CN101857666B - Cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof - Google Patents
Cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cellulose ether grafted and modified temperature-sensitive hydrogel and a preparation method thereof. The cellulose ether grafted and modified temperature-sensitive hydrogel is prepared by taking a hydroxypropyl cellulose (HPC) marcomolecular RAFT molecule as a chain transfer agent and adding a monomer, N-isopropylacrylamide (NIPAM), and a cross-linking agent in an organic solvent for reaction at the temperature of 60 to 100 DEG C for 24 to 48h by a reversible addition-fragmentation chain transfer (RAFT) polymerization method. The hydrogel has the advantages of adjustable higher mechanical strength and fast (de)swelling performance so as to be widely used in the fields of biomedical sciences, target drug controlled release, substance separation, biosensors, switching valves, chemical reaction control and the like.
Description
Technical field
The present invention relates to polymer arts, particularly a kind of cellulose ether grafted and modified temperature-sensitive hydrogel and preparation method thereof.
Background technology
Poly N-isopropyl acrylamide (PNIPAM) is a kind of temperature sensing polymer that typically has lower critical solution temperature (LCST).Near the variation that the crosslinked hydrogel that obtains of PNIPAM is can the perception outside temperature LCST small is also carried out unexpected suction or dehydration, thereby makes the volume of self that discontinuous reversible violent contraction or expansion occur.The PNIPAM hydrogel has been widely used in control release, enzyme immobilization, memory temperature-sensitive switch, the sensor field of medicine.
The mechanical strength of the PNIPAM homopolymerization hydrogel of traditional method polymerization is poor, and (going) swelling equilibrium time is long, can not directly utilize, therefore must be to its modification.In recent years, active controllable free-radical polymerisation is high molecular synthetic for special constructions such as block, pectination, stars by people's broad research; Wherein, RAFT polymerization (RAFT polymerization) has the advantages such as the monomer range of choice is wide, reaction conditions is not harsh, controllability is good.Journal of Polymer Science Part A:Polym Chem 2005,43:2615～2624 have reported with the RAFT polymerization and have obtained comb type grafting PNIPAM hydrogel, this hydrogel has fast-response and very high swelling ratio; But this, the network structure intensity of this hydrogel is low, and is very easily destroyed.
Summary of the invention
The object of the invention is to overcome the shortcoming that exists in prior art, the cellulose ether grafted and modified temperature-sensitive hydrogel that a kind of mechanical strength is high, the speed of response is fast is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned cellulose ether grafted and modified temperature-sensitive hydrogel.
Purpose of the present invention is achieved through the following technical solutions:
A kind of cellulose ether grafted and modified temperature-sensitive hydrogel comprises following component by weight percentage:
Initiator 0.1～3%
Cellulose macromolecule trithio ester chain-transfer agent 8.7%～16%
Linking agent 2～8%.
Described NIPA: the mass ratio of cellulose macromolecule trithio ester chain-transfer agent is preferably (3～20): 1; More preferably mass ratio is (5～15): 1.
Described initiator is one or more mixtures in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or dilauroyl peroxide.The consumption of described initiator is preferably and accounts for 0.5～2% of reaction raw materials gross weight.
Described cellulose macromolecule trithio ester chain-transfer agent is that trithio ester chain-transfer agent and the hydroxypropylcellulose (HPC) by Z group band carboxyl makes under catalyst action; In the trithio ester chain-transfer agent of described Z group band carboxyl and hydroxypropylcellulose, the mol ratio of glucosyl residue unit is 1: (3～20) are preferably 1: (5～15); Described catalyzer is dicyclohexylcarbodiimide (DCC).The structural formula of the trithio ester chain-transfer agent of described Z group band carboxyl is formula 1:
Formula 1
Described linking agent is N, one or more mixtures in N '-methylene-bisacrylamide, dimethacrylate glycol ether ester or Ethylene glycol dimethacrylate.The consumption of described linking agent is preferably and accounts for 3～6% of reaction raw materials gross weight.
Also comprise organic solvent in described cellulose ether grafted and modified temperature-sensitive hydrogel.Described organic solvent is one or more mixtures in N-Methyl pyrrolidone, Isosorbide-5-Nitrae-dioxane, N,N-dimethylacetamide.
a kind of preparation method of cellulose ether grafted and modified temperature-sensitive hydrogel, comprise the steps: at first will to account for 80～87% NIPA (NIPAM) of reaction raw materials gross weight, account for 0.1～3% initiator of reaction raw materials gross weight, account for 8.7～16% cellulose macromolecule trithio ester chain-transfer agent of reaction raw materials gross weight, 2～8% the linking agent that accounts for the reaction raw materials gross weight joins in organic solvent, be uniformly dispersed under magnetic agitation, then vacuumize and remove the logical nitrogen-sealed of oxygen, reacted in the oil baths of 60～100 ℃ or airbath 12～48 hours, again the gained gel is steeped in deionized water, remove impurity, obtain cellulose ether grafted and modified temperature-sensitive hydrogel.
Preferred 24～48 hours of the reaction times of described oil bath or airbath.
Described with gained gel bubble in deionized water, be to adopt the deionized water of 5～25 ℃ to soak 3～7 days, uninterruptedly change water every day.
The principle of work that the present invention adopts is: the present invention is take hydroxypropylcellulose (HPC) macromole RAFT molecule as chain-transfer agent, add monomer NIPA, initiator, linking agent, solvent, prepared hydroxypropylcellulose macromole grafting NIPA (PNIPAM) hydrogel with RAFT polymerization (RAFT).This hydrogel is due to the mode of hydroxypropylcellulose with macromole RAFT is incorporated in hydrogel by RAFT graft polymerization NIPAM monomer, when keeping the quick response of material and susceptibility, by regulating the density of RAFT molecule on HPC and NIPAM monomer amount ratio, HPC molecular weight and HPC macromole, can obtain different swelling behaviors.Simultaneously, the existence of HPC also makes hydrogel have porous and super pore structure, thereby obtains desirable swelling rate.
The present invention compared with prior art has following advantage and effect:
(1) temperature-sensitive hydrogel of the present invention has adjustable swelling ratio, fast response characteristic, higher mechanical strength, its speed of response to temperature is very fast and be reversible, when improving the hydrogel mechanical strength and not changing its susceptibility, has excellent swelling behavior.
(2) temperature-sensitive hydrogel of the present invention has biocompatibility, can be applied to that drug targeting control to discharge and the sensor field.
Description of drawings
Fig. 1: the deswelling dynamics figure of hydrogel of the present invention under 37 ℃.
Fig. 2: the figure of Swelling Dynamics again of hydrogel of the present invention under 15 ℃.
Fig. 3: the equilibrium swelling of hydrogel of the present invention is than temperature dependency figure.
Fig. 4: the DSC thermogram of hydrogel of the present invention.
(a is that different polymerization methodses are on the impact of hydrogel deswelling dynamics performance; B is that on the HPC macromole, different chains shift functional group's density to the impact of hydrogel deswelling dynamics performance; C is monomer and the impact of the different feed ratio of HPC macromolecular chain transfer agent on hydrogel deswelling dynamics performance; D is the impact of different molecular weight HPC on hydrogel deswelling dynamics performance in HPC macromolecular chain transfer agent.)
Embodiment
Below in conjunction with embodiment, the present invention is done further detailed description, but embodiments of the present invention are not limited to this.
Embodiment 1
add 2g monomer NIPA (NIPAM) in polymerization bottle, 0.02g initiator azo two isobutyls fine (AIBN), 0.06g linking agent N, N ' methylene-bisacrylamide (N, N '-Methylenebisacrylamide), 0.2g hydroxypropylcellulose Macro RAFT agent a (the RAFT molecular density is 1 RAFT molecule of every 10 glucosyl residues), 12.36g solvent 1, 4 dioxane, seal after vacuumizing logical nitrogen with water pump, heat 70 ℃, 48 hours, crosslinked gel bubble is soaked in 15 ℃ of deionized waters uninterruptedly change water 5 day every day, until with the solvent in gel, the small molecules such as non-reacted molecules and by product eliminates, then hydrogel is taken out being placed in watch-glass from water, wiped away surface-moisture, be placed on refrigerator and cooled and freeze 12h, put into freeze drier lyophilize 16 hours, obtain the ether of cellulose grafting PNIPAM hydrogel NH110a of freeze-drying.
This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 13.4.
Embodiment 2
Add 2g monomer NIPA in polymerization bottle, 0.02g initiator azo two isobutyls are fine, 0.06g linking agent N, N ' methylene-bisacrylamide, 0.2g hydroxypropylcellulose Macro RAFT agent b (the RAFT molecular density is 1 RAFT molecule of every 5 glucosyl residues), 12.36g solvent 1,4 dioxane, seal after vacuumizing logical nitrogen with water pump, all the other steps obtain hydrogel NH110b with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 20.4.
Embodiment 3
Add 2g monomer NIPA in polymerization bottle, 0.02g initiator azo two isobutyls are fine, 0.06g linking agent N, N ' methylene-bisacrylamide, 0.2g hydroxypropylcellulose Macro RAFT agent c (the RAFT molecular density is 1 RAFT molecule of every 15 glucosyl residues), 12.36g solvent Isosorbide-5-Nitrae dioxane, all the other steps obtain hydrogel NH110c with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 11.3.
Add 1g monomer NIPA in polymerization bottle, 0.02g initiator azo two isobutyls are fine, 0.06g linking agent N, N ' methylene-bisacrylamide, 0.2g hydroxypropylcellulose Macro RAFT agent a (the RAFT molecular density is 1 RAFT molecule of every 10 glucosyl residues), 6.18g solvent 1,4 dioxane, seal after vacuumizing logical nitrogen with water pump, all the other steps obtain the ether of cellulose grafting PNIPAM hydrogel NH15a of freeze-drying with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 38.
Add 1.5g monomer NIPA in polymerization bottle, 0.015g initiator azo two isobutyls are fine, 0.045g linking agent N, N ' methylene-bisacrylamide, 0.1g hydroxypropylcellulose Macro RAFT agent a (the RAFT molecular density is 1 RAFT molecule of every 10 glucosyl residues), 8.24g solvent Isosorbide-5-Nitrae dioxane, all the other steps obtain the ether of cellulose grafting PNIPAM hydrogel NH115a of freeze-drying with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 14.
Add 2g monomer NIPA in polymerization bottle, 0.02g initiator azo two isobutyls are fine, 0.06g linking agent N, N ' methylene-bisacrylamide, 0.2g (the RAFT molecular density is 1 RAFT molecule of every 10 glucosyl residues to hydroxypropylcellulose Macro RAFT agent aRT-M, the HPC model is RT-M, molecular weight is about 150000), 12.36g solvent 1,4 dioxane, seal after vacuumizing logical nitrogen with water pump, all the other steps obtain the ether of cellulose grafting PNIPAM hydrogel NHRT-M110a of freeze-drying with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 24.
Embodiment 7
Add 2g monomer NIPA (NIPAM) in polymerization bottle, 0.02g initiator azo two isobutyls are fine, 0.06g linking agent N, N ' methylene-bisacrylamide, (the RAFT molecular density is 1 RAFT molecule of every 10 glucosyl residues to 0.2 hydroxypropylcellulose Macro RAFT agent aRT-J, the HPC model is RT-J, molecular weight is about 40000), 12.36g solvent Isosorbide-5-Nitrae dioxane, all the other steps obtain hydrogel NHRT-J110a with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 9.8.
Add 1g monomer NIPA in polymerization bottle, 0.01g initiator azo two isobutyls are fine, 0.03g linking agent N, N ' methylene-bisacrylamide, 0.2g hydroxypropylcellulose Macro RAFT agent c, 12.36mg solvent Isosorbide-5-Nitrae dioxane, all the other steps obtain the cellulose graft hydrogel NH15c of freeze-drying with embodiment 1.This hydrogel reached swelling equilibrium in 40 minutes, reached swelling equilibrium in 2 hours, and swelling ratio is 25.
Embodiment 9
Add 2g monomer NIPA in polymerization bottle, 0.02g initiator benzoyl peroxide, 0.06g linking agent N, N ' methylene-bisacrylamide, 0.2g hydroxypropylcellulose Macro RAFT agent a, 12.34g solvent N-Methyl pyrrolidone, seal after vacuumizing logical nitrogen, heat 60 ℃, 48 hours, all the other steps were with embodiment 1.
Add 2g monomer NIPA (NIPAM) in polymerization bottle, 0.02g initiator azo two is fine different heptan, 0.06g linking agent Ethylene glycol dimethacrylate, 0.2 hydroxypropylcellulose Macro RAFT agent a, 11.24g solvent N,N-dimethylacetamide, seal after vacuumizing logical nitrogen, heat 100 ℃, 48 hours, all the other steps were with embodiment 1.
Comparative Examples
Comparative Examples is respectively with the PNIPAM hydrogel (PNIPAM) that does not contain HPC of traditional radical polymerization with do not contain the temperature-sensitive hydrogel (PNIPAM (RAFT)) that the small molecules trithio ester chain-transfer agent RAFT polymerization of HPC prepares, and preparation condition is the same with HPC grafting PNIPAM temperature-sensitive hydrogel preparation method.
The performance test example
The cellulose graft temperature-sensitive hydrogel that embodiment is prepared, temperature-sensitive hydrogel PNIPAM, the PNIPAM (RAFT) of the not cellulose RAFT for preparing with Comparative Examples carry out performance test:
(1) deswelling dynamics test: hydrogel is reached swelling equilibrium in 15 ℃ of deionized waters, in fast transfer to 37 ℃ deionized water, hydrogel can shrink dehydration and go swelling.At regular intervals, measure the weight W of hydrogel
t, until its weight is near constant.Calculated retention rate (Water Retention, WR) WR=(t is the weight of the weight-xerogel of gel constantly)/(weight of the weight-xerogel of swelling equilibrium state gel) of water in hydrogel by following formula.Make hydrogel WR～t relation curve, namely get hydrogel 37 ℃ remove swelling (contraction) kinetic curve, as shown in Figure 1.In Fig. 1, a is that polymerization process is on the impact of hydrogel deswelling dynamics; B is the impact of RAFT molecule different densities on the hydrogel deswelling dynamics on cellulose macromolecule; C is that different feed ratio are on the impact of hydrogel deswelling dynamics; D is that the hydroxypropylcellulose different molecular weight is on the impact of hydrogel deswelling dynamics.As seen from Figure 1, NH15a has similar deswelling dynamics feature to PNIPAM (RAFT), just can discharge in front 2 minutes more than 90% in conjunction with water, and conventional P NIPAM hydrogel 10min can only discharge the water less than 50%.NH110a is similar to the deswelling dynamics of conventional P NIPAM hydrogel.Along with RAFT molecular density on cellulose macromolecule increases, go swelling rate and the degree of hydrogel all increase to some extent; Along with the increase of cellulose macromolecule RAFT content, go swelling rate and the degree of hydrogel also obviously improve.
(2) Swelling Dynamics experiment again: swelling rate (the reswelling ratio is called for short rSR) again: rSR=100 * (W
t-W
d)/W
d(W
dXerogel weight).In Fig. 2, a is that polymerization process is on the hydrogel impact of Swelling Dynamics again; B be on cellulose macromolecule RAFT molecule different densities on the hydrogel impact of Swelling Dynamics again; C is that different feed ratio are on the hydrogel impact of Swelling Dynamics again; D is that the hydroxypropylcellulose different molecular weight is on the hydrogel impact of Swelling Dynamics again.As seen from Figure 2, NH15a has the similar performance of Swelling Dynamics again to PNIPAM (RAFT) hydrogel, can almost reach swelling equilibrium in initial 5 minutes, and swelling ratio is 41 and 45, for the highest in all gels.NH110b, NHRT-M110a and conventional P NIPAM hydrogel can reach the swelling ratio of 20 left and right, but swelling rate is compared with NH15a and PNIPAM (RAFT) slowly.The swelling rate again of NH110a, NH110c, NH115a and NHRT-J110a is all very fast, can reach near balance at front 5 minutes, but swelling ratio is relatively low.
(3) equilibrium swelling of hydrogel is than the measurement of (SR): measure hydrogel at the equilibrium swelling ratio of 2～45 ℃ with weighting method.SR is the quality W of water when at certain temperature, hydrogel reaches the swelling equilibrium state
sThe quality W of gel during to weight with vacuum-drying
dRatio: SR=W
s/ W
dFig. 3 a is that polymerization process is on the impact of swelling behavior ratio, can find out, the PNIPAM hydrogel PNIPAM (RAFT) of simple small molecules RAFT polymerization, swelling ratio is very high, but this hydrogel is very fragile, even can not guarantee after suction to bear own wt and keep shape; And in hydrogel of the present invention, mass ratio m (HPC macromolecular chain transfer agent): m (NIPAM)=1: 5 o'clock, the swelling ratio of gained hydrogel equals to PNIPAM (RAFT) hydrogel, this explanation gained hydrogel of the present invention reaches excellent degree of swelling, has also improved the mechanical strength of hydrogel simultaneously.Fig. 3 c is that different feed ratio are on the impact of swelling ratio, illustrate when the ratio of cellulose macromolecule RAFT improves, swelling ratio can surmount hydrogel that small molecules RAFT polymerization obtains or suitable with it, this may be due to, when cellulose macromolecule RAFT content is 1/10 and 1/15, the molecule of grafting mostly is crosslinked agent and connects, and when the plain macromole RAFT content of dimension is 1/5, just has the remaining grafting molecular chain that is not crosslinked to become and freely wave chain.Fig. 3 b is the impact of RAFT molecule different densities on the swelling behavior ratio on cellulose macromolecule, and as seen along with the increase of RAFT molecular density on each HPC molecule, the swelling ratio performance improves.Fig. 3 d be different HPC molecular weight on the impact of swelling behavior ratio, can find out the increase along with molecular weight, the swelling ratio performance improves.
(4) dsc analysis of hydrogel: first allow hydrogel reach swelling equilibrium before mensuration.20 ℃～40 ℃ of measurement ranges, temperature rise rate is 2 ℃/min, dry nitrogen atmosphere, flow rate 50ml/min, result such as Fig. 4.As seen from Figure 4, all less than obviously impact, although HPC has certain wetting ability, LCST still depends on the close and distant water balance of PNIPAM on LCST for the density of RAFT molecule, hydroxypropylcellulose molecular weight and NIPAM and the cellulosic charging capacity of RAFT.
Claims (8)
1. cellulose ether grafted and modified temperature-sensitive hydrogel is characterized in that: comprise by weight percentage following raw material components:
Described NIPA: the mass ratio of cellulose macromolecule trithio ester chain-transfer agent is (3～20): 1;
Described cellulose ether grafted and modified temperature-sensitive hydrogel prepares by following method: at first will account for 80～87% NIPA of reaction raw materials gross weight, 0.1～3% the initiator that accounts for the reaction raw materials gross weight, 8.7～16% the cellulose macromolecule trithio ester chain-transfer agent that accounts for the reaction raw materials gross weight, 2～8% the linking agent that accounts for the reaction raw materials gross weight and join in organic solvent, be uniformly dispersed under magnetic agitation, then vacuumize and remove the logical nitrogen-sealed of oxygen, reacted in the oil baths of 60～100 ℃ or airbath 12～48 hours; Again the gained gel is steeped in deionized water, remove impurity, obtain cellulose ether grafted and modified temperature-sensitive hydrogel.
2. cellulose ether grafted and modified temperature-sensitive hydrogel according to claim 1, it is characterized in that: described initiator is one or more mixtures in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide or dilauroyl peroxide.
3. cellulose ether grafted and modified temperature-sensitive hydrogel according to claim 1, it is characterized in that: described cellulose macromolecule trithio ester chain-transfer agent is that trithio ester chain-transfer agent and the hydroxypropylcellulose by Z group band carboxyl makes under catalyst action; In the trithio ester chain-transfer agent of described Z group band carboxyl and hydroxypropylcellulose, the mol ratio of glucosyl residue unit is 1:(3～20); Described catalyzer is dicyclohexylcarbodiimide.
4. cellulose ether grafted and modified temperature-sensitive hydrogel according to claim 1, it is characterized in that: described linking agent is N, one or more mixtures in N '-methylene-bisacrylamide, dimethacrylate glycol ether ester or Ethylene glycol dimethacrylate.
5. cellulose ether grafted and modified temperature-sensitive hydrogel according to claim 1, it is characterized in that: described cellulose ether grafted and modified temperature-sensitive hydrogel comprises organic solvent; Described organic solvent is one or more mixtures in N-Methyl pyrrolidone, Isosorbide-5-Nitrae-dioxane, N,N-dimethylacetamide.
6. the preparation method of the described cellulose ether grafted and modified temperature-sensitive hydrogel of claim 1～5 any one, it is characterized in that comprising the steps: at first accounting for 80～87% NIPA of reaction raw materials gross weight, account for 0.1～3% initiator of reaction raw materials gross weight, account for 8.7～16% cellulose macromolecule trithio ester chain-transfer agent of reaction raw materials gross weight, 2～8% the linking agent that accounts for the reaction raw materials gross weight joins in organic solvent, be uniformly dispersed under magnetic agitation, then vacuumize and remove the logical nitrogen-sealed of oxygen, reacted in the oil baths of 60～100 ℃ or airbath 12～48 hours, again the gained gel is steeped in deionized water, remove impurity, obtain cellulose ether grafted and modified temperature-sensitive hydrogel.
7. the preparation method of cellulose ether grafted and modified temperature-sensitive hydrogel according to claim 6, it is characterized in that: the reaction times of described oil bath or airbath is 24～48 hours.
8. the preparation method of cellulose ether grafted and modified temperature-sensitive hydrogel according to claim 6 is characterized in that: described with gained gel bubble in deionized water, be to adopt the deionized water of 5～25 ℃ to soak 3～7 days, uninterruptedly change water every day.
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| US9063138B2 (en) | 2009-10-15 | 2015-06-23 | Robert Bosch Gmbh | Device and method for indirect electronic condition control in biomolecule detection platforms |
| CN102304194A (en) * | 2011-05-19 | 2012-01-04 | 上海大学 | Thermal sensitivity adjustable biocompatible core-shell structured polymer nanogel and preparation method thereof |
| CN102432774B (en) * | 2011-09-01 | 2013-03-20 | 中科院广州化学有限公司 | Biodegradable temperature response hydrogel and preparation method thereof |
| WO2013106790A1 (en) * | 2012-01-12 | 2013-07-18 | Robert Bosch Gmbh | Device and method for indirect electronic condition control in biomolecule detection platforms |
| CN104801286B (en) * | 2015-05-14 | 2017-04-12 | 安徽大学 | Graphene oxide hydroxy propyl cellulose composite hydrogel as well as preparing method and application thereof |
| CN107266635B (en) * | 2017-05-31 | 2019-07-02 | 中南林业科技大学 | A kind of nano-cellulose compound temperature-sensitive type hydrogel and preparation method thereof |
| CN109826015B (en) * | 2019-01-30 | 2021-03-26 | 广西大学 | temperature-sensitive/pH dual-response intelligent nanofiber material and preparation method and application thereof |
| CN110407980B (en) * | 2019-08-14 | 2021-12-14 | 中国林业科学研究院林产化学工业研究所 | Preparation method of cellulose high-molecular surfactant-based pH and temperature dual-response type composite hydrogel |
| CN112592431A (en) * | 2020-12-16 | 2021-04-02 | 陈凤春 | Degradable cellulose grafted acrylic acid-based high-water-absorptivity hydrogel and preparation method thereof |
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