CN101985484A - Novel temperature stimuli responsive macromonomer - Google Patents
Novel temperature stimuli responsive macromonomer Download PDFInfo
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- CN101985484A CN101985484A CN2009100601746A CN200910060174A CN101985484A CN 101985484 A CN101985484 A CN 101985484A CN 2009100601746 A CN2009100601746 A CN 2009100601746A CN 200910060174 A CN200910060174 A CN 200910060174A CN 101985484 A CN101985484 A CN 101985484A
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Abstract
The invention relates to a novel temperature stimuli responsive macromonomer, which can regulate and control response temperature by a molecular designing method according to the actual application. A method for preparing the macromonomer comprises a step of preparing functional amino-terminated polymer intermediate by polymerization of diacetone acrylamide and water soluble monomer, and a step of generating the macromonomer by substitution reaction of the amino-terminated polymer intermediate and acryloyl chloride. The temperature stimuli responsive macromonomer has wide raw material sources and relatively low cost, and the preparation method is relatively simple and is easy for industrialization.
Description
Technical field
The present invention relates to class thermal stimulus response macromonomer and preparation thereof, belong to intelligent water-soluble polymer field.
Background technology
Stimulation-response type water-soluble polymers (Stimuli-responsive water-soluble polymer) be self to external world the slight change of environment (stimulation) make response, produce a class water-soluble polymer of the variation even the sudden change of corresponding physical structure and chemical property.External stimulus can be temperature, pH, ionic strength (ionogen), electric field and light etc., and wherein thermal stimulus response type water-soluble polymers is the more class of research.Often contain functional groups such as ehter bond, substituted amide and hydroxyl in the thermal stimulus response type water-soluble polymers, as poly-(N-N-isopropylacrylamide) (PNIPAM), polyoxyethylene ether (PEO), polyvinylpyrrolidone (PVP) etc., this type of water-soluble polymers outstanding feature is to have significant hydrodynamic volume to change in response process, can be effective to water treatment, improve oil recovery, can control drug release, fluid drag-reduction, aspects such as personal-care supplies.The stimuli responsive type polymkeric substance has caused the research interest that researcher is more and more denseer, and has become important research object in this field, forward position day by day owing to its wide application prospect.In recent years, the research of thermal stimulus response type water-soluble polymers emerges many achievements.But because at present synthesis temperature stimuli responsive type water soluble polymer material required function monomer cost is expensive and be not easy to obtain, so the application of base polymer material has been subjected to great restriction.
Therefore, be more widely used in order to make thermal stimulus response type water-soluble polymers, must synthetic extensive, the lower-cost thermal stimulus response type of a kind of raw material sources function monomer.
Summary of the invention
At the higher and technology height of existing thermal stimulus response type function monomer cost problem such as maintain secrecy, the present invention utilizes the principle of molecular designing, utilize diacetone-acryloamide(DAA) and water-soluble monomer, swash the response type function monomer by the synthetic a kind of novel temperature of two-step approach.
Described water-soluble monomer is one or more in acrylamide, Methacrylamide, N methacrylamide, N,N-DMAA and the N hydroxymethyl acrylamide.
The present invention has following advantage:
1, raw material sources are extensive, obtain easily;
2, cost of material is relatively low, so cost is lower;
3, synthesis technique is simple relatively, is easy to industrialization;
4, response temperature is adjustable, and Application Areas is wider.
The response temperature (be often referred to low critical temperature (LCST)) of the present invention by the novel thermal stimulus of molecular designing synthetic response macromonomer can be by changing macromonomer the conditions such as salinity of composition, concentration, pH and solution regulate and control, the performance of macromonomer is seen accompanying drawing.
The preparation method of macromonomer of the present invention comprises the steps:
Method one:
(1) in reactor, add the distilled water of certain volume, a certain proportion of monomer (A) diacetone-acryloamide(DAA) and water-soluble monomer (B), stirring and dissolving, the concentration of solution are controlled at solution temperature between 20-75 ℃ between 8-40%, logical high-purity N
230min-1h adds a certain amount of water soluble starter (ammonium persulphate, Potassium Persulphate, Sodium Persulfate) and chain-transfer agent mercaptoethylamine (AETHCl), continues logical N
2React 8-12h, reaction solution is poured into to precipitate in the excessive acetone separates out polymkeric substance, use the acetone purified polymer then 3 times, vacuum-drying obtains holding the intermediate polymer of amido.
(2) in reactor, the end amine based polymer of a certain amount of step (1) gained is dissolved in the non-proton organic solvent of certain volume, solution temperature is controlled between 5-10 ℃, under stirring state, slowly splash into a certain amount of acrylate chloride, continue to stir 8h, reaction solution is poured into to precipitate in the excessive acetone then and separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer.
Method two:
In reactor, add a certain amount of non-proton organic solvent, a certain proportion of monomer (A) diacetone-acryloamide(DAA) and water-soluble monomer (B), stirring and dissolving, the concentration of solution are controlled at solution temperature between 55-75 ℃ between 8-30%, logical high-purity N
230min-1h adds a certain amount of oil-soluble initiator (Diisopropyl azodicarboxylate, dibenzoyl peroxide) and chain-transfer agent mercaptoethylamine (AETHCl), continues logical N
2Reaction 8-12h, then reaction solution is cooled off, its temperature is controlled between 5-10 ℃, under stirring state, slowly splash into a certain amount of acrylate chloride, temperature is raised to 25 ℃ and continues to stir 8h, reaction solution is poured into to precipitate in the excessive acetone then and separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer.
The typical chemical equation of the inventive method can be expressed as:
The assay method of the LCST of macromonomer is as follows:
Accurately take by weighing a certain amount of novel thermal stimulus response type macromonomer, be made into the aqueous solution of prescribed concentration, pH and brine concentration with deionized water, this solution is joined in the quartz colorimetric utensil that light path is 1cm, measure the variation of transmittance with UV-4802 type (You Nike company) ultraviolet-visible spectrophotometer (setting drawing is seen accompanying drawing) of repacking, with transmittance temperature is mapped, the pairing temperature of 50% initial transmittance is defined as the LCST of this macromonomer.
Description of drawings
Ultraviolet-visible spectrophotometer device synoptic diagram after Fig. 1 repacking.
The transmittance of the different concns macromonomer solution of Fig. 2 embodiment of the invention is with variation of temperature.
The concentration of the macromonomer solution of Fig. 3 embodiment of the invention is to the influence of macromonomer LCST.
The pH of the macromonomer solution of Fig. 4 embodiment of the invention is to the influence of macromonomer LCST.
NaCl is to the influence of macromonomer LCST in the macromonomer solution of Fig. 5 embodiment of the invention.
Embodiment
The present invention is further described below in conjunction with concrete embodiment:
Embodiment 1:
(1) thermometer is being housed, the 500mL Wolff bottle reactor of electric mixer and nitrogen ingress pipe places water bath with thermostatic control, in reactor, add the 38.34g diacetone-acryloamide(DAA) then, 24.16 acrylamide and 250mL water, stirring and dissolving, temperature of reaction is controlled at 30 ℃, stir 300 rev/mins, logical high purity nitrogen 30min, add water-soluble radical initiator Potassium Persulphate 0.50g and chain-transfer agent AETHCl 0.68g, continue logical nitrogen reaction 8h, reaction solution is poured in the excessive acetone precipitation separates out polymkeric substance, use the acetone purified polymer then 3 times, vacuum-drying obtains holding the intermediate polymer of amido.
(2) thermometer is being housed, in the 250mL Wolff bottle reaction of electric mixer and reinforced dropping funnel, add 150mL DMF, under high degree of agitation, intermediate polymer 20g with (1) gained, slowly join in the reactor, make its dissolving, add the 10mL acrylate chloride at dropping funnel then, temperature is cooled to drip acrylate chloride between 5-8 ℃ under agitation condition, drips off in 1h, strict control rate of addition during dropping, guarantee that temperature of reaction is no more than 8 ℃, temperature of reaction is controlled at 25 ℃ then, reaction 8h, reaction solution is poured in the excessive acetone precipitation separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer, and the response temperature of macromonomer is at 45-55 ℃.
Embodiment 2:
(1) thermometer is being housed, the 500mL Wolff bottle reactor of electric mixer and nitrogen ingress pipe places water bath with thermostatic control, in reactor, add the 44.01g diacetone-acryloamide(DAA) then, 18.49g acrylamide and 250mL water, stirring and dissolving, temperature of reaction is controlled at 30 ℃, stir 300 rev/mins, logical high purity nitrogen 30min, add water-soluble radical initiator Potassium Persulphate 0.50g and chain-transfer agent AETHCl 0.58g, continue logical nitrogen reaction 8h, reaction solution is poured in the excessive acetone precipitation separates out polymkeric substance, use the acetone purified polymer then 3 times, vacuum-drying obtains holding the intermediate polymer of amido.
(2) thermometer is being housed, in the 250mL Wolff bottle reactor of electric mixer and reinforced dropping funnel, add 150mL DMF, under high degree of agitation, intermediate polymer 20g with (1) gained, slowly join in the reactor, make its dissolving, add the 10mL acrylate chloride at dropping funnel then, temperature is cooled to drip acrylate chloride between 5-8 ℃ under agitation condition, drips off in 1h, strict control rate of addition during dropping, guarantee that temperature of reaction is no more than 8 ℃, temperature of reaction is controlled at 25 ℃ then, reaction 8h, reaction solution is poured in the excessive acetone precipitation separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer, and the response temperature of macromonomer is at 27-32 ℃.
Embodiment 3:
(1) thermometer is being housed, the 500mL Wolff bottle reactor of electric mixer and nitrogen ingress pipe places water bath with thermostatic control, in reactor, add the 48.83g diacetone-acryloamide(DAA) then, 13.67g acrylamide and 250mL water, stirring and dissolving, temperature of reaction is controlled at 30 ℃, stir 300 rev/mins, logical high purity nitrogen 30min, add water-soluble radical initiator Potassium Persulphate 0.5g and chain-transfer agent AETHCl 0.5g, continue logical nitrogen reaction 8h, reaction solution is poured in the excessive acetone precipitation separates out polymkeric substance, use the acetone purified polymer then 3 times, vacuum-drying obtains holding the intermediate polymer of amido.
(2) thermometer is being housed, in the 250mL Wolff bottle reactor of electric mixer and reinforced dropping funnel, add 150mL DMF, under high degree of agitation, intermediate polymer 20g with (1) gained, slowly join in the reactor, make its dissolving, add the 10mL acrylate chloride at dropping funnel then, temperature is cooled to drip acrylate chloride between 5-8 ℃ under agitation condition, drips off in 1h, strict control rate of addition during dropping, guarantee that temperature of reaction is no more than 8 ℃, temperature of reaction is controlled at 25 ℃ then, reaction 8h, reaction solution is poured in the excessive acetone precipitation separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer, and the response temperature of macromonomer is at 8-12 ℃.
Embodiment 4:
Thermometer is being housed, electric mixer, in the 2L four neck vial reactors of reinforced dropping funnel and nitrogen ingress pipe, add 1.5L DMF, 235.0g diacetone-acryloamide(DAA) and 65.0g acrylamide, stirring and dissolving, temperature of reaction is controlled at 75 ℃, stir 300 rev/mins, logical high purity nitrogen 30min, add oil soluble radical initiator Diisopropyl azodicarboxylate 2.4g and chain-transfer agent AETHCl 3.2g, continue logical nitrogen reaction 8h, stop logical nitrogen then, reaction is cooled between 5-8 ℃, add the 50mL acrylate chloride at dropping funnel, under agitation condition, drip acrylate chloride, drip off in 1.5h, strict control rate of addition guarantees that temperature of reaction is no more than 8 ℃ during dropping, temperature of reaction is controlled at 25 ℃ then, react 8h, reaction solution is poured into to precipitate in the excessive acetone separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer, and the response temperature of macromonomer is at 45-55 ℃.
Embodiment 5:
Thermometer is being housed, electric mixer, in the 2L four neck vial reactors of reinforced dropping funnel and nitrogen ingress pipe, add 1.5L DMF, 211.2g diacetone-acryloamide(DAA) and 88.8g acrylamide, stirring and dissolving, temperature of reaction is controlled at 75 ℃, stir 300 rev/mins, logical high purity nitrogen 30min, add oil soluble radical initiator Diisopropyl azodicarboxylate 2.4g and chain-transfer agent AETHCl 3.2g, continue logical nitrogen reaction 8h, stop logical nitrogen then, reaction is cooled between 5-8 ℃, add the 50mL acrylate chloride at dropping funnel, under agitation condition, drip acrylate chloride, drip off in 1h, strict control rate of addition guarantees that temperature of reaction is no more than 8 ℃ during dropping, temperature of reaction is controlled at 25 ℃ then, react 8h, reaction solution is poured into to precipitate in the excessive acetone separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer, and the response temperature of macromonomer is at 27-32 ℃.
Embodiment 6:
Thermometer is being housed, electric mixer, in the 2L four neck vial reactors of reinforced dropping funnel and nitrogen ingress pipe, add 1.5L DMF, 234.4g diacetone-acryloamide(DAA) and 65.6g acrylamide, stirring and dissolving, temperature of reaction is controlled at 75 ℃, stir 300 rev/mins, logical high purity nitrogen 30min, add oil soluble radical initiator Diisopropyl azodicarboxylate 2.4g and chain-transfer agent AETHCl 3.2g, continue logical nitrogen reaction 8h, stop logical nitrogen then, reaction is cooled between 5-8 ℃, add the 50mL acrylate chloride at dropping funnel, under agitation condition, drip acrylate chloride, drip off in 1.5h, strict control rate of addition guarantees that temperature of reaction is no more than 8 ℃ during dropping, temperature of reaction is controlled at 25 ℃ then, react 8h, reaction solution is poured into to precipitate in the excessive acetone separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer, and the response temperature of macromonomer is at 8-12 ℃.
Embodiment 7:
The macromonomer of accurate weighing embodiment, being made into mass concentration with deionized water is a series of aqueous solution of 0.4-10.0%, the pH of solution is 7.3, the transmittance of measuring its serial aqueous solution with the ultraviolet-visible spectrophotometer after the repacking is with variation of temperature, and concentration is seen accompanying drawing to macromonomer LCST influence.
Embodiment 8:
The macromonomer of accurate weighing embodiment, being made into pH with deionized water is that series mass concentration between the 2-10 is 0.6% aqueous solution, the transmittance of measuring its serial aqueous solution with the ultraviolet-visible spectrophotometer after the repacking is with variation of temperature, and pH sees accompanying drawing to macromonomer LCST influence.
Embodiment 9:
The macromonomer of accurate weighing embodiment, being made into mass concentration with the NaCl aqueous solution of different concns is the 0.6% serial aqueous solution, the pH of solution is 7.3, the transmittance of measuring its serial aqueous solution with the ultraviolet-visible spectrophotometer after the repacking is with variation of temperature, and NaCl sees accompanying drawing to macromonomer LCST influence.
Claims (9)
1. a novel thermal stimulus responds macromonomer, it is the intermediate polymer that is generated the end amido by monomer (A) and monomer (B) copolymerization, generate macromonomer with the acrylate chloride reaction then, the intermediate polymer that it is characterized in that the described end amido that generates by following material molar ratio reaction
Monomer A 30～70%;
Monomers B 30～70%.
2. a kind of novel thermal stimulus response macromonomer as claimed in claim 1, it is characterized in that: monomer (A) is a diacetone-acryloamide(DAA).
3. a kind of novel thermal stimulus response macromonomer as claimed in claim 1, it is characterized in that: monomer (B) is one or more in water-soluble monomer acrylamide, Methacrylamide, N methacrylamide, N,N-DMAA and the N hydroxymethyl acrylamide.
4. one kind prepares the method that a kind of according to claim 1 novel thermal stimulus responds macromonomer, it is characterized in that comprising that the following step poly-:
(1) in reactor, add the distilled water of certain volume, a certain proportion of monomer (A) diacetone-acryloamide(DAA) and water-soluble monomer (B), stirring and dissolving, the concentration of solution are controlled at solution temperature between 20-70 ℃ between 8-40%, logical high-purity N
230min-1h adds a certain amount of water soluble starter and chain transfer, continues logical N
2React 8-12h, reaction solution is poured into to precipitate in the excessive acetone separates out polymkeric substance, use the acetone purified polymer then 3 times, vacuum-drying obtains holding the intermediate polymer of amido;
(2) in reactor, the end amine based polymer of a certain amount of step (1) gained is dissolved in the non-proton organic solvent of certain volume, solution temperature is controlled between 5-10 ℃, under stirring state, slowly splash into a certain amount of acrylate chloride, continue to stir 8h, reaction solution is poured into to precipitate in the excessive acetone then and separates out macromonomer, use acetone purifying macromonomer 3 times then, vacuum lyophilization gets the functional macromolecule monomer.
5. method as claimed in claim 4 is characterized in that: described water soluble starter is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
6. method as claimed in claim 4 is characterized in that: described chain-transfer agent is mercaptoethylamine (AETHCl).
7. one kind prepares the method that a kind of according to claim 1 novel thermal stimulus responds macromonomer, it is characterized in that: in reactor, add a certain amount of non-proton organic solvent, a certain proportion of monomer (A) diacetone-acryloamide(DAA) and water-soluble monomer (B), stirring and dissolving, the concentration of solution is controlled at solution temperature between 55-75 ℃ between 8-20%, logical high-purity N
230min-1h adds a certain amount of oil-soluble initiator and chain-transfer agent, continues logical N
2Reaction 8-12h, then reaction solution is cooled off, its temperature is controlled between 5-10 ℃, under stirring state, slowly splash into a certain amount of acrylate chloride, temperature is raised to 25 ℃ and continues to stir 8h, reaction solution is poured into to precipitate in the excessive acetone then and separates out macromonomer, use the acetone purified polymer then 3 times, vacuum lyophilization gets the functional macromolecule monomer.
8. method as claimed in claim 7 is characterized in that: described oil-soluble initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
9. method as claimed in claim 7 is characterized in that: described chain-transfer agent is mercaptoethylamine (AETHCl).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892846A (en) * | 2015-05-22 | 2015-09-09 | 贵州师范学院 | Thermosensitive amphipathic cation polymer used as filter aid of phosphoric acid filter system |
| CN107099005A (en) * | 2017-05-07 | 2017-08-29 | 四川大学 | A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof |
| CN111019043A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | CO (carbon monoxide)2/N2Switch type temperature-sensitive polymer and preparation method thereof |
-
2009
- 2009-07-29 CN CN2009100601746A patent/CN101985484A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104892846A (en) * | 2015-05-22 | 2015-09-09 | 贵州师范学院 | Thermosensitive amphipathic cation polymer used as filter aid of phosphoric acid filter system |
| CN107099005A (en) * | 2017-05-07 | 2017-08-29 | 四川大学 | A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof |
| CN107099005B (en) * | 2017-05-07 | 2019-04-02 | 四川大学 | A kind of CO based on inierpeneirating network structure2Response type polymer microballoon and preparation method thereof |
| CN111019043A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | CO (carbon monoxide)2/N2Switch type temperature-sensitive polymer and preparation method thereof |
| CN111019043B (en) * | 2019-12-12 | 2021-07-13 | 贵州师范学院 | CO (carbon monoxide)2/N2Switch type temperature-sensitive polymer and preparation method thereof |
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Application publication date: 20110316 |