CN103936925A - Preparation method of random copolymer with ion response and temperature sensitivity - Google Patents
Preparation method of random copolymer with ion response and temperature sensitivity Download PDFInfo
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- CN103936925A CN103936925A CN201410096965.5A CN201410096965A CN103936925A CN 103936925 A CN103936925 A CN 103936925A CN 201410096965 A CN201410096965 A CN 201410096965A CN 103936925 A CN103936925 A CN 103936925A
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Abstract
The invention discloses a preparation method of a random copolymer with ion response and temperature sensitivity. The method comprises the following steps: dissolving a pyridine compound, N-vinyl pyrrolidone, an initiator and a chain transfer agent in a solvent, and carrying out reversible addition-fragmentation chain transfer active polymerization to prepare the random copolymer. The random copolymer prepared through the method can self-assemble in water to form a stable micelle, the formed micelle can simultaneously load and release hydrophilic and hydrophobic medicines, and the random copolymer has a wide application prospect in the fields of medical treatment, targeted therapy, heavy metal adsorption, polymer brush preparation and static spinning.
Description
Technical field
The invention belongs to macromolecule polymer material and field of compound material, be specifically related to a kind of preparation method of the random copolymers with Ion response and temperature sensitivity.
Background technology
As everyone knows, intelligent macromolecule, the particularly polymer of Ion response and temperature sensitivity, due to its good biocompatibility, in recent years, be applied widely at medicine and chemical field, particularly the important application in industrial heavy metal adsorption and oral targeting drug delivery system has caused concern widely.Poly N-vinyl pyrrolidone (PNVP), as the temperature sensing polymer of a quasi-representative, is applied in the fields such as bio-pharmaceutical control release.
The polymerization of reversible addition-fracture chain transfer activity, it is RAFT living polymerization, great advantage is that applicable monomer scope is wide, the designed capacity of molecule is strong, can be used for preparing block, random, grafting, the multipolymer such as star-like, be a kind of fast, the polymerization methods of efficient, mild condition, be all widely used in various fields such as biology, medicine, chemosynthesis.
In recent years, the research of intelligent macromolecule is the focus of research always.Chinese patent CN102898586 has reported a kind of composite intelligent polymer photon crystal based on biological template bionic preparation with pH response, the polymer composites with photon crystal structure has good spectral response to specific pH, thereby has potential application prospect in chemical sensitisation field.Chinese patent CN102757538 has reported and has utilized emulsifier-free emulsion polymerization to synthesize a kind of novel pH, temperature dual response microgel, and the biomacromolecule that this microgel comprises part has good biocompatibility and biological degradability, can be widely used in the base material such as pharmaceutical carrier and biosensor.Chinese patent CN101033282 has reported a kind of ion identification type intelligent macromolecule material, and this kind of material has Thermo-sensitive, can also, by the specific alkalimetal ion of identification, cause that volume, the transmittance etc. of polymer materials changes.
Summary of the invention
The object of the invention is to overcome prior art defect, a kind of preparation method of the random copolymers with Ion response and temperature sensitivity is provided.
Concrete technical scheme of the present invention is as follows:
A kind of preparation method of the random copolymers with Ion response and temperature sensitivity, pyridine compounds, NVP, initiator, chain-transfer agent are dissolved in solvent, prepare described random copolymers by the polymerization of reversible addition-fracture chain transfer activity.
In a preferred embodiment of the invention, comprise the steps:
(1) purification of pyridine compounds and NVP: pyridine compounds and excessive siccative are obtained to the monomer pyridine compounds after purification by vacuum distillation apparatus, NVP (NVP) mistake adsorption column is removed to stopper and obtain the NVP after purification;
(2) prepare described random copolymers: NVP, pyridine compounds, chain-transfer agent and initiator after purifying are dissolved in solvent with the mol ratio of 1～10:1～10:0.04～0.8:0.01～0.15, after continuous freeze thawing is degassed at 65～70 DEG C of polymerization 40～60h of argon gas, the sudden cold stopped reaction of liquid nitrogen, in precipitation agent, precipitate, vacuum-drying obtains random copolymers again.
Further preferred, described siccative is anhydrous magnesium sulfate or CaH
2, the material of described adsorption column is neutral alumina or alkali alumina, described precipitation agent is methyl alcohol, acetonitrile, methanol/ethyl acetate or ether/sherwood oil.
Further preferred, described pyridine compounds is 4-vinylpridine (4VP), 2-methyl-5-vinylpyrine, 2-vinyl pyridine, styryl pyridine or 1,2-di(4-pyridyl)ethylene.
Further preferred, described chain-transfer agent is dithiobenzoic acid cumyl ester (CDB) or lauryl mercaptan.
Further preferred, described initiator is AIBN, BPO/DMA or BPO.
Further preferred, described solvent is THF or toluene.
The invention has the beneficial effects as follows:
1, prepared by method of the present invention a kind ofly has ion responsitivity and temperature sensitivity random copolymers can be self-assembled into stable micella in water, simultaneously load of the micella forming and discharge hydrophilic and dewatering medicament, in pharmaceutical carrier, targeted therapy, metal adsorption, prepare the aspect such as polymer brush and electrostatic spinning and have good application prospect;
2, preparation method of the present invention is by RAFT living polymerization, prepare functional type random copolymers, make full use of efficient, the mild condition of RAFT polymerization, quick, the applicable wide feature of monomer scope, prepare the random copolymers of functional type, for the strong parents' multipolymer of structural controllability provides a new synthetic route.
Brief description of the drawings
P4VP-co-PNVP prepared by Fig. 1, the embodiment of the present invention 1
1h NMR nuclear magnetic spectrogram;
P4VP-co-PNVP random copolymers prepared by Fig. 2, the embodiment of the present invention 1 transmission electron microscope photo that is self-assembled into stable micella in water.
Embodiment
By reference to the accompanying drawings technical scheme of the present invention is further detailed and is described by embodiment below.
Embodiment 1
(1) purification of 4VP and NVP
By 4VP(200mL) and CaH
2(5g) join in 500mL round-bottomed flask, by vacuum distillation apparatus, the monomer 4VP that obtains purifying, productive rate is Y
1be 90%, then by NVP(200mL) the parlkaline alumina column monomer NVP that obtains purifying, productive rate is 93%.
(2) preparation of P4VP-co-PNVP
By 4VP(1.5mmol); NVP(1.5mmol); CDB(0.0136g); AIBN(0.00164g) be dissolved in the THF of 3mL; after degassed 3～5 times of the continuous freeze thawing of liquid nitrogen under argon shield 65 DEG C of polymerizations, the sudden cold stopped reaction of liquid nitrogen after reaction 48h, selecting methanol/ethyl acetate (6:1) volume ratio is 1:20 repeated precipitation 3 times; vacuum-drying obtains orange-red product P 4VP-co-PNVP, productive rate Y
2be 70%.
In above-mentioned steps, described siccative can also be anhydrous magnesium sulfate, and the material of above-mentioned adsorption column can also be alkali alumina, and above-mentioned precipitation agent can also be methyl alcohol, acetonitrile or ether/sherwood oil.Above-mentioned chain-transfer agent can also be lauryl mercaptan, and above-mentioned initiator can also be BPO/DMA or BPO, and above-mentioned solvent can also be toluene.
The mol ratio of above-mentioned NVP, pyridine compounds, chain-transfer agent and initiator can change in following ranges: 1～10:1～10:0.04～0.8:0.01～0.15, above-mentioned reaction conditions can also be at 65～70 DEG C of polymerization 40～60h of argon gas.
The structural formula of gained P4VP-co-PNVP is as follows:
Fig. 1's
1h nuclear magnetic spectrogram shows δ
h/ppmbe that disappear two keys of explanation pyridine compounds 4VP of 5.267,5.303 and 6.651 spectrum peaks react, 5.58, spectrum peak, 6.15ppm place disappear explanation NVP above pair keys open reaction.Thereby prove the carrying out of reaction.The transmission electron microscope picture of Fig. 2, can observe the nano-micelle of obvious nucleocapsid structure, analyzes by DLS, and this micella has good thermostability.
Embodiment 2～5
With embodiment 1 technique, the 4VP thing in step changes 2-methyl-5-vinylpyrine, 2-vinyl pyridine, styryl pyridine, 1,2-di(4-pyridyl)ethylene into, obtains different products collection efficiency Y
1, Y
2as shown in the table:
| Embodiment | Azole compounds | Y 1/% | Y 2/% |
| 2 | 2-methyl-5-vinylpyrine | 88 | 71 |
| 3 | 2-vinyl pyridine | 91 | 75 |
| 4 | Styryl pyridine | 85 | 62 |
| 5 | 1,2-di(4-pyridyl)ethylene | 90 | 65 |
Embodiment 6
There is the preparation of the random copolymers micella of Ion response and temperature sensitivity
In with graduated test tube, dissolve P4VP-co-PNVP(3mg prepared by embodiment 1 with 1mL THF), speed with 0.5mL/min slowly splashes into 3mL water in solution, after at normal temperatures uncovered leave standstill, dropping to 3mL place until liquid level is after THF volatilizees completely, sample test.
(1), in the micella forming, analyze and in micellar solution, add configuration metal ions Zn with DLS
2+and Cu
2+, to find adding after a certain amount of metal ion, the size of micella changes, and illustrates that this functional type random copolymers has ion responsitivity.
(2) in the micella forming, by the transmitance of the micellar solution under uv analyzer test differing temps, there is catastrophe point at 42 DEG C in this responsive to temperature type multipolymer, and 42 DEG C is its minimum critical temperature of dissolving each other.
The above, be only preferred embodiment of the present invention, therefore can not limit according to this scope of the invention process, the equivalence done according to the scope of the claims of the present invention and description changes and modifies, and all should still belong in the scope that the present invention contains.
Claims (7)
1. one kind has the preparation method of the random copolymers of Ion response and temperature sensitivity, it is characterized in that: pyridine compounds, NVP, initiator, chain-transfer agent are dissolved in solvent, prepare described random copolymers by the polymerization of reversible addition-fracture chain transfer activity.
2. the preparation method of a kind of random copolymers with Ion response and temperature sensitivity as claimed in claim 1, is characterized in that: comprise the steps:
(1) purification of pyridine compounds and NVP: the monomer pyridine compounds after pyridine compounds and excessive siccative are obtained purifying by vacuum distillation apparatus, the NVP after NVP is crossed to adsorption column and removed stopper and obtain purifying;
(2) prepare described random copolymers: NVP, pyridine compounds, chain-transfer agent and initiator after purifying are dissolved in solvent with the mol ratio of 1～10:1～10:0.04～0.8:0.01～0.15, after continuous freeze thawing is degassed at 65～70 DEG C of polymerization 40～60h of argon gas, the sudden cold stopped reaction of liquid nitrogen, in precipitation agent, precipitate, vacuum-drying obtains random copolymers again.
3. the preparation method of a kind of random copolymers with Ion response and temperature sensitivity as claimed in claim 2, is characterized in that: described siccative is anhydrous magnesium sulfate or CaH
2, the material of described adsorption column is neutral alumina or alkali alumina, described precipitation agent is methyl alcohol, acetonitrile, methanol/ethyl acetate or ether/sherwood oil.
4. the preparation method of a kind of random copolymers with Ion response and temperature sensitivity as claimed in claim 1 or 2, it is characterized in that: described pyridine compounds is 4-vinylpridine, 2-methyl-5-vinylpyrine, 2-vinyl pyridine, styryl pyridine or 1,2-di(4-pyridyl)ethylene.
5. the preparation method of a kind of random copolymers with Ion response and temperature sensitivity as claimed in claim 1 or 2, is characterized in that: described chain-transfer agent is dithiobenzoic acid cumyl ester or lauryl mercaptan.
6. the preparation method of a kind of random copolymers with Ion response and temperature sensitivity as claimed in claim 1 or 2, is characterized in that: described initiator is AIBN, BPO/DMA or BPO.
7. the preparation method of a kind of random copolymers with Ion response and temperature sensitivity as claimed in claim 1 or 2, is characterized in that: described solvent is THF or toluene.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430499A (en) * | 2016-09-28 | 2017-02-22 | 顺德职业技术学院 | Preparation method of binary polymer molecule brush heavy metal chelating agent |
| CN106467327A (en) * | 2016-09-28 | 2017-03-01 | 顺德职业技术学院 | The preparation method of ter-polymers molecular brush heavy metal chelating agent |
| CN106496577A (en) * | 2016-09-28 | 2017-03-15 | 顺德职业技术学院 | The preparation method of thermosensitive type ter-polymers molecular brush heavy metal chelating agent |
| CN106496574A (en) * | 2016-09-28 | 2017-03-15 | 顺德职业技术学院 | The preparation method of thermosensitive type heavy metal chelating agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085819A1 (en) * | 2007-12-27 | 2009-07-09 | Bausch & Lomb Incorporated | Surface active segmented block copolymers |
| CN102718933A (en) * | 2012-07-06 | 2012-10-10 | 厦门大学 | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof |
| CN102952236A (en) * | 2011-08-29 | 2013-03-06 | 南开大学 | Molecularly imprinted polymeric microsphere resin applicable to aqueous solution system and preparing method thereof |
-
2014
- 2014-03-14 CN CN201410096965.5A patent/CN103936925A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009085819A1 (en) * | 2007-12-27 | 2009-07-09 | Bausch & Lomb Incorporated | Surface active segmented block copolymers |
| CN102952236A (en) * | 2011-08-29 | 2013-03-06 | 南开大学 | Molecularly imprinted polymeric microsphere resin applicable to aqueous solution system and preparing method thereof |
| CN102718933A (en) * | 2012-07-06 | 2012-10-10 | 厦门大学 | Polyhedral oligomeric silsesquioxane-based amphiphilic triblock copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》: "Controlled Nitroxide-Mediated and Reversible Addition–Fragmentation Chain Transfer Polymerization of N-Vinylpyrrolidone: Synthesis of Block Copolymers with Styrene and 2-Vinylpyridine", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》, vol. 44, no. 1, 21 November 2005 (2005-11-21), pages 659 - 665 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430499A (en) * | 2016-09-28 | 2017-02-22 | 顺德职业技术学院 | Preparation method of binary polymer molecule brush heavy metal chelating agent |
| CN106467327A (en) * | 2016-09-28 | 2017-03-01 | 顺德职业技术学院 | The preparation method of ter-polymers molecular brush heavy metal chelating agent |
| CN106496577A (en) * | 2016-09-28 | 2017-03-15 | 顺德职业技术学院 | The preparation method of thermosensitive type ter-polymers molecular brush heavy metal chelating agent |
| CN106496574A (en) * | 2016-09-28 | 2017-03-15 | 顺德职业技术学院 | The preparation method of thermosensitive type heavy metal chelating agent |
| CN106496574B (en) * | 2016-09-28 | 2019-05-17 | 顺德职业技术学院 | The preparation method of thermosensitive type heavy metal chelating agent |
| CN106496577B (en) * | 2016-09-28 | 2019-05-17 | 顺德职业技术学院 | The preparation method of thermosensitive type polymer molecule brush heavy metal chelating agent |
| CN106467327B (en) * | 2016-09-28 | 2019-06-07 | 顺德职业技术学院 | The preparation method of quadripolymer molecular brush heavy metal chelating agent |
| CN106430499B (en) * | 2016-09-28 | 2019-07-05 | 顺德职业技术学院 | The preparation method of ter-polymers molecular brush heavy metal chelating agent |
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