.Then weigh 1mg product C to be dissolved in 0.3mL dimethyl sulfoxide and 4mL acetone and mix homogeneously, dropped in reactant liquor by constant pressure funnel.System is reacted under argon shield, and reaction temperature is 80 DEG C, and the response time is 8 hours.Reaction is cooled to room temperature after terminating, and filters, and dialysis is dried, and i.e. obtains the required product temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel.
Embodiment 4
Benzaldehyde 10.94mL, hydroxy benzaldehyde 4.547g is dissolved in 350mL propanoic acid, is warming up to 140 DEG C and refluxes 3 hours, then pipettes in addition 40mL propanoic acid by 10mL pyrroles's (newly distillation) with liquid-transfering gun and dilutes with 60mL propanoic acid, constant pressure funnel drips 1 hour, and 145 DEG C are refluxed 7 hours.Dilution cool overnight in methanol, carry out twice column chromatography purification respectively and obtain product A.1.26g product A, 0.3mL 6-chloro-1-hexanol, 0.3g potassium carbonate is dissolved in 200mL N,N-dimethylacetamide, reaction backflow 12 hours.Dissolving with dichloromethane after being spin-dried for N,N-dimethylacetamide, and extract with water, dichloromethane extract is dried overnight with anhydrous magnesium sulfate after concentrating.Mother solution is collected through column chromatography and is obtained product B.0.73g product B, 0.12g triethylamine, 40mL N, N-diethylformamide is placed in 100mL round-bottomed flask.Under the conditions of ice bath 0 DEG C, being dissolved in by 0.25g methacrylic chloride in 10mLN, N-diethylformamide and dropwise dripping in round-bottomed flask under magnetic agitation, 30 DEG C are stirred overnight.Filtering, be spin-dried for after solution extracting with dchloromethane and with saline, add anhydrous magnesium sulfate and be dried overnight after extraction, crude product column chromatography purifies, and flushing liquor is dichloromethane, obtains product C.By N after 30g recrystallization, N-methylene-bisacrylamide, 1g NIPA and 10mg Surfactant SDS are dissolved in 100mL deionized water, system gets rid of air-treatment 30 minutes by extraction argon, and under 450rpm rotating speed, mechanical agitation is heated to 85 DEG C and keeps constant temperature simultaneously.System adds initiator sodium peroxydisulfate subsequently and causes emulsion polymerization.Then weigh 6mg product C to be dissolved in 1.5mL dimethyl sulfoxide and 25mL acetone and mix homogeneously, dropped in reactant liquor by constant pressure funnel.System is reacted under argon shield, and reaction temperature is 85 DEG C, and the response time is 9 hours.Reaction is cooled to room temperature after terminating, and filters, and dialysis is dried, and i.e. obtains the required product temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel.
Embodiment 5
Benzaldehyde 5.47mL, hydroxy benzaldehyde 2.2735g is dissolved in 300mL propanoic acid, is warming up to 125 DEG C and refluxes 4 hours, then pipettes in addition 20mL propanoic acid by 5.5mL pyrroles's (newly distillation) with liquid-transfering gun and dilutes with 35mL propanoic acid, constant pressure funnel drips 35 minutes, and 145 DEG C are refluxed 6 hours.Dilution cool overnight in methanol, carry out twice column chromatography purification respectively and obtain product A.0.60g product A, 0.10mL 6-chloro-1-hexanol, 0.13g potassium carbonate is dissolved in 90mL N, N-diethylformamide, reaction backflow 20 hours.Dissolving with dichloromethane after being spin-dried for N, N-diethylformamide, and extract with water, dichloromethane extract is dried overnight with anhydrous magnesium sulfate after concentrating.Mother solution is collected through column chromatography and is obtained product B.0.38g product B, 0.08g triethylamine, 25mL N,N-dimethylacetamide is placed in 50mL round-bottomed flask.Under the conditions of ice bath 0 DEG C, being dissolved in 7mL N,N-dimethylacetamide by 0.07g methacrylic chloride and dropwise dripping in round-bottomed flask under magnetic agitation, 40 DEG C are stirred overnight.Filtering, be spin-dried for after solution extracting with dchloromethane and with saline, add anhydrous magnesium sulfate and be dried overnight after extraction, crude product column chromatography purifies, and flushing liquor is dichloromethane, obtains product C.By N after 18g recrystallization, N-methylene-bisacrylamide, 0.6g NIPA and 5mg surfactant sodium dodecyl base benzene sulfonic acid sodium salt are dissolved in 50mL deionized water, system gets rid of air-treatment 35 minutes by extraction nitrogen, and under 470rpm rotating speed, mechanical agitation is heated to 75 DEG C and keeps constant temperature simultaneously.System adds initiator potassium persulfate subsequently and causes emulsion polymerization.Then weigh 4.5mg product C to be dissolved in 3mL dimethyl sulfoxide and 12mL acetone and mix homogeneously, dropped in reactant liquor by constant pressure funnel.System is reacted under nitrogen protection, and reaction temperature is 75 DEG C, and the response time is 7.5 hours.Reaction is cooled to room temperature after terminating, and filters, and dialysis is dried, and i.e. obtains the required product temperature containing porphyrin and many kinds of metal ions dual responsiveness block copolymer gel.
Claims (6)
1. the temperature containing porphyrin and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, it is characterised in that specifically comprise the following steps that
(1) hydroxy benzaldehyde and benzaldehyde being added sequentially in propanoic acid according to the mol ratio of 1:3, mix homogeneously, the volume ratio of hydroxy benzaldehyde and propanoic acid is 1:(30 ~ 50)；Liquid after mix homogeneously is warming up to 120 ~ 150 DEG C, and mechanical agitation refluxes 1 ~ 5 hour；Then dose volume mark is the new steaming pyrrole propanoic acid solution of 10%, and used by pyrrole propanoic acid solution, volume is 1:3 ~ 1:4 with the volume ratio of benzaldehyde and hydroxy benzaldehyde propionic acid solution cumulative volume；The new pyrrole propanoic acid solution that steams is added drop-wise in the propionic acid solution of benzaldehyde and hydroxy benzaldehyde by constant pressure funnel, and time for adding is 30 minutes ~ 1 hour, and reaction temperature is 120 ~ 150 DEG C, and the response time is 4～8 hours；Reaction terminate after, dilute, cool down, purify, wash dry；
(2) being dissolved in solvent orange 2 A by products therefrom in potassium carbonate, 6-chloro-1-hexanol and step (1), system reaction temperature is 10 ~ 50 DEG C, and the response time is 12 ~ 24 hours；Wherein: in potassium carbonate, 6-chloro-1-hexanol and step (1), the mol ratio of products therefrom is 1:(1.1 ~ 1.2): 1；Reaction extracts after terminating, filters, purifies, is dried；
(3) products therefrom and acid binding agent B in step (2) being dissolved in anhydrous solvent C, the liquid ice bath after mix homogeneously is cooled to 0 DEG C, obtains the mixing liquid after ice bath；Then methacrylic chloride is dissolved in anhydrous solvent C, it is added drop-wise in the mixing liquid after ice bath by constant pressure funnel, wherein in step (2), the mol ratio of products therefrom, acid binding agent B and methacrylic chloride is 1:(1.2 ~ 1.5): (1.2 ~ 1.5), system reaction temperature is 10 ~ 50 DEG C, and the response time is 12 ~ 24 hours；Reaction extracts, washs after terminating, column chromatography purifies, precipitates, is vacuum dried；
(4) by N after recrystallization, N-methylene-bisacrylamide, NIPA and surfactant D are dissolved in deionized water in proportion, system gets rid of air-treatment 30 minutes ~ 1 hour by extraction argon or nitrogen, under 400 ~ 600rpm rotating speed, mechanical agitation is heated to 70 ~ 90 DEG C and keeps constant temperature simultaneously, system adds initiator E subsequently and causes emulsion polymerization, obtain reactant liquor；Then weigh in the mixed solution that products therefrom in step (3) is dissolved in dimethyl sulfoxide and acetone composition, mix homogeneously, dropped in described reactant liquor by constant pressure funnel；Wherein: N, in N-methylene-bisacrylamide, NIPA, surfactant D, initiator E and step (3), the mol ratio of products therefrom monomer is 1:(30 ~ 50): (1.5 ~ 3): (1 ~ 5): (0.1 ~ 0.5), the volume ratio of deionized water, dimethyl sulfoxide and acetone is 1:(0.001 ~ 0.01): (0.1 ~ 1)；System is reacted under argon or nitrogen are protected, and reaction temperature is 70 ~ 90 DEG C, and the response time is 7 ~ 10 hours；Reaction is cooled to room temperature after terminating, and filters, dialyses and dry, i.e. obtaining required product.
A kind of temperature containing porphyrin the most according to claim 1 and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, it is characterized in that described in step (2), solvent orange 2 A is N, dinethylformamide, N, one or more in N-diethylformamide or N,N-dimethylacetamide.
A kind of temperature containing porphyrin the most according to claim 1 and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, is characterized in that acid binding agent B is one or more in triethylamine, ethylenediamine or propane diamine.
A kind of temperature containing porphyrin the most according to claim 1 and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, it is characterized in that described in step (3), anhydrous solvent C is N, dinethylformamide, N, one or more in N-diethylformamide or N,N-dimethylacetamide.
A kind of temperature containing porphyrin the most according to claim 1 and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, is characterized in that described in step (4), surfactant D is one or more in dodecylbenzene sodium sulfonate or dodecyl sodium sulfate.
A kind of temperature containing porphyrin the most according to claim 1 and the preparation method of many kinds of metal ions dual responsiveness block copolymer gel, is characterized in that initiator E described in step (4) is one or both in Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate.
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