CN1197888C - Thermo-sensitive water-soluble high-molecular material - Google Patents
Thermo-sensitive water-soluble high-molecular material Download PDFInfo
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- CN1197888C CN1197888C CN 01145646 CN01145646A CN1197888C CN 1197888 C CN1197888 C CN 1197888C CN 01145646 CN01145646 CN 01145646 CN 01145646 A CN01145646 A CN 01145646A CN 1197888 C CN1197888 C CN 1197888C
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Abstract
The present invention relates to a thermo-sensitive water-soluble high-molecular material which is a copolymer formed by the monomers of 5 to 95 weight portions of N-isopropyl acrylamide, 0.1 to 80 weight portions of 1-vinyl-2-pyrrolidinone and 0.1 to 30 weight portions of acrylic acid (AA) according to requirements. The copolymer has the thermal reversible and water-soluble characteristics, namely so called an environmental inductive type macromolecule or an intelligent macromolecule, precipitation can occur in an aqueous solution thereof when temperature rises to a certain temperature (LCST), and the precipitation can be dissolved on the contrary. The precipitation temperature can be adjusted via changing monomer composition proportion, the VPD content can be improved so as to enhance material LCST to 80 DEG C and increase the water solubility of the material. The AA content can be improved so as to reduce the LCST to 20 DEG C and increase-COOH group quantity, and the copolymer has the advantage of high reactivity. Therefore, the new material has large LCST adjusting range via control the proportion of the monomers, and a large quantity of reactive groups are on the macromolecules.
Description
Technical field
The present invention relates to a kind of macromolecular material, particularly relate to a kind of thermo-sensitive water-soluble high-molecular material (thermal responsive, water-soluble polymers).
Background technology
Many polymers solns have the phenomenon of cloud point (cloud point), and polymkeric substance begins to have solid precipitation to come out under this temperature and makes the solution appearance vaporific.Most polymkeric substance-solvent systems can descend and reduction solubleness along with temperature, yet opposite phenomenon then appears in many water-soluble polymerss in the aqueous solution, that is polymkeric substance produces precipitation on the contrary under higher temperature, and this specified temp is called " than lower critical solution temperature " (LCST; Lower Critical solution temperature).If this kind is by being clear to the vaporific reversible that is changed to, releases the control system or be applied in purifying or separate some predetermined substance just this polymers soln can be applicable to the medicine of thermal-induction type.This kind has the polymer of hot reversible water soluble characteristic, promptly so-called intelligent polymer (smart polymer) a kind of.
The application of water-soluble intelligent polymer aspect separation and purification is present developing new technology, and its future is at field institute roles such as biological medicine, environmental protection, resources, and is very important, will be a kind of critical material.Yet there is following defective:
1. the material of prior art, the reactive group that can be used to grasp predetermined substance is positioned at the two ends terminal group, so reactive group is few, and when the application of back segment, usefulness is undesirable.For example, please refer to BioconjugateChem., 4,341-346 (1993).
2. the present water-soluble high molecular LCST of temperature-sensitive has a certain distance apart from people's body temperature, more than at least three degree, can't be used in the intravital intelligent medicine of people and release control.The polymer that disclosed for No. 5969052 of United States Patent (USP) for example, its operating temperature range is little, and LCST is below 34 ℃.
Therefore, for the application that makes thermo-sensitive water-soluble high-molecular can be more wide, more reach perfection, be necessary to seek the road of improvement at the problems referred to above.
Summary of the invention
In view of this, one of purpose of the present invention just provides a kind of thermo-sensitive water-soluble high-molecular material, and it has adjustable cloud point on a large scale.
Two of purpose of the present invention just provides a kind of thermo-sensitive water-soluble high-molecular material, and it has a large amount of reactive functional group bases, can improve separation and purification usefulness.
Three of purpose of the present invention just provides a kind of thermo-sensitive water-soluble high-molecular material, and the cloud point that it has near body temperature (about about 37 ℃) is applied in the intelligent prosecutor face of releasing of human body medicine.
Above-mentioned purpose of the present invention is achieved in that a kind of thermo-sensitive water-soluble high-molecular material, comprising by the formed multipolymer of following monomer:
5～95 weight part N-N-isopropylacrylamide;
0.1～80 weight part l-vinyl-2-pyrrolidones; And
0.1～30 parts by weight of acrylic acid that depends on the needs.
Thermo-sensitive water-soluble high-molecular material of the present invention, wherein the cloud point of this material is between 20～80 ℃.
Thermo-sensitive water-soluble high-molecular material of the present invention, wherein the molecular weight of this material is between 1000～25000.
Thermo-sensitive water-soluble high-molecular material of the present invention, wherein this material is to carry out copolymerization in the presence of a chain-transfer agent, and the addition of described chain-transfer agent is 1～10% of all monomer weights.
Thermo-sensitive water-soluble high-molecular material of the present invention, wherein said chain-transfer agent are the 3-thiohydracrylic acid.
A kind of thermo-sensitive water-soluble high-molecular material, wherein the cloud point of this material comprises by the formed multipolymer of following monomer between 36.5～38.5 ℃:
(a) N-N-isopropylacrylamide; And
(b) l-vinyl-2-pyrrolidone,
Wherein (a): mol ratio (b) about 8～10: 1.
A kind of thermo-sensitive water-soluble high-molecular material, wherein the cloud point of this material is between 36.5～3g.5 ℃, and it comprises by the formed multipolymer of following monomer:
(a) N-N-isopropylacrylamide;
(b) l-vinyl-2-pyrrolidone; And
(c) vinylformic acid,
Wherein (a): (b): mol ratio (c) about 1～3: 1: 1～2.
A kind of thermo-sensitive water-soluble high-molecular material, it has following formula:
N=5～70 wherein; N=5～70; Y=0～70.
Thermo-sensitive water-soluble high-molecular material according to the present invention is by the formed multipolymer of following monomer: (a) 5～95 weight part N-N-isopropylacrylamide (N-isopropyl acrylamide; NIP); (b) 0.1～80 weight part l-vinyl-2-pyrrolidone (1-vinyl-2-pyrrolidinone; VPD); And (c) 0.1～30 parts by weight of acrylic acid (acrylic acid of depend on the needs (optionally); AA).When changing monomeric proportion of composing, can adjust temperature of precipitation, the LCST of material is improved, and can improve the water-soluble of material; And when the content of AA rises LCST is reduced, and the amount of COOH reactive group increases.Therefore, utilize the monomeric ratio of control, make this kind novel material have the LCST that can adjust on a large scale, and a large amount of reactive groups are arranged on polymer.
Thermo-sensitive water-soluble high-molecular of the present invention is to carry out copolymerization by (a) N-N-isopropylacrylamide (NIP), (b) l-vinyl-2-pyrrolidone (VPD) to form, and can optionally add (c) vinylformic acid (AA) monomer and carry out copolymerization, as following reaction formula:
N=5～70 wherein; M=5～70; Y=0～70.
Add l-vinyl-2-pyrrolidone (VPD) monomer among the present invention and can improve the cloud point (Cloud point or LCST) of material, when VPD content rises, can make the LCST of material be increased to 80 ℃.Moreover, because VPD itself has good wetting ability, therefore also can increase the water-soluble of material.In addition, the present invention can optionally add the third monomer: vinylformic acid (AA) monomer reduces the cloud point of material, can make the LCST of material be reduced to 20 ℃ when AA content rises.Therefore, by the proportion of composing of control monomer NIP, VPD, AA, can adjust LCST on a large scale in the present invention, solve the too small deficiency of well known materials temperature-sensitive scope from 20～80 ℃.
Aspect rerum natura, about 40～50% (polymer/polymers+water) of the solubleness of NIP polymkeric substance, and the solubleness of NIP-VPD co-polymer can be increased to 50～60%
Again, the third monomer of the present invention: vinylformic acid (AA) monomer, except can reducing the LCST, but owing to itself have reactive activity base (COOH), so after polymerization, can significantly increase the reactive group quantity of material, to solve the very few problem of well known materials reactive group.
Macromolecular material of the present invention can be applicable to aspects such as discharging control, separation and purification and biological sensor on the biotechnology.In a preferred embodiment of the present invention, be to utilize (a) N-N-isopropylacrylamide (NIP) and (b) l-vinyl-2-pyrrolidone (VPD) to carry out copolymerization, to synthesize LCST between 36.5～38.5 ℃, the thermo-sensitive water-soluble high-molecular material that is suitable for body temperature, wherein (a): mol ratio (b) preferable about 8～10: 1.In another preferred embodiment, also can add (c) vinylformic acid (AA) monomer simultaneously and carry out copolymerization, to synthesize LCST between 36.5～38.5 ℃ thermo-sensitive water-soluble high-molecular material, (a) at this moment: (b): mol ratio (c) preferable about 1～3: 1: 1～2.
Above-mentioned monomer of the present invention can begin to carry out free radical copolymerization under the existence of agent together, and the temperature of reaction is about 30～150 ℃, and is preferable with 45～80 ℃ especially.Initiator used herein is preferable with superoxide or azo class (azo) catalyzer.Superoxide initiator commonly used comprises; Percarbonic acid isopropyl esters (isopropyl percarbonate), benzoyl peroxide (benzoyl peroxide), dilauroyl peroxide (lauroyl peroxide), acetyl peroxide (acetyl peroxide) etc.Azo class initiator commonly used comprises: 2,2 '-azobis isobutyronitrile (2,2 '-azo-bis-isobutyronitrile; AIBN), 1, the two cyclohexanenitriles (1,1 '-azo-bis (cyclohexanecarbonitrile)), 2 of 1 '-azo, 2 '-azo two (2, the 4-methyl pentane nitrile) (2,2 '-azo-bis (2,4-dimethylvaleronitrile)) etc.
The addition of initiator can be 0.002% to 1% of monomer weight and does not wait, but is preferably 0.03% to 0.3% of monomer weight.
Copolymerization of the present invention can add the molecular weight size of a chain-transfer agent with the control macromolecular material.The addition of chain-transfer agent can be from 1～10% of monomer weight, and chain-transfer agent adds many more, and molecular weight is more little.The molecular weight of macromolecular material of the present invention is approximately from 1000～25000.Any chain-transfer agent that is used for modifying Raolical polymerizable all can be used on the present invention in any known technology, for example the straight or branched alkyl sulfhydryl of carbon number 2-2 1 (alkyl thiols), mercaptan acid (mercapto acids) or fluoridize mercaptan (fluorinated thiols) etc.
Macromolecular material of the present invention can be according to known manner with bulk polymerization (bulkpolymerlzation) or solution polymerization (solution polymerization) and synthesize.Solution polymerization is to be dissolved in above-mentioned monomer in the appropriate solvent earlier, the content of solvent can reach 90%, appropriate solvent includes ketone, ethers, alcohols, ester class, amine etc., for example acetone, methylethylketone, isopropyl acetate, ether, ethanol, butanols, dimethyl formamide (DMF) etc.In addition, macromolecular material of the present invention also can use in salt brine solution (aqueous brine) in the mode of suspension polymerization (suspensionpolymerization) synthetic, and with inorganic acid salt or water-soluble organic polymer as stablizer.
Embodiment
For above-mentioned and other purposes of the present invention, feature and advantage can be become apparent, cited below particularlyly go out preferred embodiment, be described in detail below:
Embodiment 1
Get 5g monomer N-N-isopropylacrylamide (NIP) and be dissolved among the 35g DMF, slowly stir, it is dissolved fully.Then, add 5g monomer l-vinyl-2-pyrrolidone (VPD) and 0.11g chain-transfer agent 3-thiohydracrylic acid (MPA).After being warming up to 70 ℃, add 0.04g initiator 2,2 '-azobis isobutyronitrile (AIBN) reaction 5 hours.Reacted body lotion is concentrated, slowly splash in the ether, filtration can get faint yellow powder.
Co-polymer (NIP: VPD=1: 1 mol ratio) be dissolved in the deionized water with gained, solid content 20%, heating rate with 2 ℃ of per minutes in nitrogen heats up, measure LCST with heat difference scan-type calorimeter (DSC), and measure its molecular weight with GPC (gel partition chromatography).
According to above-mentioned experimental procedure, obtain NIP: VPD=2 successively: 1, other two groups of co-polymers of 10: 1 mol ratios, and measure its LCST and molecular weight.The gained result as shown in Table 1, along with the ratio of VPD increases, LCST rises to 54.8 ℃ from 37.4 ℃.
Table 1
| NIP∶VPD | 1∶1 | 2∶1 | 10∶1 |
| LCST(℃) | 54.8 | 39.4 | 37.4 |
| Molecular weight | 12000 | 20000 | 18000 |
Embodiment 2
Get 5g monomer N-N-isopropylacrylamide (NIP) and be dissolved among the 50g DMF, slowly stir, it is dissolved fully.Then, add 5g monomer l-vinyl-2-pyrrolidone (VPD), 3.185g vinylformic acid (AA) monomer and 0.15g chain-transfer agent 3-thiohydracrylic acid (MPA).After being warming up to 70 ℃, add 0.06g initiator 2,2 '-azobis isobutyronitrile (AIBN) reaction 5 hours.Reacted solution is concentrated, slowly splash in the ether, filtration can get faint yellow powder.
Co-polymer (NIP: VPD: AA=1: 1: 1 mol ratio) be dissolved in the deionized water with gained, solid content 20%, heating rate with 2 ℃ of per minutes in nitrogen heats up, measure LCST with heat difference scan-type calorimeter (DSC), and measure its molecular weight with GPC (gel partition chromatography).
According to above-mentioned experimental procedure, obtain NIP: VPD: AA=2 successively: other two groups of co-polymers of 1: 2,2: 1: 4 mol ratios, and measure its LCST and molecular weight.The gained result as shown in Table 2, along with the ratio of AA increases, LCST drops to 26.1 ℃ from 39.7 ℃.
Table 2
| NIP∶VPD∶AA | 1∶1∶1 | 2∶1∶2 | 2∶1∶4 |
| LCST(℃) | 39.7 | 38.4 | 26.1 |
| Molecular weight | 10000 | 18000 | 13000 |
Though the present invention discloses as above with preferred embodiment, so it is not in order to limiting the present invention, anyly is familiar with this operator, and change of being made and retouching without departing from the spirit and scope of the present invention all should be within the scope of the present invention.
Claims (7)
1. thermo-responsive water-soluble high-molecular material comprises by the formed multipolymer of following monomer:
A.5-95 weight part N-N-isopropylacrylamide;
B.0.1-80 weight part 1-vinyl-2-pyrrolidone;
And have a following structural formula:
N=5-70 wherein; N=5-70; Y=0-70;
And the molecular weight of above-mentioned multipolymer is between 1000-25000.
2. thermo-responsive water-soluble high-molecular material as claimed in claim 1, described monomer also comprises the 0.1-30 parts by weight of acrylic acid.
3. as claimed in claim 1 or 2, it is characterized in that the cloud point of this material is between 20-80 ℃.
4. thermo-responsive water-soluble high-molecular material as claimed in claim 1 or 2 is characterized in that, this material is to carry out copolymerization in the presence of a chain-transfer agent, and the addition of this chain-transfer agent is the 1-10% of all monomer weights.
5. thermo-responsive water-soluble high-molecular material as claimed in claim 4 is characterized in that, described chain-transfer agent is the 3-thiohydracrylic acid.
6. thermo-responsive water-soluble high-molecular material as claimed in claim 1 or 2, the cloud point of this material are between 36.5-38.5 ℃, and wherein the mol ratio of a: b is 8-10: 1.
7. thermo-responsive water-soluble high-molecular material as claimed in claim 1 or 2, its cloud point be between 36.5-38.5 ℃, wherein the about 1-3 of the mol ratio of a: b: c: 1: 1-2.
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| CN1987640B (en) * | 2005-12-23 | 2010-05-05 | 乐凯集团第二胶片厂 | Silver halide light sensitive material |
| CN101585897B (en) * | 2009-06-16 | 2010-12-01 | 广东工业大学 | Water-solubility copolymer with amantadine-containing pendant group and preparation method thereof |
| KR20170126936A (en) * | 2015-03-04 | 2017-11-20 | 다우 글로벌 테크놀로지스 엘엘씨 | As an excipient for effective solubilization of a water-insoluble material from a solid mixture, |
| CN115260394B (en) * | 2022-06-30 | 2024-02-23 | 海安启弘纺织科技有限公司 | Preparation method of phase-conversion microcapsule for intelligent temperature-regulating textile |
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