CN104193893B - A kind of shape-memory polymer based on glycine betaine and preparation method thereof - Google Patents
A kind of shape-memory polymer based on glycine betaine and preparation method thereof Download PDFInfo
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- 229920000431 Shape-memory polymer Polymers 0.000 title claims abstract description 41
- KWIUHFFTVRNATP-UHFFFAOYSA-N Trimethylglycine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229960003237 betaine Drugs 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- ROOXNKNUYICQNP-UHFFFAOYSA-N Ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 230000000845 anti-microbial Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical class C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010526 radical polymerization reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000011084 recovery Methods 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 210000002540 Macrophages Anatomy 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- UBMXFGVZFUYLSN-UHFFFAOYSA-O [NH4+].CCCS(O)(=O)=O Chemical compound [NH4+].CCCS(O)(=O)=O UBMXFGVZFUYLSN-UHFFFAOYSA-O 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001580 bacterial Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- -1 Hydroxyl sulfo betaine Chemical compound 0.000 description 2
- 210000003024 Macrophages, Peritoneal Anatomy 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 230000000844 anti-bacterial Effects 0.000 description 2
- 230000003373 anti-fouling Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 239000000560 biocompatible material Substances 0.000 description 2
- 210000004027 cells Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 210000004369 Blood Anatomy 0.000 description 1
- 210000001124 Body Fluids Anatomy 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N Peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000001464 adherent Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000005445 natural product Substances 0.000 description 1
- 229930014626 natural products Natural products 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000242 pagocytic Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940117986 sulfobetaine Drugs 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present invention relates to shape-memory material field, disclose a kind of shape-memory polymer based on glycine betaine and preparation method thereof.This polymer is by unsaturated glycine betaine monomer, and acrylic monomer, the function monomer such as ethylene glycol divinyl ether class monomer carries out radical polymerization under the effect of initiator and forms.Prepared shape-memory polymer based on glycine betaine has thermal shape memory performance and wet sensitive sense shape-memory properties, and meanwhile, it also has preferable anti-microbial property and good biocompatibility.This shape-memory polymer all has huge application potential at engineering, building, daily life and the aspect such as medical.
Description
Technical field
The present invention relates to shape-memory material field, particularly relate to a kind of shape memory polymers based on glycine betaine
Thing and preparation method thereof.
Background technology
Shape-memory material refers to perception environmental change (such as the stimulation of temperature, power, electromagnetism, solvent etc.),
And respond this change, its state parameter (such as shape, position, strain etc.) is adjusted, thus returns
The material of state is preset again to it.According to the difference of incentive condition, shape-memory material can be divided into thermic
Responsive type, photic responsive type, electroluminescent responsive type and chemical co-ordination type etc..At present, domestic and international researcher is
Use the multiple thermal shape memory polymer of method development and application chemically and physically, but its combination property
Universal the most not ideal enough.Thermal shape memory polymer, to meet the application in biomedical clinical, needs tool
The gentle incentive condition that standby close with body body temperature or biotic environment adapts, and the biocompatibility of appropriateness
With combination properties such as suitable intensities.Therefore, develop that cost is relatively low, combination property is superior, processing is simple,
The thermal shape memory polymer of good biocompatibility is the most theoretical and the developing direction of applied research.
Betaine type amphoteric ionomer, refers to that structure is similar to natural product glycine betaine, ties at same monomer
Structure has a base polymer of cation and anion simultaneously.Common sulphonic acid betaine type ampholytic monomer is main
Have: vinyl pyridine derivative, acrylamide derivative and methacrylate derivative.By these monomers
Homopolymerization under certain condition or with other neutral monomer copolymerization can prepare net charge be zero, there is anti-poly-electrolysis
The amphiphilic polymers of matter solution behavior.Amphoteric ion polymer by force and contains because of its Heat stability is good, hydration capability
The wait quaternary ammonium salt cationic of number and the sulfonate anionic that are susceptible to solution ph impact is had extremely to close
Note.Hydroxyl sulfo betaine not only has all advantages of zwitterionic compound, also have resisting high-concentration acid,
Alkali, salt, good emulsibility, dispersibility and antistatic behaviour, and there is sterilization and press down mouldiness, viscoelasticity
Deng.
The emphasis of the shape-memory polymer always research of the application in terms of biologic medical, domestic and international medical circle
It is devoted to medical macromolecular materials intelligent with the researcher of material educational circles, and is applied to biomedical sector.
But, the biocompatibility of the most of shape-memory polymers studied at present remains to be further improved.Face
Bed research finds, polyurethane shape memory polymer can cause the inflammatory reaction of body in being chronically implanted human body.
Therefore, there is good biocompatibility and the superior shape memory of combination property gathers in the urgent need to exploitation is a kind of
Compound, to meet the application needs in biomedical clinical.
Summary of the invention
The technical problem to be solved is to provide one to have shape-memory properties and good biological phase
The betaine type polymer of capacitive.
The technical solution adopted in the present invention is to provide a kind of shape-memory polymer based on glycine betaine, by
The monomer A of 1～50 weight portions, 1～50 weight portion monomer B and 1～20 weight portions monomer C polymerization
Form；
Wherein, the formula of monomer A isR1For H or CH3, R2For O or
Person NH, R3For CH3,CH2CH3, CH2CH2CH3In any one, Y is COO, SO3,PO3
In any one；
The formula of monomer B isWherein R1It is H or CH3；
The formula of monomer C isWherein n=1～5.
The present invention also provides for the preparation method of described shape-memory polymer, comprises the following steps: by 1～50
The monomer A and 1 of weight portion～the monomer B of 50 weight portions is placed in reaction vessel, adds water and stirs；?
Described reaction vessel adds the monomer C of 1～20 weight portions, adds water further and stir；Add and cause
Agent, insulation reaction obtains described shape-memory polymer；
Wherein, the formula of monomer A isR1For H or CH3, R2For O or
Person NH, R3For CH3,CH2CH3, CH2CH2CH3In any one, Y is COO, SO3,PO3
In any one；
The formula of monomer B isWherein R1It is H or CH3；
The formula of monomer C isWherein n=1～5.
Compared with prior art, the beneficial effects of the present invention is: prepare copolymerization by Raolical polymerizable
Thing, introduce unsaturated glycine betaine monomer A make polymer have betaine polymer good biocompatibility and
Anti-microbial property；Introduce acrylic monomer B so that forming hydrogen bond structure on polymer molecular chain and controlling or shadow
Ring the shape-memory properties of shape-memory polymer；It addition, introduce ethylene glycol divinyl ether class monomer C,
Make polymer form cross-linked network structure, improve shape-memory properties and stablize the structure of polymer.The present invention
Prepared shape-memory polymer has good biocompatibility and excellent shape-memory properties, Ke Yi great
Big improve its in biological medicine, medical treatment, the application of the aspect such as weaving.Described shape-memory polymer is all right
It is applied to antifouling paint, biomaterial surface modification, polymerizable type permanent anti-static agent, salt-resistant type polymer
Deng, also there is huge application potential at engineering, building, daily life and the aspect such as medical.
Accompanying drawing explanation
Fig. 1 is the cyclic tension curve chart of DMAPS-AA polymer prepared by embodiment 1；
Fig. 2 is DMAPS-AA polymer anti-microbial property test curve figure prepared by embodiment 1；
Fig. 3 is the infrared spectrogram of DMAPS-AA polymer prepared by embodiment 2；
Fig. 4 is the sample shape Recovery Process schematic diagram of DMAPS-AA polymer prepared by embodiment 3；
Fig. 5 is the electron scanning after DMHAS-AA polymer prepared by embodiment 4 is cultivated with macrophage
Microscope figure；
Fig. 6 is that the inversion fluorescence after DMAC-AA polymer prepared by embodiment 5 is cultivated with macrophage shows
Micro mirror observes picture.
Detailed description of the invention
In order to make the technical problem to be solved, technical scheme and beneficial effect clearer,
Below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that tool described herein
Body embodiment only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of shape-memory polymer based on glycine betaine, by 1～50 weight portions
Monomer A, 1～50 the monomer B and 1～the monomer C of 20 weight portions of weight portion be polymerized.
Wherein, the formula of monomer A isR1For H or CH3, R2For O or
Person NH, R3For CH3,CH2CH3, CH2CH2CH3In any one, Y is COO, SO3,PO3
In any one；
The formula of monomer B isWherein R1It is H or CH3；
The formula of monomer C isWherein n=1～5.
The preparation method of this betaine type shape-memory polymer, comprises the following steps:
(1) the monomer A and 1 of 1～50 weight portions～the monomer B of 50 weight portions is placed in reaction vessel,
Add water and stir；
(2) in described reaction vessel, add the monomer C of 1～20 weight portions, add water further and stir；
(3) adding initiator, insulation reaction obtains described shape-memory polymer；
Wherein, the formula of monomer A isR1For H or CH3, R2For O or
Person NH, R3For CH3,CH2CH3, CH2CH2CH3In any one, Y is COO, SO3,PO3
In any one；
The formula of monomer B isWherein R1It is H or CH3；
The formula of monomer C isWherein n=1～5.
Wherein, the initiator that reaction is used is free radical water soluble starter, including Ammonium persulfate., over cure
Acid potassium or redox type initiators etc., initiator is configured to the water-soluble of mass fraction 1wt% before addition
Liquid, preparation and the adition process of initiator are carried out in inert gas shielding atmosphere.The consumption of initiator is single
Body A, monomer B and the 0.5～2.0% of tri-kinds of monomer gross masses of monomer C.By three kinds of lists in step (2)
Body stirs to be placed in water-bath and is heated to about 65 DEG C, the initiator that will configure with Dropping funnel
Aqueous solution is added dropwise in reaction vessel by several times.Insulation reaction 4～6 hours, reaction terminates, and is cooled to room temperature,
Get final product discharging.The water added in preparation process is deionized water, and the amount added water controls making described shape
The mass percentage concentration of memory polymer is 20～30wt%.
The present invention prepares copolymer by Raolical polymerizable, introduces unsaturated glycine betaine monomer A and makes polymerization
Thing has good biocompatibility and the anti-microbial property of betaine polymer；Introduce acrylic monomer B thus
Make to be formed on polymer molecular chain the shape-memory properties that hydrogen bond structure controls or affects shape-memory polymer；
It addition, introduce ethylene glycol divinyl ether class monomer C, make polymer form cross-linked network structure, improve shape
Shape memory performance and the structure stablizing polymer.
The present invention is explained further below by way of specific embodiment.
Embodiment 1
By the N of 30g, N-dimethyl (methylacryoyloxyethyl) ammonium propane sulfonic acid inner salt (DMAPS)
Join in reaction vessel with 50g acrylic acid (AA), add deionized water and stir.Add 20g
Triethyleneglycol divinylether, in reaction vessel, stirs further, adds deionized water regulation and makes
The final concentration (mass percentage concentration) of three kinds of monomer total amounts is 20%.Under nitrogen protection, by 1g over cure
Acid ammonium is dissolved in 100mL deionized water, makes the initiator solution that concentration is 1wt%.Heating in water bath
Initiator solution, when temperature rises to 65 DEG C, is added dropwise to reaction vessel with Dropping funnel by reaction vessel by several times
In.Insulation reaction 4 hours, reaction is cooled to room temperature after terminating and gets final product discharging, it is thus achieved that based on DMAPS-AA
Shape-memory polymer.
Shape-memory properties is tested: the shape memory to prepared polymer based on DMAPS-AA
Can test, test result is as shown in Figure 1.The shape fixed rate of this polymer is calculated from Fig. 1
Being about 96%, shape recovery rate is about 92%, has preferable shape-memory properties.
Anti-microbial property is tested: prepared polymer based on DMAPS-AA is carried out anti-microbial property test,
As a example by polymer anti-escherichia coli (E.coli8099) performance, experimental result is as shown in Figure 2.From Fig. 2
In it will be seen that add 900 μ g/mL polymer solutions sample, represent the OD of bacterial concentration600Be worth along with
Incubation time prolongation is gradually increased, and shows that amount of bacteria gets more and more.Incubation time solution thin within 4 hours
Bacterium amount increase is the most inconspicuous, and this illustrates that polymer based on DMAPS-AA has and necessarily suppresses bacterial reproduction
Effect.From Fig. 2 it can also be seen that after the consumption of antibacterial polymer solution is more than 1900 μ g/mL, its
OD600Value did not increase in 24 hours, is continuously 0, does not i.e. have antibacterial to occur.This result shows base
Bacterial reproduction just can be effectively suppressed after the polymer volume of DMAPS-AA is more than 1900 μ g/mL.
Embodiment 2
By 20g N, N-dimethyl (methylacryoyloxyethyl) ammonium propane sulfonic acid inner salt (DMAPS) and
50g acrylic acid (AA) joins in reaction vessel, adds deionized water and stirs.Add 10g
Diethylene glycol divinyl ether, in reactor, stirs further, adds deionized water regulation and makes three
It is 23% that kind monomer total amount accounts for the mass percent of aqueous solution total amount.Under nitrogen protection, by 1g persulfuric acid
Ammonium is dissolved in 100mL deionized water, makes the initiator solution that concentration is 1wt%.Heating in water bath is anti-
Answer container when temperature rises to 65 DEG C, with Dropping funnel, initiator solution is added dropwise to reaction vessel by several times
In.Insulation reaction 4 hours, reaction is cooled to room temperature after terminating and gets final product discharging, it is thus achieved that based on DMAPS-AA
Shape-memory polymer.
The infrared spectrogram of prepared polymer based on DMAPS-AA is as it is shown on figure 3, represent sulfonic acid
(SO3 -) infrared absorption peak of structure has 1036cm-1, and at 960cm-1Place detects and represents quaternary amine
Salt structure (> N+) infrared absorption peak, this polymer prepared by explanation is a kind of based on sulfonate and season
The amphoteric ion polymer of amine salt.
Embodiment 3
By 15g N, N-dimethyl (methylacryoyloxyethyl) ammonium propane sulfonic acid inner salt (DMAPS) and
50g methacrylic acid (MA) joins in reaction vessel, adds deionized water and stirs.Add
5g ethylene glycol divinyl ether, in reactor, stirs further, adds deionized water regulation and makes three
Plant monomer total amount and account for the mass percent 25% of aqueous solution total amount.Under nitrogen protection, by 1g Ammonium persulfate.
It is dissolved in 100mL deionized water, makes the initiator solution that concentration is 1wt%.Heating in water bath for reaction
Initiator solution, when temperature rises to 65 DEG C, is added dropwise in reaction vessel by several times by container with Dropping funnel.
Insulation reaction 4 hours, reaction is cooled to room temperature after terminating and gets final product discharging, it is thus achieved that based on DMAPS-MA
Shape-memory polymer.
Testing its actual recovery of shape effect, the shape recovery process schematic diagram of sample is as shown in Figure 4.Wherein,
Fig. 4 a is shape-memory material original state；Fig. 4 b is the transitory state after deformable polymer is fixed；Fig. 4 c
It it is the polymer state at 50 DEG C of beginning deformation recoveries；Fig. 4 d is polymer shape of deformation recovery when 70 DEG C
State；Fig. 4 e is polymer shape when 80 DEG C after deformation recovery.From fig. 4, it can be seen that it is prepared
Polymer can effectively reply its original shape at 80 DEG C, has preferable recovery of shape performance.It addition,
Experiment also finds when the sample that deformation is fixing is placed in the aqueous solution of 37 DEG C, the temporary shapes energy of polymer
In 10 minutes, it is returned to rapidly its original shape, shows that this polymer is in blood heat and body fluid condition
Under there is preferable recovery of shape performance.
Embodiment 4
By the N of 30g, N-dimethyl-N-methacryiamidopropyl-N-propane sulfonic acid inner salt (DMHAS)
Join in reaction vessel with 50g acrylic acid (AA), add deionized water and stir.Add 20g
Triethyleneglycol divinylether, in reactor, stirs further, adds deionized water regulation and makes three
Plant monomer total amount and account for the mass percent 23% of aqueous solution total amount.Under nitrogen protection, by 1g Ammonium persulfate.
It is dissolved in 100mL deionized water, makes the initiator solution that concentration is 1wt%.Heating in water bath for reaction
Initiator solution, when temperature rises to 65 DEG C, is added dropwise in reaction vessel by several times by container with Dropping funnel.
Insulation reaction 4 hours, reaction is cooled to room temperature after terminating and gets final product discharging, it is thus achieved that based on DMHAS-AA
Shape-memory polymer.
By sample and the Turnover of Mouse Peritoneal Macrophages of prepared polymer based on DMHAS-AA
(RAW264.7) after co-cultivation 24 is little, fix 3h in 4 DEG C with in 2.5% glutaraldehyde solution, use
After PBS carrying out washing treatment, room temperature is dried, sample by ion sputtering gold-plated after, SEM observe huge bites thin
Born of the same parents' form, its electronic scanner microscope observed result is as shown in Figure 5, it can be seen that with polymer co-cultivation
Rear macrophage is adherent well, and containing more pseudopod, phagocytic activity is good.Polymer tool obtained by this law
There is preferable biocompatibility, do not affect normal cell activity and can be applied to biomedicine field efficiently and safely.
Embodiment 5
By 2-(2-methacryl oxidation ethosulfate base) acetate (DMAC) and the 50g of 30g
Acrylic acid (AA) joins in reaction vessel, adds deionized water and stirs.Add 20g tri-second
Divinyl ether, in reactor, stirs further, adds deionized water regulation, makes three kinds
Monomer total amount accounts for the mass percent 30% of aqueous solution total amount.Under nitrogen protection, by molten for 1g Ammonium persulfate.
Solution, in 100mL deionized water, makes the initiator solution that concentration is 1wt%.Heating in water bath for reaction is held
Initiator solution, when temperature rises to 65 DEG C, is added dropwise in reaction vessel by several times by device with Dropping funnel.Protect
Temperature reaction 4 hours, reaction is cooled to room temperature after terminating and gets final product discharging, it is thus achieved that shape based on DMHAS-AA
Shape memory polymer.
The sample of prepared polymer based on DMHAS-AA and Turnover of Mouse Peritoneal Macrophages
(RAW264.7), after co-cultivation 24 is little, fluorescence inverted biological microscope is used directly to observe macrophage
Form, as shown in Figure 6, it is seen that suspension cell form profile understands, form of diverse, in oval, table
The growth of bright mouse macrophage is normal, and prepared polymer based on DMAC-AA has preferable biology
The compatibility.
In sum, shape-memory polymer prepared by the present invention has good biocompatibility and excellent
Shape-memory properties, can be greatly improved its in biological medicine, medical treatment, the application of the aspect such as weaving.Described
Shape-memory polymer can also be applied to that antifouling paint, biomaterial surface be modified, polymerizable type forever resists
Electrostatic agent, salt-resistant type polymer etc., also have huge at engineering, building, daily life and the aspect such as medical
Application potential.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (9)
1. a shape-memory polymer with biocompatibility based on glycine betaine, it is characterised in that institute
State shape-memory polymer by the monomer A of 1～50 weight portions, 1～50 monomer B and 1～20 of weight portion
The monomer C of weight portion is polymerized；
Wherein, the formula of monomer A isR1For H or CH3, R2For O or
Person NH, R3For CH3,CH2CH3, CH2CH2CH3In any one, Y is COO, SO3,PO3
In any one；
The formula of monomer B isWherein R1It is H or CH3；
The formula of monomer C isWherein n=1～5.
2. a preparation method for the shape-memory polymer with biocompatibility based on glycine betaine, it is special
Levy and be, comprise the following steps: the monomer A and 1 of 1～50 weight portions～the monomer B of 50 weight portions is put
In reaction vessel, add water and stir；The monomer C of 1～20 weight portions is added in described reaction vessel,
Add water further and stir；Adding initiator, insulation reaction obtains described shape-memory polymer；
Wherein, the formula of monomer A isR1For H or CH3, R2For O or
Person NH, R3For CH3,CH2CH3, CH2CH2CH3In any one, Y is COO, SO3,PO3
In any one；
The formula of monomer B isWherein R1It is H or CH3；
The formula of monomer C isWherein n=1～5.
The preparation method of shape-memory polymer the most according to claim 2, it is characterised in that described
The consumption of initiator is monomer A, monomer B and the 0.5～2.0% of tri-kinds of monomer gross masses of monomer C.
4. according to the preparation method of the shape-memory polymer described in Claims 2 or 3, it is characterised in that
Described initiator is configured to the aqueous solution of mass fraction 1wt% before addition.
The preparation method of shape-memory polymer the most according to claim 4, it is characterised in that described
Preparation and the adition process of initiator are carried out in inert gas shielding atmosphere.
The preparation method of shape-memory polymer the most according to claim 4, it is characterised in that described
Initiator is at least one in Ammonium persulfate., potassium peroxydisulfate and redox initiator.
The preparation method of shape-memory polymer the most according to claim 2, it is characterised in that described
The temperature of insulation reaction is 65 DEG C, and the response time is 4～6 hours.
The preparation method of shape-memory polymer the most according to claim 2, it is characterised in that described
The amount added water is so that the mass percentage concentration of described shape-memory polymer is 20～30wt%.
The preparation method of shape-memory polymer the most according to claim 2, it is characterised in that described
Water is deionized water.
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| CN201410357273.1A CN104193893B (en) | 2014-07-24 | A kind of shape-memory polymer based on glycine betaine and preparation method thereof | |
| PCT/CN2014/091019 WO2016011729A1 (en) | 2014-07-24 | 2014-11-13 | Betaine-based shape memory polymer and preparation method therefor |
| US15/243,953 US10005866B2 (en) | 2014-07-24 | 2016-08-22 | Betaine-based shape memory polymer and preparation method thereof |
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| CN201410357273.1A CN104193893B (en) | 2014-07-24 | A kind of shape-memory polymer based on glycine betaine and preparation method thereof |
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| US5043396A (en) * | 1988-12-28 | 1991-08-27 | Nippon Zeon Co., Ltd. | Novel crosslinked polymer having shape memorizing property, method of its use, and molded article having shape memory |
| CN1662583A (en) * | 2002-06-17 | 2005-08-31 | 日本电气株式会社 | Biodegradable resin, biodegradable resin composition, biodegradable molded object, and process for producing biodegradable resin |
| CN1894313A (en) * | 2003-12-12 | 2007-01-10 | 日本电气株式会社 | Reshapable shape-memory resin excelling in shape recovery capability and shaped item of the resin having been crosslinked |
| CN103923275A (en) * | 2014-03-18 | 2014-07-16 | 深圳大学 | Amphoteric betaine polycarboxylic acid water reducing agent and preparation method thereof |
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| US5043396A (en) * | 1988-12-28 | 1991-08-27 | Nippon Zeon Co., Ltd. | Novel crosslinked polymer having shape memorizing property, method of its use, and molded article having shape memory |
| CN1662583A (en) * | 2002-06-17 | 2005-08-31 | 日本电气株式会社 | Biodegradable resin, biodegradable resin composition, biodegradable molded object, and process for producing biodegradable resin |
| CN1894313A (en) * | 2003-12-12 | 2007-01-10 | 日本电气株式会社 | Reshapable shape-memory resin excelling in shape recovery capability and shaped item of the resin having been crosslinked |
| CN103923275A (en) * | 2014-03-18 | 2014-07-16 | 深圳大学 | Amphoteric betaine polycarboxylic acid water reducing agent and preparation method thereof |
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