CN1142221C - Thermal shape memory gel material and its prepn - Google Patents
Thermal shape memory gel material and its prepn Download PDFInfo
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- CN1142221C CN1142221C CNB00129850XA CN00129850A CN1142221C CN 1142221 C CN1142221 C CN 1142221C CN B00129850X A CNB00129850X A CN B00129850XA CN 00129850 A CN00129850 A CN 00129850A CN 1142221 C CN1142221 C CN 1142221C
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- gel
- polyelectrolyte
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- cationic surfactant
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract 4
- 230000002194 synthesizing effect Effects 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000008961 swelling Effects 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 3
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XVCDQXABFKLFCH-UHFFFAOYSA-M sodium;n-prop-2-enoylsulfamate Chemical compound [Na+].[O-]S(=O)(=O)NC(=O)C=C XVCDQXABFKLFCH-UHFFFAOYSA-M 0.000 claims 1
- -1 vinyl acetate ester Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 150000001450 anions Chemical class 0.000 abstract 1
- 238000010276 construction Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000005022 packaging material Substances 0.000 abstract 1
- 238000003672 processing method Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 46
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012781 shape memory material Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- OPRIWFSSXKQMPB-UHFFFAOYSA-N 2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].OS(=O)(=O)CC(C)(C)NC(=O)C=C OPRIWFSSXKQMPB-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BOIPLBSSQGMAAC-UHFFFAOYSA-N [Na].OS(=O)(=O)CC(C)NC(=O)C=C Chemical compound [Na].OS(=O)(=O)CC(C)NC(=O)C=C BOIPLBSSQGMAAC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- SYWBAWRUYFQIBG-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid;sodium Chemical compound [Na].CCC(S(O)(=O)=O)NC(=O)C=C SYWBAWRUYFQIBG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 101100189378 Caenorhabditis elegans pat-3 gene Proteins 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000007087 memory ability Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004879 molecular function Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920000431 shape-memory polymer Polymers 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- LPXFITACVAQQAL-UHFFFAOYSA-M sodium;prop-2-enoylazanide Chemical compound [Na+].[NH-]C(=O)C=C LPXFITACVAQQAL-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
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- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种新型热致形状记忆凝胶材料及其制备方法，该材料是由聚电解质凝胶网络和阳离子型表面活性剂组成的复合物，其中合成所述聚电解质网络的物质包括阴离子型电解质和交联剂。这种材料的合成、加工方法简便，形状记忆温度可由合成聚电解质凝胶的单体或组成、表面活性剂等调节控制，可用作临床外科材料、建筑套管材料、功能性包装材料及信息存储材料等。
The invention discloses a novel thermally induced shape memory gel material and a preparation method thereof. The material is a compound composed of a polyelectrolyte gel network and a cationic surfactant, wherein the material for synthesizing the polyelectrolyte network includes an anion type electrolyte and crosslinking agent. The synthesis and processing methods of this material are simple, and the shape memory temperature can be adjusted and controlled by the monomer or composition of the synthetic polyelectrolyte gel, surfactants, etc., and can be used as clinical surgical materials, construction casing materials, functional packaging materials and information storage materials, etc.
Description
Technical field
The present invention relates to thermal shape memory gel material and preparation method thereof.
Background technology
The thermal shape memory macromolecular material is meant at a certain temperature distortion and can be in room temperature fixing and keep most of deformation for a long time, when reaching a certain specific response temperature when heating up, can be returned to the polymer materials of shape before the distortion again very soon again.This shape-memory material adopts temperature control, is easy to preparation and processing, is the most active field in the present shapememory polymer research and development.
The thermal shape memory macromolecular material has two phase structure usually, can reversibly solidify and the remollescent anti-phase but promptly remember the stationary phase of initial state and vary with temperature.Polyisoprene class (TPI) (Yao Wei, Song Jingshe, He Aihua etc.; Elastomerics, 1995,5 (4), 1), crosslinked polyethylene class (XLPE) (Nojiri A, Shiina N., Nakae H. etc., U.S. Pat 3 965 054,1976), polynorbornene class (Zhu Menglin; The exploitation of shape-memory material and application; The Shijiazhuang chemical industry, 1992,2,16), polyurethanes (Anda Norihiko; Day disclosure special permission communique, clear 59-227 438,1984) be present main thermal shape memory macromolecular material, they all are the shape memory high molecule materials after single polymer body ties up to molecular function modification and structural adjustment.
Polymer gel lies down the report of shape-memory material because it lacks physical strength, lacks ordered structure on molecular level.The long Tian Yiren professor's of Japan research group has reported by acrylic or methacrylic acid methyl esters and synthetic two kinds of shape memory gel (the Osada Yoshihito that obtain of long-chain aliphatic acrylate copolymerization; Nature, 1995,376,219), their hydrophobic parts can be assembled the formation crystal structure in water, and crystallization that produces along with variation of temperature and noncrystalline phase transformation cause the modulus generation great variety of gel, make gel have the function of thermal shape memory.
This thermal shape memory gel is the gel of copoly type, and its composition is subjected to that comonomer is reactive to be influenced, and the scope of can select, regulating is little; The influence that the crystalline region non-crystalline region transformation that gelatinous material thermal shape memory ability is played a decisive role is formed by copolymerization product is very big, but the complicacy of copolyreaction makes shortage control this regional effective means that forms; Thereby can not on purpose regulate the shape memory temperature of material.
Summary of the invention
The object of the present invention is to provide a kind of thermal shape memory gel material, its transition temperature can be regulated by the composition by matrix material in the zone of broad, thereby increase the purpose of shape memory gel material molecular designing, enlarge the application of hydrogel in the thermal shape memory polymeric material field.
Another object of the present invention is to provide the preparation method of this thermal shape memory gel material.
The invention provides a kind of thermal shape memory gel material, it is characterized in that described material forms mixture by polyelectrolyte gel network and cationic surfactant, wherein the material of synthetic described polyelectrolyte network comprises anionic ionogen and the linking agent methylene-bisacrylamide that is selected from vinylformic acid, sodium acrylate, methacrylic acid, sodium methacrylate or acrylamido sodium sulfonate, described cationic surfactant is a cetyl trimethylammonium bromide, and the content of water is 0-30wt% in described polyelectrolyte network.
In the present invention, the material of synthetic described polyelectrolyte network comprises that also one or more are selected from the component of acrylamide, methyl methacrylate, methacrylic acid isopropyl esters, vinyl acetate.
The content of anionic ionogen in described polyelectrolyte network is 20-80mol%, preferred 35-65mol%.Before desolventizing was handled, the total monomer content of institute's synthetic polyelectrolyte gel network was generally 1～2 mol among the present invention.
In described polyelectrolyte network, the anionic ionogen can be acrylic or methacrylic acid compounds (as a sodium acrylate, sodium methacrylate), also can be sulfonic compound (as acrylamido propanesulfonic acid sodium); Other component can be acrylate derivative (as acrylamide), methacrylic acid analog derivative (as the methacrylic acid isopropyl esters) and vinyl esters derivative (as vinyl acetate).
In described polyelectrolyte network, water-content is 0-30% (weight) after processed.
In thermal shape memory gel material of the present invention, the number of alkyl carbon atoms is 8-36 in the described cationic surfactant, and for example cationic surfactant can be cetyl trimethylammonium bromide etc.
The method of synthetic thermal shape memory gel mixture provided by the invention is: the synthetic polyelectrolyte gel network of method that adopts solution polymerization earlier, make its abundant swelling in appropriate solvent, reach behind the swelling equilibrium with an amount of cats product solution and mix, compound fully after, remove or part is removed and desolvated.
The polyelectrolyte gel in the thermal shape memory gel material of the present invention and the surfactant molecule of oppositely charged are by the structure of electrostatic interaction formation high-sequential, and this ordered structure can become unordered under heat effect.The great variety of the mechanical property that produces when utilizing gel compound system its composite structure under temperature variation that orderly, the unordered variation taken place, the shape memory function of realization material.Thermal shape memory gel material deformation temperature of the present invention can be controlled by the chain length of tensio-active agent, also can control by the composition of polynary polyelectrolyte gel network.
Thermal shape memory gel mixture of the present invention is compared with other shape-memory material, the motivating force difference of shape memory, preparation technology is simple, DEFORMATION RESPONSE temperature broad, response temperature can be regulated control by the composition of polyelectrolyte gel network or the chain length of cats product, and the polyelectrolyte gel-in-matrix has good biological tissue consistency.Thermal shape memory gel matrix material of the present invention can be used for Clinical Surgery's material, aspects such as building shell material, functional packing material and information storage material.
Description of drawings
Fig. 1 is the thermal shape memory mechanism of polyelectrolyte gel composite.
Embodiment
Embodiment 1:
Synthetic polyelectrolyte gel network in deionized water, isocyatic vinylformic acid and acrylamide solution are mixed, with the 1mol% Potassium Persulphate is initiator, the 1mol% methylene-bisacrylamide is a linking agent, in 60 ℃ of polymerizations 24 hours, obtain water white transparency polyacrylic acid-co-acrylamide gel.
After reaching swelling equilibrium in this gel immersion deionized water, take out, put into the isocyatic cetyl trimethylammonium bromide aqueous solution of acrylic acid solution compound, compound fully after, with the weight percentage of this mixture gel in drying at room temperature to water is below 30%, promptly get memory temperature and be 80 ℃ shape memory gel, deformation-recovery rate can reach 85%.
Embodiment 2:
Synthetic polynary polyelectrolyte gel network in organic solvent, the dimethyl sulphoxide solution of isocyatic 2-methyl-2-acrylamido propanesulfonic acid sodium and methyl methacrylate is mixed, with the 1mol% Diisopropyl azodicarboxylate is initiator, the 1mol% methylene-bisacrylamide is a linking agent, in 60 ℃ of polymerizations 24 hours, obtain the poly-2-methyl of water white transparency-2-acrylamido propanesulfonic acid sodium-co-methyl methacrylate gel.
This gel is immersed flush away dimethyl sulfoxide (DMSO) in the deionized water, after fully being swelling to swelling equilibrium, take out, put into 2-methyl-isocyatic cetyl trimethylammonium bromide aqueous solution of 2-acrylamido propanesulfonic acid sodium solution compound, compound fully after, this mixture gel in drying at room temperature to constant weight (water-content is 0%), is promptly got deformation temperature and be 104 ℃ shape memory gel, and deformation-recovery rate can reach 80%.
Embodiment 3:
Synthetic polyelectrolyte gel network in deionized water adds 1mol% Potassium Persulphate and 1mol% methylene-bisacrylamide in the 1mol/L acrylic acid aqueous solution, in 60 ℃ of polymerizations 24 hours, obtain the water white transparency carbopol gel.
After reaching swelling equilibrium in this gel immersion deionized water, take out, put into the isocyatic cetyl trimethylammonium bromide aqueous solution of acrylic acid solution compound, compound fully after, with the weight percentage of this mixture gel in drying at room temperature to water is below 30%, promptly get deformation temperature and be 97 ℃ shape memory gel, deformation-recovery rate can reach 65%.
Embodiment 4:
Synthetic polyelectrolyte gel network in organic solvent, in the dimethyl sulphoxide solution of 1mol/L 2-methyl-2-acrylamido propanesulfonic acid sodium, add 1mol% Diisopropyl azodicarboxylate and 1mol% methylene-bisacrylamide, in 60 ℃ of polymerizations 24 hours, obtain the poly-2-methyl of water white transparency-2-acrylamido propanesulfonic acid sodium gel.
This gel is immersed flush away dimethyl sulfoxide (DMSO) in the deionized water, after fully being swelling to swelling equilibrium, take out, put into 2-methyl-isocyatic cetyl trimethylammonium bromide aqueous solution of 2-acrylamido propanesulfonic acid sodium solution compound, compound fully after, this mixture gel in drying at room temperature, is promptly got deformation temperature and be 123 ℃ shape memory gel, and deformation-recovery rate can reach 67%.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB00129850XA CN1142221C (en) | 2000-10-20 | 2000-10-20 | Thermal shape memory gel material and its prepn |
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| CNB00129850XA CN1142221C (en) | 2000-10-20 | 2000-10-20 | Thermal shape memory gel material and its prepn |
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| CN1350033A CN1350033A (en) | 2002-05-22 |
| CN1142221C true CN1142221C (en) | 2004-03-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11504685B1 (en) | 2021-09-27 | 2022-11-22 | Suzhou Yisheng Optical Material Co., Ltd. | Processing equipment and processing technology of gel microsphere material |
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| CN111499782B (en) * | 2020-05-14 | 2021-03-23 | 浙江大学 | High-strength physical hydrogel based on polyelectrolyte/surfactant composite and preparation method thereof |
| CN114523685B (en) * | 2022-01-28 | 2023-04-21 | 华南理工大学 | A flame-retardant fast software driver based on shape memory effect and its preparation method and application |
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| US11504685B1 (en) | 2021-09-27 | 2022-11-22 | Suzhou Yisheng Optical Material Co., Ltd. | Processing equipment and processing technology of gel microsphere material |
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