CN101402713B - Process for producing hydrogel with optical activity - Google Patents
Process for producing hydrogel with optical activity Download PDFInfo
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- CN101402713B CN101402713B CN2008102270512A CN200810227051A CN101402713B CN 101402713 B CN101402713 B CN 101402713B CN 2008102270512 A CN2008102270512 A CN 2008102270512A CN 200810227051 A CN200810227051 A CN 200810227051A CN 101402713 B CN101402713 B CN 101402713B
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Abstract
The invention relates to a method for preparing a hydrogel with optical activity, which pertains to the field of polymer material. The method comprises the following steps: firstly, an N-propargyl amide monomer with double bond is synthesized, the monomer is then copolymerized with N-propargyl amide, N-propargyl carbamide or N-propargyl sulfonamide monomer with chiral substituent to synthesize a copolymer with stable helical structure and rather high optical activity; then the copolymer obtained is dissolved in a chloroform solvent, propyl acrylamide (NIPAm) and N, N`- methylene bisacrylamide(Bis) are dissolved in chloroform, the NIPAm dissolved is added into the copolymer solution and heated up to 45 DEG C to 90 DEG C under the protection of nitrogen; an evocating agent AIBN is added under the protection of nitrogen, reaction lasts for 30min to 24h and then a yellow clear gel is obtained. The gel is put into the chloroform solvent to be soaked and cleaned for a plurality of times, dried, soaked and swollen by deionized water and then the hydrogel is obtained. The prepared hydrogel has optical activity.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of preparation method with optical activity hydrogel.
Background technology
Optical active polymer has not available excellent properties of general polymer and wide application prospect, be subjected to paying attention to widely, and can forming the polymkeric substance of regular secondary structure (as spirane structure), main chain is even more important comparatively speaking, using value is also more arranged, have high optical activity because of this class optical active polymer shows " chirality amplification " effect usually.
Spiral is a kind of chiral structure, be that left hand helix is the mirror that can not overlap with right-handed helix, therefore, if it is optionally synthetic or in polymkeric substance, induce generation a kind of spiral wherein, this polymkeric substance will have opticity, even do not have chiral centre on its main chain or the side chain.The discovery that the macromolecular history of spiral can be traced back to the helical conformation of natural macromolecular.Nineteen thirty-seven Hanes has proposed the spirane structure of polysaccharide.Nineteen fifty, early stage Pauling proposed the spirane structure of native peptides, and Watson and Crick find the spirane structure of DNA jointly in the near future, and these two discoveries are the main weight break points in biomacromolecule field.Nineteen fifty-five Nata finds that the isotactic polypropylene presents spirane structure under solid-state, and this discovery is the synthetic macromolecular beginning of spiral, makes to obtain various spiropolymers today.
So far human synthetic spiropolymer mainly contains polyacetals, polysilane, poly-isocyanide, polymeric polyisocyanate, polymkeric substance and some oligopolymer such as polyacetylene class, wherein some polymkeric substance shows the not available characteristic of general polymer, as: the chiral catalysis performance, the chiral recognition performance, optical activity etc.
The intelligent macromolecule hydrogel is a kind of hydrophilic macromolecule cross-linked network, and it can be by the subtle change in the perception external world, and generation reversible volume changes mutually or gel-sol changes mutually.The variation in this external world comprises ionic strength, solution composition, light, pressure, sound, specific molecule recognition system of temperature, pH value, strength of electric field, magneticstrength, solution etc.This environment-responsive of intelligent aqueous gel capable makes it at aspects such as concentrating of artificial-muscle, chemical valve, bioseparation, organized enzyme embedding, dilute solution wide application prospect be arranged.Especially based on the macromolecule hydrogel of poly-(N-N-isopropylacrylamide) (hereinafter to be referred as NIPAm), PNIPAm when extraneous temperature variation owing to the behavior that changes mutually of uniqueness is subjected to extensive and deep research.
The present invention is on the basis of existing hydrogel, allow NIPAm and the spiral macromonomer copolymerization that has two keys, the performance of hydrogel is improved, not only can improve the LCST of PNIPAm hydrogel, the more important thing is to make hydrogel have very strong optical activity, improved the range of application of PNIPAm hydrogel greatly.
Summary of the invention
Application prospect at present optical active polymer and hydrogel, the purpose of this invention is to provide a kind of preparation method with optical activity hydrogel, this method is by the synthetic one amides monomer that has two keys, can synthesize with the chiral monomer copolymerization then and have two keys, have very high light simultaneously and learn active spiropolymer, to have optically active spiropolymer and the synthetic hydrogel of N-isopropylacrylamide copolymerization by radical polymerization then, the hydrogel of preparation not only has the temperature sensitive property of general hydrogel, have more very strong optical activity, improve the range of application of hydrogel greatly.
The present invention is achieved through the following technical solutions: a kind of optical activity hydrogel that has is synthesized in design, may further comprise the steps:
1. at first relate to a kind of new compound, its structural formula is as follows;
R is alkyl or aromatic base in the formula; Specific operation process is as follows:
It is abundant with mol ratio to be that 1: 1: 1 end bit strip has carboxylic acid, carbonochloridic acid isobutyl ester, the methylmorpholine of two keys to dissolve in the organic solvent stirring at room successively, add the propargylamine that the same mol ratio of carboxylic acid of two keys is arranged with the end bit strip then, keep temperature to stir 1～24h for 0～30 ℃, filter out precipitation, with the alkali neutralization, the back rotary evaporation that dewaters gets crude product to filtrate after pickling, recrystallization obtains compound then.
2. the invention still further relates to by above-mentioned monomer and other chiral monomers and obtain multipolymer, its structure is as follows:
Wherein R is alkyl or aromatic group; R` is the group with chirality, and m, n are integer.
The invention still further relates to the concrete preparation method of above-mentioned polymkeric substance:
1) synthon
2) get
With one of the propargyl amides monomer that contains chiral radicals, propargyl sulfonamides monomer or three kinds of monomers of propargyl ureas monomer 1: 4 in molar ratio～1: 20 mixed, the mixing back is dissolved under nitrogen protection and forms solution in the organic solvent; Metal catalyst also is dissolved under nitrogen protection and forms solution in the organic solvent, after treating fully dissolving, the mixing of two solution is obtained mixing solutions, and one of propargyl amides monomer, propargyl sulfonamides monomer or three kinds of monomers of propargyl ureas monomer are 50: 1～500: 1 with the mol ratio of metal catalyst;
3) above-mentioned mixing solutions is poured in the precipitation agent behind-35 ℃～90 ℃ following polyase 13 0min～24h;
4) post precipitation filtration drying obtains having the multipolymer of the amides of two keys;
What use when adopting organic solvent in the above step all is same solvent.
Organic solvent: tetrahydrofuran (THF), trichloromethane, methylene dichloride, N, dinethylformamide, 1,4-dioxane, dimethyl sulfoxide (DMSO) or toluene also can adopt the binary mixture of above-mentioned solvent as solvent;
Precipitation agent: normal hexane, methyl alcohol.
Obtain characterizing after the above-mentioned polymkeric substance, characterization method comprises:
(1) use gel permeation chromatography (GPC) to measure the molecular weight and the molecular weight distribution of polymkeric substance;
(2) secondary structure of usefulness ultraviolet-visible spectrum (UV-vis) and circular dichroism spectrum (CD) characterize polymers is to determine whether having helical conformation;
3. the invention still further relates to a kind of preparation method of hydrogel, the concrete operations step is as follows:
Getting above-mentioned multipolymer, N-isopropylacrylamide and linking agent is dissolved in the organic solvent under nitrogen protection; Get initiator and under nitrogen protection, be dissolved in and obtain initiator solution in the organic solvent, treat fully dissolving after, at 45 ℃～90 ℃ initiator solution is added multipolymer, N-isopropylacrylamide and linking agent and under nitrogen protection, is dissolved in the formed solution of organic solvent; Keep 45 ℃～90 ℃ of temperature, nitrogen protection is reaction 30min～24h down, and products therefrom was soaked 7～14 days with organic solvent, dries after removing impurity, and swelling promptly gets and has optically active hydrogel in deionized water then.
Each parameter can be by following adjustment:
Multipolymer: account for 1%～50% of final solution mass percent
Linking agent: account for 1%～5% of final solution mass percent
Initiator: account for 1%～5% of final solution mass percent
Obtain above-mentioned hydrogel and characterize later on, measure its spirane structure and optical activity with ultraviolet-visible spectrum (UV-vis) and circular dichroism spectrum (CD).
Measurement result shows, under suitable solvent and reaction times, can obtain having very high light and learn active hydrogel, this hydrogel not only has the swelling property of ortho-water gel, water-absorbent, temperature sensitive property and its using value, more have in its structure and have chiral radicals, have very strong optical activity, can be used for chiral recognition and fractionation, have wide applicating and exploitation prospect.
Description of drawings:
Fig. 1 a is the circular dichroism spectrogram of hydrogel among the embodiment 1;
Fig. 1 b is the uv-absorbing spectrogram of hydrogel among the embodiment 1
Fig. 2 a is the circular dichroism spectrogram of hydrogel among the embodiment 2
Fig. 2 b is the uv-absorbing spectrogram of hydrogel among the embodiment 1
Fig. 3 a is the circular dichroism spectrogram of hydrogel among the embodiment 7;
Fig. 3 b is the uv-absorbing spectrogram of hydrogel among the embodiment 7;
Fig. 4 a is the circular dichroism spectrogram of hydrogel among the embodiment 8;
Fig. 4 b is the uv-absorbing spectrogram of hydrogel among the embodiment 8;
Fig. 5 a is the circular dichroism spectrogram of hydrogel among the embodiment 12;
Fig. 5 b is the uv-absorbing spectrogram of hydrogel among the embodiment 12.
Embodiment
Embodiment 1
The first step synthon: the adding of 2.4ml vinylformic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, methylmorpholine 4.4ml, stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 30 ℃ reaction 1h, take out the solids removed by filtration by product, filtrate is respectively cleaned three times with acid, alkali, the aqueous solution successively, remove moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body; IR (KBr): 3292 (N-H), 2118 (H-C ≡ C), 1659 (C=O), 1536,1406,1118cm
-1,
1H-NMR (CDCCl3,600MHz, 25 ℃, δ): 6.15～6.17 (C
HH=CH), 5.63～5.65 (CH
H=CH), 6.25～6.27 (CH2=C
H), 2.20～2.22 (C
H≡ C), 4.06～4.08 (CH ≡ CC
H 2), 7.24 (NH).
Get above-mentioned monomer 0.0090g and chiral monomer N-propargyl urea
(0.0925g mol ratio 1:4), rhodium catalyst 0.0011g is dissolved in 1mlCHCl respectively
3In, under nitrogen protection, catalyzer is joined in the solvent monomer ,-35 ℃ of following reaction 24h, question response finishes to add the normal hexane precipitation, filter the 0.0734g multipolymer; Multipolymer number-average molecular weight 2000, molecular weight distributing index 1.32, cis-structure 100%;
Get above-mentioned multipolymer 0.0093g, NIPAm0.327g, N, N`-methylene-bisacrylamide 0.0032g; AIBN0.0032g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 24h
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
Embodiment 2
The first step synthon: the adding of 2.4ml vinylformic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, methylmorpholine 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 0 ℃ reaction 24h, take out the solids removed by filtration by product, filtrate is respectively cleaned three times with acid, alkali, the aqueous solution successively, removes moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body; IR (KBr): 3292 (N-H), 2118 (H-C ≡ C), 1659 (C=O), 1536,1406,1118cm
-1,
1H-NMR (CDCCl3,600MHz, 25 ℃, δ): 6.15～6.17 (C
HH=CH), 5.63～5.65 (CH
H=CH), 6.25～6.27 (CH2=C
H), 2.20～2.22 (C
H≡ C), 4.06～4.08 (CH ≡ CC
H 2), 7.24 (NH).
Get above-mentioned monomer 0.0090g and chiral monomer N-propargyl urea
(0.4510g mol ratio 1:20), rhodium catalyst 0.0275g is dissolved in 1mlCHCl respectively
3In, under nitrogen protection, catalyzer is joined in the solvent monomer, 60 ℃ of following reaction 30min, question response finishes to add methanol extraction, filter the 0.4734g multipolymer; Multipolymer number-average molecular weight 12000, molecular weight distributing index 2.42, cis-structure 100%;
Hydrogel is synthetic: get above-mentioned multipolymer 0.0300g, NIPAm0.2670g, N, N`-methylene-bisacrylamide 0.0030g; AIBN0.0150g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 30min
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
Embodiment 3
The first step synthon: the adding of 2.4ml vinylformic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, methylmorpholine 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 15 ℃ reaction 12h, take out the solids removed by filtration by product, filtrate is used acid successively, alkali, the aqueous solution respectively cleans three times, remove moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body, IR (KBr): 3292 (N-H), 2118 (H-C ≡ C), 1659 (C=O), 1536,1406,1118cm
-1,
1H-NMR (CDCCl3,600MHz, 25 ℃, δ): 6.15～6.17 (C
HH=CH), 5.63～5.65 (CH
H=CH), 6.25～6.27 (CH2=C
H), 2.20～2.22 (C
H≡ C), 4.06～4.08 (CH ≡ CC
H 2), 7.24 (NH).
Get above-mentioned monomer 0.0090g and chiral monomer N-propargyl urea
(0.2267g mol ratio 1:10), rhodium catalyst 0.0055g is dissolved in 1mlCHCl respectively
3In, under nitrogen protection, catalyzer is joined in the solvent monomer ,-35 ℃ of following reaction 24h, question response finishes to add the normal hexane precipitation, filter the 0.2134g multipolymer; Multipolymer number-average molecular weight 21000, molecular weight distributing index 1.88, cis-structure 100%;
Hydrogel is synthetic: get above-mentioned multipolymer 0.0300g, NIPAm0.2640g, N, N`-methylene-bisacrylamide 0.0060g; AIBN0.0080g is dissolved in 0.5mlCHCl respectively
3Cause down at 50 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 12h
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
The first step synthon: the adding of 2.4ml vinylformic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, methylmorpholine 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 30 ℃ reaction 4h, take out the solids removed by filtration by product, filtrate is respectively cleaned three times with acid, alkali, the aqueous solution successively, removes moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body; IR (KBr): 3292 (N-H), 2118 (H-C ≡ C), 1659 (C=O), 1536,1406,1118cm
-1,
1H-NMR (CDCCl3,600MHz, 25 ℃, δ): 6.15～6.17 (C
HH=CH), 5.63～5.65 (CH
H=CH), 6.25～6.27 (CH2=C
H), 2.20～2.22 (C
H≡ C), 4.06～4.08 (CH ≡ CC
H 2), 7.24 (NH).
Multipolymer is synthetic with embodiment 3
Hydrogel is synthetic: get above-mentioned multipolymer 0.0300g, NIPAm0.2610g, N, N`-methylene-bisacrylamide 0.0090g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 2h
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
Embodiment 5
The first step synthon: with embodiment 4
Multipolymer is synthetic: with embodiment 3
Hydrogel is synthetic: get above-mentioned multipolymer 0.0300g, NIPAm0.2580g, N, N`-methylene-bisacrylamide 0.0120g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 30min
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
The first step synthon: with embodiment 4
Multipolymer is synthetic: with embodiment 3
Hydrogel is synthetic: get above-mentioned multipolymer 0.0300g, NIPAm0.2550g, N, N`-methylene-bisacrylamide 0.0150g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 5h
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
Embodiment 3, embodiment 4, embodiment 5, embodiment 6 are that to come its circular dichroism spectrogram of synthetic hydrogel and uv absorption spectra and embodiment 1 and embodiment 2 similar all be very strong absorption peak to occur at the 360nm place to the alkynes third urea monomer.
Embodiment 7
The first step synthon: the adding of 2.4ml5-hexenoic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, morphine quinoline 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 0 ℃ reaction 24h, take out the solids removed by filtration by product, filtrate is respectively cleaned three times with acid, alkali, the aqueous solution successively, removes moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body.IR(KBr)：3295(N-H)，2115(H-C≡C)，1639(C＝O)，1533，1249，1118cm
-1，
1H-NMR(CDCCl3，600MHz，25℃，δ)：6.15～6.17(C
HH＝CH)，5.63～5.65(CH
H＝CH)，6.25～6.27(CH2＝C
H)，2.20～2.22(C
H≡C)，4.06～4.08(CH≡CC
H 2)，7.24(NH).
Get above-mentioned monomer 0.0090g and chiral monomer N-propargyl sulphonamide
1842g (mol ratio 1:10), rhodium catalyst 0.0035g is dissolved in respectively in the 1ml toluene, under nitrogen protection, catalyzer is joined in the solvent monomer, 90 ℃ are reacted 30min down, question response finish to add the normal hexane precipitation, filter the 0.1415g multipolymer, multipolymer number-average molecular weight 31000, molecular weight distributing index 1.42, cis-structure 100%;
Get above-mentioned multipolymer 0.0269g, NIPAm0.2687g, N, N`-methylene-bisacrylamide 0.0030g; AIBN0.0030g is dissolved in respectively in the 0.5ml toluene solution and causes down at 90 ℃, get the yellow-green colour transparent aquagel behind the 1h, hydrogel is removed impurity with changing a solution every day in DMF solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
The first step synthon: the adding of 2.4ml5-hexenoic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, morphine quinoline 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 30 ℃ reaction 1h, take out the solids removed by filtration by product, filtrate is respectively cleaned three times with acid, alkali, the aqueous solution successively, removes moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body.IR(KBr)：3295(N-H)，2115(H-C≡C)，1639(C＝O)，1533，1249，1118cm
-1，
1H-NMR(CDCCl3，600MHz，25℃，δ)：6.15～6.17(C
HH＝CH)，5.63～5.65(CH
H＝CH)，6.25～6.27(CH2＝C
H)，2.20～2.22(C
H≡C)，4.06～4.08(CH≡CC
H 2)，7.24(NH).
Multipolymer is synthetic: with embodiment 7
Synthetic water gel: get above-mentioned multipolymer 0.0269g, NIPAm0.2687g, N, N`-methylene-bisacrylamide 0.0060g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 10h the yellow-green colour transparent aquagel, hydrogel is changed a solution with the DMF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 9
The first step synthon: the adding of 2.4ml5-hexenoic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, morphine quinoline 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 15 ℃ reaction 12h, take out the solids removed by filtration by product, filtrate is used acid successively, alkali, the aqueous solution respectively cleans three times, remove moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body, IR (KBr): 3295 (N-H), 2115 (H-C ≡ C), 1639 (C=O), 1533,1249,1118cm
-1,
1H-NMR (CDCCl3,600MHz, 25 ℃, δ): 6.15～6.17 (C
HH=CH), 5.63～5.65 (CH
H=CH), 6.25～6.27 (CH2=C
H), 2.20～2.22 (C
H≡ C), 4.06～4.08 (CH ≡ CC
H 2), 7.24 (NH).
Multipolymer is synthetic: with embodiment 7
Synthetic water gel: get above-mentioned multipolymer 0.0269g, NIPAm0.2657g, N, N`-methylene-bisacrylamide 0.0090g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 30min the yellow-green colour transparent aquagel, hydrogel is changed a solution with the DMF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
The first step synthon: the adding of 2.4ml5-hexenoic acid is equipped with in the 500ml flask of 200mlTHF, treat to dissolve fully the back and add carbonochloridic acid isobutyl ester 4.56ml, morphine quinoline 4.4ml stirring at room treats that fully the dissolving back adds the 1.94ml propargylamine, behind controlled temperature to the 30 ℃ reaction 6h, take out the solids removed by filtration by product, filtrate is used acid successively, alkali, the aqueous solution respectively cleans three times, remove moisture content with anhydrous siccative then, with Rotary Evaporators revolve steam the pale yellow oily liquid body, IR (KBr): 3295 (N-H), 2115 (H-C ≡ C), 1639 (C=O), 1533,1249,1118cm
-1,
1H-NMR (CDCCl3,600MHz, 25 ℃, δ): 6.15～6.17 (C
HH=CH), 5.63～5.65 (CH
H=CH), 6.25～6.27 (CH2=C
H), 2.20～2.22 (C
H≡ C), 4.06～4.08 (CH ≡ CC
H 2), 7.24 (NH).
Multipolymer is synthetic: with embodiment 7
Synthetic water gel: get above-mentioned multipolymer 0.0269g, NIPAm0.2627g, N, N`-methylene-bisacrylamide 0.0120g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 12h the yellow-green colour transparent aquagel, hydrogel is changed a solution with the DMF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 11
The first step synthon: with embodiment 10
Multipolymer is synthetic: with embodiment 7
Synthetic water gel: get above-mentioned multipolymer 0.0269g, NIPAm0.2597g, N, N`-methylene-bisacrylamide 0.0150g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 12h the yellow-green colour transparent aquagel, hydrogel is changed a solution with the DMF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 9, embodiment 10, embodiment 11 all are very strong absorption peak to occur at the 420nm place for propargyl sulfamide monomer comes its circular dichroism spectrogram of synthetic hydrogel and uv absorption spectra and embodiment 7 and embodiment 8 similar.
Embodiment 12
The first step synthon: with embodiment 4
Get above-mentioned monomer 0.0168g and chiral monomer N-propargyl acid amides
(0.2596g mol ratio 1:10), rhodium catalyst 0.0059g is dissolved in 1mlCHCl respectively
3In, under nitrogen protection, catalyzer is joined in the solvent monomer, 30 ℃ of following reaction 1h, question response finishes to add the normal hexane precipitation, filter the 0.2610g multipolymer;
Synthetic water gel: get above-mentioned multipolymer 0.0450g, NIPAm0.2550g, Vinylstyrene 0.01ml; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 8h the yellow-green colour transparent aquagel, hydrogel is changed a solution with the THF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 13: the first step synthon: with embodiment 4
Multipolymer is synthetic: with embodiment 12
Synthetic water gel: get above-mentioned multipolymer 0.0600g, NIPAm0.2400g, N, N`-methylene-bisacrylamide 0.0030g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, get yellow-green colour transparent aquagel, hydrogel CHCl behind the 30min
3Change a solution and remove impurity every day in solution soaking one week, and the oven dry back adds deionized water by its abundant swelling, hydrogel characterizes respectively.
Embodiment 14: the first step synthon: with embodiment 4
Multipolymer is synthetic: with embodiment 12
Synthetic water gel: get above-mentioned multipolymer 0.0900g, NIPAm0.2100g, N, N`-methylene-bisacrylamide 0.0030g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 6h the yellow-green colour transparent aquagel, hydrogel is changed a solution with the THF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 15: the first step synthon: with embodiment 4
Multipolymer is synthetic: with embodiment 12
Synthetic water gel: get above-mentioned multipolymer 0.1500g, NIPAm0.1500g, N, N`-methylene-bisacrylamide 0.0030g; AIBN0.0030g is dissolved in 0.5mlCHCl respectively
3Cause down at 60 ℃ in the solution, behind the 30min the yellow-green colour transparent aquagel, hydrogel is changed a solution with the THF solution soaking and remove impurity one every day in week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 16: the first step synthon: with embodiment 4
Multipolymer is synthetic: with embodiment 12
Synthetic water gel: get above-mentioned multipolymer 0.1500g, NIPAm0.1500g, N, N`-methylene-bisacrylamide 0.0030g; BPO (dibenzoyl peroxide) 0.0030g is dissolved in respectively in the 0.5ml toluene solution and causes down at 60 ℃, get the yellow-green colour transparent aquagel behind the 30min, hydrogel is removed impurity with changing a solution every day in THF solution soaking one week, the oven dry back adds deionized water by its abundant swelling, gets hydrogel and characterizes respectively.
Embodiment 13, embodiment 14, embodiment 15, embodiment 16 all are very strong absorption peak to occur at the 375nm place for the propargyl amide monomer comes its circular dichroism spectrogram of synthetic hydrogel and uv absorption spectra and embodiment 12 similar.
Claims (3)
1. the preparation method with optical activity hydrogel is characterized in that, comprises that step is as follows:
1) synthon
R is alkyl or aromatic base in the formula;
2) get
With one of the propargyl amides monomer that contains chiral radicals, propargyl sulfonamides monomer or three kinds of monomers of propargyl ureas monomer 1: 4 in molar ratio～1: 20 mixed, the mixing back is dissolved under nitrogen protection and forms solution in the organic solvent; Rhodium catalyst also is dissolved under nitrogen protection and forms solution in the organic solvent, after treating fully dissolving, the mixing of two solution is obtained mixing solutions, and one of propargyl amides monomer, propargyl sulfonamides monomer or three kinds of monomers of propargyl ureas monomer are 50: 1～500: 1 with the mol ratio of rhodium catalyst;
3) above-mentioned mixing solutions is poured in the precipitation agent behind-35 ℃～90 ℃ following polyase 13 0min～24h; Precipitation agent is normal hexane or methyl alcohol;
4) post precipitation filtration drying obtains having the multipolymer of the amides of two keys;
5) getting above-mentioned multipolymer, N-isopropylacrylamide and linking agent is dissolved in the organic solvent under nitrogen protection; Get initiator and under nitrogen protection, be dissolved in and obtain initiator solution in the organic solvent, treat fully dissolving after, at 45 ℃～90 ℃ initiator solution is added multipolymer, N-isopropylacrylamide and linking agent and under nitrogen protection, is dissolved in the formed solution of organic solvent;
6) keep 45 ℃～90 ℃ of temperature, nitrogen protection is reaction 30min～24h down, and products therefrom was soaked 7～14 days with organic solvent, dries after removing impurity, and swelling promptly gets and has optically active hydrogel in deionized water then;
What use when adopting organic solvent in the above step all is same solvent.
2. the preparation method with optical activity hydrogel according to claim 1, it is characterized in that: organic solvent is tetrahydrofuran (THF), trichloromethane, methylene dichloride, N, dinethylformamide, 1,4-dioxane, dimethyl sulfoxide (DMSO) or toluene, the perhaps binary mixture of above-mentioned solvent.
3. the preparation method with optical activity hydrogel according to claim 1 is characterized in that: linking agent is N in the step 5), N`-methylene-bisacrylamide or Vinylstyrene; Initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
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| CN113321773B (en) * | 2021-05-21 | 2022-07-12 | 浙江理工大学 | Chiral chromatographic packing of substituted polyacetylene grafted divinylbenzene microsphere and preparation method thereof |
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