CN104211970B - Supermolecular hydrogel material for constructing calixarene and preparation method of supermolecular hydrogel material - Google Patents

Abstract

The invention discloses a supermolecular hydrogel material for constructing calixarene and a preparation method of the supermolecular hydrogel material. The supermolecular hydrogel material is prepared from dodecyl modified sulfonated calix[4]arene (SC4AD) and methyl viologen modified polyvinyl alcohol under the interaction of supermolecules. The preparation method comprises the steps of self-aggregating SC4AD in a water liquid to form a micelle; and crosslinking the SC4AD micelle through PVA-MV by virtue of the host-guest bonding capacity of viologen and sulfonated calixarene to form the supermolecular hydrogel which is stable at room temperature. The supermolecular hydrogel material which is stable at room temperature is obtained by using a simple, convenient and feasible liquid mixing way by virtue of the advantage that a specific group of the viologen as a guest can be identified by the sulfonated calixarene. Compared with methods for synthesizing other hydrogels, the method disclosed by the invention has the advantages of simplicity in operation and high yield and is a convenient and effective hydrogel preparation method. The supermolecular hydrogel material has a wide application prospect in the field of materials.

Description

A kind of supramolecular hydrogel glue material constructed by calixarenes and preparation method thereof

Technical field

The invention belongs to intellectual material technical field, the preparation of particularly a kind of supramolecular hydrogel constructed by calixarenes And application.

Background technology

Water is organic important component part, and water is reconciled and adjusted biological bioprocess complicated in vivo（Referring to：L. Fang, S. Basu, C. H. Sue, A. C. Fahrenbach, J. F. Stoddart,J. Am. Chem. Soc.2011,133, 396-399.）.The gel being formed in aqueous, that is, hydrogel, since last century the fifties End starts, and synthesis hydrogel is defined as an important field of research（Referring to E. A. Appel, J. del Barrio, X. J. Loh, O. A. Scherman,Chem. Soc. Rev.2012, 41,6195-6214.）.This mainly due to It has application widely, including the material on super absorbent material, chemistry and bio-matrix, storage material, bio-pharmaceutical Transmission and construction bioengineered tissue（Referring to：M. P. Lutolf,Nat. Mater.2009,8, 451-453； (2) K. Y. Lee, D. J. Mooney,Chem. Rev.2001,101, 1869-1879.）.Because covalent interaction is handed over The hydrogel that linked polymer segment is constructed has the shortcomings of crosslink density is uneven, and preparation is difficult, light transmission is poor, is moved with special State noncovalent interaction carrys out cross linked polymer segment, has developed a brand-new direction-supramolecular hydrogel.The polymerization of these aqueous phases Network constitutes the interesting soft material of a class, and these materials have attracting property such as stimulating responsive and self-repairability Can, improve their dynamic property and real world applications（Referring to：L. Yu, J. Ding,Chem. Soc. Rev.2008,37, 1473-1481）.These materials are expected to be applied to biomedical correlational study and can be selective Imitate the viscoelasticity of human tissue（Referring to：M. de Loos, B. L. Feringa, J. H. van Esch,Eur. J. Org. Chem.2005, 3615-3631.）.Therefore, the development of supramolecular hydrogel gets more and more people's extensive concerning.

However, not all of noncovalent interaction is all effectively in aqueous, in order to solve this problem, water The big ring receptor of dissolubility, such as cyclodextrin, calixarenes and Cucurbituril etc., it is already used to as preparing the new of supramolecular hydrogel Method（Referring to：J. W. Steed, J. A. Foster,Angew. Chem. Int. Ed.2010,49, 6718- 6724.）.The micro-molecular hydrogel of cup [4] aromatic hydrocarbons modified based on proline is got more and more people's extensive concerning（Referring to：T. Becker, C. Y. Goh, F. Jones, M. J. McIldowie, M. Mocerino, M. I. Ogden,Chem. Commun.2008,33, 3900-3092; (2) C. Y. Goh, T. Becker, D. H. Brown, B. W. Skelton, F. Jones, M. Mocerino, M. I. Ogden,Chem. Commun.2011,47, 6057- 6059; (3) J. Zhang, D. S. Guo, L. H. Wang, Z. Wang, Y. Liu,Soft Mater. 2011,7, 1756-1762）.Sulfonated calixarenes are the important derivants of a class of calixarenes, have good water solublity, do not have hemolytic poison Property, there is extensive inclusion property.The Sulfonated calixarenes binding ability stronger to purpurine class object, for us further using sulphur Change calixarenes are constructed supramolecular hydrogel and are provided theoretical foundation（Referring to：Guo, D.-S.、 Wang, L.-H.、 Liu, Y.J. Org. Chem.2007,72, 7775-7778）.But, still it is rarely reported based on the hydrogel of sulfonation cup [4] aromatic hydrocarbons.

Content of the invention

It is an object of the invention to provide a kind of supramolecular hydrogel glue material constructed by calixarenes and preparation method thereof, this surpasses Molecule hydrogel material is the new gel rubber material of a class.Purpurine is had to the formation of gel with the interaction of Sulfonated calixarenes Conclusive effect.

Technical scheme：

A kind of supramolecular hydrogel glue material constructed by calixarenes, modifies sulfonation cup [4] aromatic hydrocarbons by dodecyl（SC4AD） Modify polyvinyl alcohol with methyl viologen（PVA-MV）Interacted by supermolecule and formed, it constructs the concrete structure of primitive such as Under：

.

A kind of preparation method of the supramolecular hydrogel glue material constructed by calixarenes, comprises the steps：

1) dodecyl modifies sulfonation cup [4] aromatic hydrocarbons（SC4AD）Preparation：

Cup [4] aromatic hydrocarbons is dissolved in acetonitrile, adds sodium hydride, be heated to reflux more than 0.5 hour under nitrogen protection, Ran Houjia Enter bromododecane hydrocarbon, continue backflow 48 hours, after being cooled to room temperature, filter and be spin-dried for solvent, add dichloromethane dissolving, point Not Yong 0.2mol/L hydrochloric acid and distilled water wash organic faciess 3-5 time, add anhydrous sodium sulfate drying 8-10 hour, filter out dry Drying prescription, the silica gel post separation of the crude product in solution after concentration, eluant is 1 for volume ratio:1 dichloromethane-petroleum ether solution, The dodecyl obtaining white modifies cup [4] aromatic hydrocarbons；

Dodecyl obtained above is modified cup [4] aromatic hydrocarbon solid and is dissolved in chloroform, adds chlorosulfonic acid, room temperature reaction 4 hours, Evaporate chloroform, be dissolved in water, with the sodium hydroxide solution of 1M, the pH of resulting solution be adjusted to neutrality, be spin-dried for solvent, gained is solid Body water-ethanol recrystallization, obtains white dodecyl and modifies sulfonation cup [4] aromatic hydrocarbons (SC4AD)；

2) methyl viologen modifies polyvinyl alcohol（PVA-MV）Preparation：

Methyl viologen modify polyvinyl alcohol according to（E. A. Appel, X. J. Loh, S. T. Jones, F. Biedermann, C. A. Dreiss, O. A. Scherman, J. Am. Chem. Soc. 2012,134, 11767- 11773）Synthesis.

3) preparation of supramolecular hydrogel glue material

Concrete grammar is：SC4AD, PVA-MV are dissolved separately in distilled water, are prepared into concentration respectively and are The solution of 0.025g/mL.Two kinds of solution of same volume are simultaneously added dropwise reagent bottle respectively with the speed of 0.5-1mL/min In, concussion shakes up, stands 30 seconds and can be prepared by supramolecular hydrogel.

Described cup [4] aromatic hydrocarbons, acetonitrile, the amount ratio of sodium hydride, bromododecane hydrocarbon and dichloromethane are 1mol: 15L : 4.25mol:5mol:37.5L.

Described dodecyl modification cup [4] aromatic hydrocarbons, chloroform, the amount ratio of chlorosulfonic acid are 1mol:3L:4.25mol.

The reaction mechanism of the present invention and product attribute：

In aqueous, SC4AD self assemble forms micelle, due to the Subjective and Objective bonded energy of purpurine and Sulfonated calixarenes Power, PVA-MV will be crosslinked together for SC4AD micelle, thus forming stable supramolecular hydrogel under room temperature.

It is an advantage of the invention that：

The present invention utilizes the identification advantage to purpurine object special groups for the Sulfonated calixarenes, is mixed by simple and feasible solution Conjunction mode, has obtained stable supramolecular hydrogel glue material under a kind of room temperature.Compared with the method for the other hydrogel of synthesis, the party Method has the advantages that simple to operate, yield is high, is a kind of method preparing hydrogel easily and effectively.This supramolecular hydrogel Material has broad application prospects in Material Field.

Brief description

Fig. 1 modifies the nuclear magnetic spectrogram of sulfonation cup [4] aromatic hydrocarbons for dodecyl.

Fig. 2 is the photo of gel formation.

Fig. 3 modifies, for dodecyl, the laser light scattering experiment that sulfonation cup [4] aromatic hydrocarbons forms micelle in aqueous.

Fig. 4 modifies, for dodecyl, the AFM pattern that sulfonation cup [4] aromatic hydrocarbons forms micelle in aqueous.

Fig. 5 is the SEM pattern of the calixarenes supramolecular hydrogel obtaining.

Specific embodiment

Embodiment

A kind of preparation method of new supramolecular hydrogel glue material, comprises the steps：

1）Dodecyl modifies the preparation of sulfonation cup [4] aromatic hydrocarbons：

By 1.7g（4mmol）Cup [4] aromatic hydrocarbons is dissolved in 60mL acetonitrile, adds 0.41g（17mmol）Sodium hydride, nitrogen is protected Under be heated to reflux 0.5 hour.Add bromododecane hydrocarbon 4.98g afterwards（20mmol）, continue backflow 48 hours.It is cooled to room Temperature, filters and is spin-dried for solvent, adds the dissolving of 100ml dichloromethane, uses 0.2mol/L hydrochloric acid respectively（3×50mL）And distilled water （50mL）Washing organic faciess.Add anhydrous sodium sulfate drying 9h afterwards.Filtration drying agent, the crude product purified by silica gel post after concentration divides From eluant is 1 for volume ratio:1 dichloromethane-petroleum ether solution, dodecyl modification cup [4] aromatic hydrocarbons obtaining white is solid Body 3.95g, yield 90%.

Obtain solid 1.1g to above-mentioned（1.0 mmol）Middle addition 3mL chloroform is placed in 10mL round-bottomed flask, room temperature Deca 0.50g（4.25mmol）Chlorosulfonic acid, reacts 4 hours.Evaporate solvent, be dissolved in 50ml distilled water, use 1M sodium hydroxide solution The pH of resulting solution is adjusted to neutrality.It is spin-dried for solvent, crude product water-ethanol recrystallization, obtain white powdery solids 1.38g, yield 92%.Fig. 1 is the nuclear magnetic spectrogram of ethyl bridging sulfonation cup [4] aromatic hydrocarbons it is shown that dodecyl modifies sulfonation cup [4] architectural feature of aromatic hydrocarbons.

2）Methyl viologen modifies polyvinyl alcohol（PVA-MV）Preparation：

Methyl viologen modify polyvinyl alcohol according to（E. A. Appel, X. J. Loh, S. T. Jones, F. Biedermann, C. A. Dreiss, O. A. Scherman, J. Am. Chem. Soc. 2012,134, 11767- 11773）Synthesis.

3) preparation of the supramolecular hydrogel constructed by calixarenes, modifies sulfonation cup [4] aromatic hydrocarbons by dodecyl（SC4AD） Modify polyvinyl alcohol with methyl viologen to be formed by supermolecule interaction, concrete grammar is：25 mg SC4AD are added 1 mL The micellar solution that SC4AD is obtained is dissolved, Fig. 3 is the laser light scattering experiment of micellar solution, and Fig. 4 is the AFM pattern of micelle in water Characterize.25mgPVA-MV is added obtained solution in 1 mL water.Two kinds of solution are dripped respectively with the speed of 0.5-1mL/min simultaneously It is added in reagent bottle, concussion shakes up, stands 30 seconds and can be prepared by supramolecular hydrogel.Fig. 5 is calixarenes supramolecular hydrogel SEM pattern.

Claims (2)

1. a kind of supramolecular hydrogel glue material constructed by calixarenes, by dodecyl modify sulfonation cup [4] aromatic hydrocarbons (SC4AD) with Methyl viologen is modified polyvinyl alcohol (PVA-MV) and is formed by supermolecule interaction, and it is as follows that it constructs the concrete structure of primitive：

2. a kind of preparation method of the supramolecular hydrogel glue material constructed by calixarenes described in claim 1, is repaiied by dodecyl Decorations sulfonation cup [4] aromatic hydrocarbons (SC4AD) and methyl viologen are modified polyvinyl alcohol and are formed by supermolecule interaction, concrete grammar It is：

1) dodecyl modifies the preparation of sulfonation cup [4] aromatic hydrocarbons (SC4AD)

Cup [4] aromatic hydrocarbons is dissolved in acetonitrile, adds sodium hydride, be heated to reflux more than 0.5 hour under nitrogen protection, be subsequently adding bromine For dodecane hydrocarbon, continue backflow 48 hours, after being cooled to room temperature, filter and be spin-dried for solvent, add dichloromethane dissolving, use respectively 0.2mol/L hydrochloric acid and distilled water wash organic faciess 3-5 time, add anhydrous sodium sulfate drying 8-10 hour, filter out drying Agent, the silica gel post separation of the crude product in solution after concentration, eluant is 1 for volume ratio:1 dichloromethane-petroleum ether solution, obtains Dodecyl to white modifies cup [4] aromatic hydrocarbons；

Dodecyl obtained above is modified cup [4] aromatic hydrocarbon solid and is dissolved in chloroform, adds chlorosulfonic acid, room temperature reaction 4 hours, evaporation Fall chloroform, be dissolved in water, with the sodium hydroxide solution of 1M, the pH of resulting solution be adjusted to neutrality, be spin-dried for solvent, gained solid is used Water-ethanol recrystallization, obtains white dodecyl and modifies sulfonation cup [4] aromatic hydrocarbons (SC4AD)；

2) preparation of supramolecular hydrogel glue material

SC4AD, methyl viologen are modified polyvinyl alcohol (PVA-MV) and be dissolved separately in distilled water, is prepared into concentration respectively and is The solution of 0.025g/mL；Two kinds of solution of same volume are simultaneously added dropwise reagent bottle respectively with the speed of 0.5-1mL/min In, concussion shakes up, stands 30 seconds and can be prepared by supramolecular hydrogel；

Wherein said cup [4] aromatic hydrocarbons, acetonitrile, the amount ratio of sodium hydride, bromododecane hydrocarbon and dichloromethane are 1mol:15L: 4.25mol:5mol:37.5L；

Described dodecyl modification cup [4] aromatic hydrocarbons, chloroform, the amount ratio of chlorosulfonic acid are 1mol:3L:4.25mol.