CN103254437B - Method for inducing azobenzene liquid crystal elastomer photoinduced deformation by silk protein - Google Patents
Method for inducing azobenzene liquid crystal elastomer photoinduced deformation by silk protein Download PDFInfo
- Publication number
- CN103254437B CN103254437B CN201210419211.XA CN201210419211A CN103254437B CN 103254437 B CN103254437 B CN 103254437B CN 201210419211 A CN201210419211 A CN 201210419211A CN 103254437 B CN103254437 B CN 103254437B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- add
- solution
- hours
- react
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Peptides Or Proteins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method for inducing azobenzene liquid crystal elastomer photoinduced deformation by silk protein, which comprises the following step: firstly generating linear polymers by hydrosilation reaction, opening residual double bonds by a photoinitiator for crosslinking, forming a crosslinked liquid crystal elastomer, using silk proteins as support membrane, and simultaneously inducing orientation of LCEs liquid crystal motifs by hydrogen bonds of silk proteins, (that is azobenzene liquid crystal motif is arranged vertically to the membrane direction in order); thereby the glass-transition temperature of the crosslinked elastomer is below the room temperature, and can response to the directivity rapidly under the ultraviolet irradiation. The invention is very simple, and only the manually simple operation is needed, and large-scale apparatuses are not needed, the method is suitable for popularization and application.
Description
Technical field
The present invention relates to a kind of method preparing light-operated responsiveness shape-changing material, be specifically related to the method for a kind of fibroin induction nitrogen benzide liquid crystal elastic body photo-deformable.
Background technology
In recent years, photo-deformable liquid crystal polymkeric substance caused the interest of academia and material circle.Mainly because this polymer film can produce deformation under ultraviolet lighting, returning to original state when visible ray photograph, when there is no battery or cable, utilizing this exotic materials can achieve luminous energy to mechanical conversion of energy.This makes this material be expected to be applied to artificial-muscle, photic stopper etc.
Take siloxanes as the side chain liquid crystalline polymer of main chain, research finds that its liquid crystal unit one end is connected on main chain by flexible spacer group, due to the good mechanical property of organosilicon material, lower second-order transition temperature, preferably temperature profile and photoelectric response faster, alignment state, without keeping the characteristic such as stable during electric field action for a long time, makes side-chain liquid crystal primitive have the liquid crystal properties such as better threshold values characteristic and recovery characteristic.Azobenzene molecule can produce the transformation of transoid conformation to cisoid conformation under ultraviolet lighting, and when azobenzene molecule is joined in liquid crystal molecule, this molecule as hot or electric, reversible photochemistry phase in version can occur under external stimulus.Therefore in conjunction with the characteristic of siloxanes and nitrogen benzide, by controlling the orientation of liquid crystal unit, the material of artificial-muscle can be prepared in theory.This material at room temperature directly utilizes light to realize the deformation of light-operated directivity.Can overcome in current research system and control orientation relative complex, response is the shortcoming such as slower several times.
Summary of the invention
For solving the problem, the invention provides the method for a kind of fibroin induction nitrogen benzide liquid crystal elastic body photo-deformable, object is to prepare a kind of simple, maneuverable light-operated responsiveness shape-changing material.
For realizing above-mentioned technical purpose, reach above-mentioned technique effect, the present invention is achieved through the following technical solutions:
A method for fibroin induction nitrogen benzide liquid crystal elastic body photo-deformable, comprises the following steps:
Step 1) P-nethoxyaniline of the 0.05mol that weighs with scale is positioned in two mouthfuls of flasks, adding the massfraction configured is the hydrochloric acid soln of 50%, stir, dropwise dripping massfraction is again the sodium nitrite solution of 40%, keep solution temperature at 0-5 DEG C in dropping process, react 1 hour, obtain brown solution one;
Weigh with scale sodium hydroxide 0.125mol, and phenol 0.075mol is positioned in the round-bottomed flask of 250ml, add 150ml water, stir, then with sodium bicarbonate, this solution PH is transferred to 8-9, be cooled to 0 DEG C, solution one is joined rapidly in this solution, react 2 hours, obtain yellow mercury oxide, suction filtration, dry, namely obtain hydroxymethoxy nitrogen benzide;
Step 2) 4.24g P-nethoxyaniline is positioned in two mouthfuls of flasks, add 1.56gNaH, then add the anhydrous DMF of 100ml, pass into nitrogen 20min, add reflux condensing tube, and be heated to 80 DEG C; Add 6-bromo-1-hexene 3.1g, react 16 hours, be cooled to room temperature, then with ethyl acetate and water extraction, add anhydrous magnesium sulfate dried overnight; Be that 5:1 crosses pillar by sherwood oil and ethyl acetate volume ratio again, obtain the nitrogen benzide liquid crystal monomer that double bond is contained in one end;
By above-mentioned, hydroxymethoxy nitrogen benzide 2.046g is positioned in two mouthfuls of flasks, adds 0.96gNaH, then add the anhydrous DMF of 100ml, pass into nitrogen 20min, add reflux condensing tube, and be heated to 80 DEG C; Add 6-bromo-1-hexene 6.19g, react 16 hours, be cooled to room temperature, then with ethyl acetate and water extraction, add anhydrous magnesium sulfate dried overnight, then be that 4:6 crosses pillar by methylene dichloride and normal hexane volume ratio, obtain the nitrogen benzide liquid crystal monomer that double bond is contained at two ends;
Step 3) get the nitrogen benzide liquid crystal monomer three (ethene glycol) divinyl ethers that mol ratio is 1:9 and above-mentioned one end containing double bond, be dissolved in 30ml dry toluene with polymethyl hydrogen siloxane, then adding (1,5-cyclooctadiene) platinum dichloride (II) molar mass is 1 × 10 of double bond
-3doubly; Be heated to 110 DEG C, react 43 hours, anhydrous and oxygen-free in strict guarantee system, reacted rear sherwood oil coagulation and obtained micro-crosslinked polymer;
Step 4) a certain amount of above-mentioned micro-crosslinked polymer is dissolved in toluene, add the light trigger that massfraction is 2%, stir, solution whirlpool is coated with film forming, under the UV-irradiation of 365nm, be added to 70 DEG C of reactions 6 hours, obtain crosslinking polymer thin film;
Step 5) the silk solution whirlpool of 5% is coated in scribbles on the slide glass of PDMS, make silk solution film forming, then the whirlpool being added with micro-crosslinked polymer solution is coated on silk, under the UV-irradiation of 365nm, be heated to 70 DEG C of reactions 6 hours, obtain fibroin support film.
Two step cross-linking methods are as follows:
The invention has the beneficial effects as follows:
1, the present invention successfully synthesizes crosslinked liquid crystal elastic body (LCEs) by two step crosslinkings, then by fibroin as support membrane, utilize hydrogen bond induction LCEs liquid crystal unit generation orientation (Azobenzene mesogen is perpendicular to the direction ordered arrangement of film) of fibroin simultaneously, make the second-order transition temperature of cross-linked elastomer below room temperature, it can the response of directivity rapidly under UV-irradiation;
2, the present invention is very simple, only needs simple manual operation, does not need, by large-scale instrument, not require much skill, be applicable to applying.
Accompanying drawing explanation
Fig. 1 is that differential scanning calorimetery (DSC) contains the sign of double bond small molecules A liquid crystal monomer to one end;
Fig. 2 is the liquid crystal texture that under polarizing microscope (POM), double bond small molecules A liquid crystal monomer is contained in one end;
Fig. 3 is that differential scanning calorimetery (DSC) is to the sign of micro-crosslinked polymer;
Fig. 4 is the liquid crystal texture of micro-crosslinked polymer under polarizing microscope (POM);
Fig. 5 is the sign to micro-crosslinked polymer under XRD;
Fig. 6 is the cis-trans isomerism transformation period figure of micro-crosslinked polymer solution ultra-violet absorption spectrum;
Fig. 7 is the reversible LCEs motion of opening the light under ultraviolet light of fibroin support film;
Fig. 8 is the sign of micro-crosslinked polymer film and fibroin support film under XRD;
Fig. 9 is fibroin support film TEM diffractogram.
Embodiment
Below with reference to the accompanying drawings and in conjunction with the embodiments, describe the present invention in detail.
A method for fibroin induction nitrogen benzide liquid crystal elastic body photo-deformable, comprises the following steps:
Step 1) P-nethoxyaniline of the 0.05mol that weighs with scale is positioned in two mouthfuls of flasks, adding the massfraction configured is the hydrochloric acid soln of 50%, stir, dropwise dripping massfraction is again the sodium nitrite solution of 40%, keep solution temperature at 0-5 DEG C in dropping process, react 1 hour, obtain brown solution one;
Weigh with scale sodium hydroxide 0.125mol, and phenol 0.075mol is positioned in the round-bottomed flask of 250ml, add 150ml water, stir, then with sodium bicarbonate, this solution PH is transferred to 8-9, be cooled to 0 DEG C, solution one is joined rapidly in this solution, react 2 hours, obtain yellow mercury oxide, suction filtration, dry, namely obtain hydroxymethoxy nitrogen benzide;
Step 2) 4.24g P-nethoxyaniline is positioned in two mouthfuls of flasks, add 1.56gNaH, then add the anhydrous DMF of 100ml, pass into nitrogen 20min, add reflux condensing tube, and be heated to 80 DEG C; Add 6-bromo-1-hexene 3.1g, react 16 hours, be cooled to room temperature, then with ethyl acetate and water extraction, add anhydrous magnesium sulfate dried overnight; Be that 5:1 crosses pillar by sherwood oil and ethyl acetate volume ratio again, obtain the nitrogen benzide liquid crystal monomer that double bond is contained in one end;
By above-mentioned, hydroxymethoxy nitrogen benzide 2.046g is positioned in two mouthfuls of flasks, adds 0.96gNaH, then add the anhydrous DMF of 100ml, pass into nitrogen 20min, add reflux condensing tube, and be heated to 80 DEG C; Add 6-bromo-1-hexene 6.19g, react 16 hours, be cooled to room temperature, then with ethyl acetate and water extraction, add anhydrous magnesium sulfate dried overnight, then be that 4:6 crosses pillar by methylene dichloride and normal hexane volume ratio, obtain the nitrogen benzide liquid crystal monomer that double bond is contained at two ends;
Step 3) get the nitrogen benzide liquid crystal monomer three (ethene glycol) divinyl ethers that mol ratio is 1:9 and above-mentioned one end containing double bond, be dissolved in 30ml dry toluene with polymethyl hydrogen siloxane, then adding (1,5-cyclooctadiene) platinum dichloride (II) molar mass is 1 × 10 of double bond
-3doubly; Be heated to 110 DEG C, react 43 hours, anhydrous and oxygen-free in strict guarantee system, reacted rear sherwood oil coagulation and obtained micro-crosslinked polymer;
Step 4) a certain amount of above-mentioned micro-crosslinked polymer is dissolved in toluene, add the light trigger that massfraction is 2%, stir, solution whirlpool is coated with film forming, under the UV-irradiation of 365nm, be added to 70 DEG C of reactions 6 hours, obtain crosslinking polymer thin film;
Step 5) the silk solution whirlpool of 5% is coated in scribbles on the slide glass of PDMS, make silk solution film forming, then the whirlpool being added with micro-crosslinked polymer solution is coated on silk, under the UV-irradiation of 365nm, be heated to 70 DEG C of reactions 6 hours, obtain fibroin support film.
Result and discussion:
1, the sign of double bond small molecules A liquid crystal monomer is contained in one end
Use differential scanning calorimetery (DSC), polarizing microscope, and the liquid crystal property of X-ray to sample characterizes.Shown in Figure 1, the result of DSC is that small molecules is once lowered the temperature, and the data of secondary temperature elevation have three melting peaks when once lowering the temperature, and secondary temperature elevation has two melting peaks explanation small molecules to be likely smectic liquid crystal.Liquid crystal texture in composition graphs 2, illustrates that the small molecules of synthesis is smectic liquid crystal.
2, the sign of micro-crosslinked polymer liquid crystal liquid crystal property
By characterizing micro-crosslinked polymer liquid crystal liquid crystal property with differential scanning calorimetery (DSC), polarizing microscope (POM) and X-Ray.The result of DSC is that polymkeric substance is once lowered the temperature, the data of secondary temperature elevation.Shown in Figure 3, can find out that polymkeric substance has two obviously heat absorption heat release phase transformation peaks. shown in Figure 4, grains of sand shape liquid crystal texture can be seen clearly.Shown in Figure 5, can find out has a very weak peak at 5 ° and at about 20 ° very very wide steamed bun peaks, can determine that linear polymer belongs to smectic liquid crystal in conjunction with DSC, POM and XRD.
3, the research of time of response
With polysiloxane be main chain polymkeric substance due to the flexibility of siloxane bond fine, the polymkeric substance of room temperature response can be obtained.The present invention's synthesis take siloxanes as the nitrogen benzide side chain liquid crystalline polymer of main chain, achieve the feature of response fast under room temperature.We are tested its cis-trans isomerism transformation period by micro-crosslinked polymer solution ultra-violet absorption spectrum, shown in Figure 6, and from UV collection of illustrative plates, we obviously see when 420s, and the absorption peak major part of transoid conformation disappears.
4, the performance study of fibroin support film
Azobenzene molecule can produce the change of conformation under UV-irradiation, is embodied on macroscopic film and just can produces deformation (bending).If azobenzene molecule is all perpendicular to film surface arrangement, the direction that film will produce ultraviolet lamp dorsad bends.Shown in Figure 7, can find out that fibroin support film UV-light can reversiblely be opened the light the motion of LCEs.
5, XRD test
In order to study the arrangement mode of Azobenzene mesogen on fibroin film, we have done X-Ray test respectively to micro-crosslinked polymer film and fibroin support film, shown in Figure 8, can find out that the characteristic peak (20 °) in fibroin support film in this body thin film disappears.Shown in Figure 9, there is a diffraction ring, illustrate and be spin-coated on Azobenzene mesogen on fibroin surface perpendicular to film surface, just can the orientation of liquid crystal unit of control LCEs by simple spin coating technique, realize photoswitch motion.
Claims (1)
1. a method for fibroin induction nitrogen benzide liquid crystal elastic body photo-deformable, is characterized in that, comprise the following steps:
Step 1) P-nethoxyaniline of the 0.05mol that weighs with scale is positioned in two mouthfuls of flasks, adding the massfraction configured is the hydrochloric acid soln of 50%, stir, dropwise dripping massfraction is again the sodium nitrite solution of 40%, keep solution temperature at 0-5 DEG C in dropping process, react 1 hour, obtain brown solution one;
Weigh with scale sodium hydroxide 0.125mol, and phenol 0.075mol is positioned in the round-bottomed flask of 250ml, add 150ml water, stir, then with sodium bicarbonate, this solution PH is transferred to 8-9, be cooled to 0 DEG C, solution one is joined rapidly in this solution, react 2 hours, obtain yellow mercury oxide, suction filtration, dry, namely obtain hydroxymethoxy nitrogen benzide;
Step 2) 4.24g P-nethoxyaniline is positioned in two mouthfuls of flasks, add 1.56gNaH, then add the anhydrous DMF of 100ml, pass into nitrogen 20min, add reflux condensing tube, and be heated to 80 DEG C; Add 6-bromo-1-hexene 3.1g, react 16 hours, be cooled to room temperature, then with ethyl acetate and water extraction, add anhydrous magnesium sulfate dried overnight; Be that 5:1 crosses pillar by sherwood oil and ethyl acetate volume ratio again, obtain the nitrogen benzide liquid crystal monomer that double bond is contained in one end;
By above-mentioned, hydroxymethoxy nitrogen benzide 2.046g is positioned in two mouthfuls of flasks, adds 0.96gNaH, then add the anhydrous DMF of 100ml, pass into nitrogen 20min, add reflux condensing tube, and be heated to 80 DEG C; Add 6-bromo-1-hexene 6.19g, react 16 hours, be cooled to room temperature, then with ethyl acetate and water extraction, add anhydrous magnesium sulfate dried overnight, then be that 4:6 crosses pillar by methylene dichloride and normal hexane volume ratio, obtain the nitrogen benzide liquid crystal monomer that double bond is contained at two ends;
Step 3) get the nitrogen benzide liquid crystal monomer three (ethene glycol) divinyl ethers that mol ratio is 1:9 and above-mentioned one end containing double bond, be dissolved in 30ml dry toluene with polymethyl hydrogen siloxane, then adding (1,5-cyclooctadiene) platinum dichloride (II) molar mass is 1 × 10 of double bond
-3doubly; Be heated to 110 DEG C, react 43 hours, anhydrous and oxygen-free in strict guarantee system, reacted rear sherwood oil coagulation and obtained micro-crosslinked polymer;
Step 4) a certain amount of above-mentioned micro-crosslinked polymer is dissolved in toluene, add the light trigger that massfraction is 2%, stir, solution whirlpool is coated with film forming, under the UV-irradiation of 365nm, be added to 70 DEG C of reactions 6 hours, obtain crosslinking polymer thin film;
Step 5) the silk solution whirlpool of 5% is coated in scribbles on the slide glass of PDMS, make silk solution film forming, then the whirlpool being added with micro-crosslinked polymer solution is coated on silk, under the UV-irradiation of 365nm, be heated to 70 DEG C of reactions 6 hours, obtain fibroin support film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419211.XA CN103254437B (en) | 2012-10-29 | 2012-10-29 | Method for inducing azobenzene liquid crystal elastomer photoinduced deformation by silk protein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419211.XA CN103254437B (en) | 2012-10-29 | 2012-10-29 | Method for inducing azobenzene liquid crystal elastomer photoinduced deformation by silk protein |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103254437A CN103254437A (en) | 2013-08-21 |
| CN103254437B true CN103254437B (en) | 2015-04-15 |
Family
ID=48958681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210419211.XA Expired - Fee Related CN103254437B (en) | 2012-10-29 | 2012-10-29 | Method for inducing azobenzene liquid crystal elastomer photoinduced deformation by silk protein |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103254437B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521446B (en) * | 2022-09-19 | 2023-07-18 | 广东省科学院生物与医学工程研究所 | Azobenzene liquid crystal polymer and preparation method and application thereof |
-
2012
- 2012-10-29 CN CN201210419211.XA patent/CN103254437B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 侧链含偶氮基的聚硅氧烷类液晶高分子及其离聚物的合成与表征;邵兵等;《高分子材料科学与工程》;20020531;第18卷(第3期);第70-76页 * |
| 偶氮类侧链聚硅氧烷液晶高分子的合成与研究;侯昭升;《万方数据知识服务平台 学位论文》;20120503;全文 * |
| 偶氮苯侧链共聚硅氧烷的合成及液晶行为的研究;候昭升等;《高分子学报》;20021231(第6期);第742-745页 * |
| 光致变色聚硅氧烷液晶高分子的合成及液晶行为;候昭升等;《高分子材料科学与工程》;20040731;第20卷(第4期);第77-80页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103254437A (en) | 2013-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Polysiloxane-based liquid crystalline polymers and elastomers prepared by thiol–ene chemistry | |
| Zu et al. | Transparent, superflexible doubly cross-linked polyvinylpolymethylsiloxane aerogel superinsulators via ambient pressure drying | |
| Cheng et al. | NIR–Vis–UV light-responsive actuator films of polymer-dispersed liquid crystal/graphene oxide nanocomposites | |
| Liu et al. | Aggregation-induced emission luminogen-functionalized liquid crystal elastomer soft actuators | |
| Wang et al. | Multi-stimuli responsive carbon nanotube incorporated polysiloxane azobenzene liquid crystalline elastomer composites | |
| Ma et al. | 3D printable, recyclable and adjustable comb/bottlebrush phase change polysiloxane networks toward sustainable thermal energy storage | |
| Michal et al. | Metallo-, thermo-, and photoresponsive shape memory and actuating liquid crystalline elastomers | |
| Kuenstler et al. | Reversible actuation via photoisomerization-induced melting of a semicrystalline poly (azobenzene) | |
| Wang et al. | Hepta (3, 3, 3-trifluoropropyl) polyhedral oligomeric silsesquioxane-capped poly (N-isopropylacrylamide) telechelics: synthesis and behavior of physical hydrogels | |
| Han et al. | Transparent photothermal heaters from a soluble NIR‐absorbing diimmonium salt | |
| Li et al. | Thermoresponsive helical poly (phenylacetylene) s | |
| Qin et al. | Tetracarboxylated azobenzene/polymer supramolecular assemblies as high-performance multiresponsive actuators | |
| WO2013159567A1 (en) | Photoelectric material preparation | |
| Fu et al. | Solar thermal storage and room-temperature fast release using a uniform flexible azobenzene-grafted polynorborene film enhanced by stretching | |
| Yang et al. | Thermo‐sensitive electrospun fibers prepared by a sequential thiol‐ene click chemistry approach | |
| JP2011219719A (en) | Polysilsesquioxane having ladder structure with photoactive group in side chain and production method of the same | |
| Gong | Anchoring of self-curable ionene-containing polyesters to electrode surface by UV irradiation and their humidity-sensitive properties | |
| CN109608564A (en) | A kind of side chain liquid crystalline polymer containing azobenzene and preparation method thereof with micro phase separation structure | |
| Seo et al. | Foldable and extremely scratch-resistant hard coating materials from molecular necklace-like cross-linkers | |
| Liu et al. | Ultraviolet and infrared two-wavelength modulated self-healing materials based on azobenzene-functionalized carbon nanotubes | |
| Shen et al. | Recyclable and reprocessable epoxy-polyhedral oligomeric silsesquioxane (POSS)/mesogenic azobenzene/poly (ethylene-co-vinyl acetate) composites with thermal-and light-responsive programmable shape-memory performance | |
| Zhu et al. | Molecular engineering of step-growth liquid crystal elastomers | |
| CN108329645A (en) | A kind of hybrid material of UV light-induced gradient-structure, preparation method and its application in terms of response transfer of shapes | |
| CN109735280A (en) | Ultraviolet light response polymer adhesive and its preparation method and application | |
| Yang et al. | Hybrid organic-inorganic dyeionogels: Reversibly pH-responsive materials based dye-ionic liquids with improved structural stability and flexibility |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20171029 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |