CN108484923B - Supermolecular polymer based on thioctic acid compound and preparation method thereof - Google Patents
Supermolecular polymer based on thioctic acid compound and preparation method thereof Download PDFInfo
- Publication number
- CN108484923B CN108484923B CN201810232611.7A CN201810232611A CN108484923B CN 108484923 B CN108484923 B CN 108484923B CN 201810232611 A CN201810232611 A CN 201810232611A CN 108484923 B CN108484923 B CN 108484923B
- Authority
- CN
- China
- Prior art keywords
- supramolecular polymer
- derivatives
- iron
- lipoic acid
- polymer
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a supramolecular polymer based on lipoic acid or/and derivatives thereof and a preparation method thereof. The supramolecular polymer is mainly obtained by hot-melting and mixing lipoic acid or/and derivatives thereof, a cross-linking agent and an iron source. Wherein the molar ratio of the lipoic acid or/and derivatives thereof, the cross-linking agent and the iron source is 2 (0.1-1.5) to 0.01-1; the lipoic acid or/and derivatives thereof is selected from: one or a mixture of more than two of the compounds shown in the formula I; the cross-linking agent is a hydrocarbon compound containing carbon-carbon unsaturated bonds, and the iron source consists of iron salt and an organic solvent capable of dissolving the iron salt. The super-molecular polymer provided by the invention has the stretchability of more than 150 times, and can be super-rapidly self-repaired at room temperature.
In the formula I, R1Is hydrogen or C1～C4Straight or branched alkyl, R2Is hydrogen or carboxyl, and n is an integer of 1 to 5.
Description
Technical Field
The invention relates to a supramolecular polymer and a preparation method thereof, in particular to a supramolecular polymer based on lipoic acid or/and derivatives thereof and a preparation method thereof.
Background
The supramolecular polymer refers to a polymer formed by self-assembly of small molecular monomers or low molecular polymers through interaction of non-covalent bonds. The factors such as pH value, temperature and illumination can cause the dissociation and recombination of non-covalent bonds of the supramolecular polymer, and the supramolecular polymer has reversibility, so that the supramolecular polymer can be used as an intelligent material for self-repairing and self-healing, and is one of the research hotspots at home and abroad in recent years.
The supramolecular polymer has wide application fields, such as modified intelligent materials, electronic devices, biological materials and the like. In recent years, the research on the application of the composition in the biological and biomedical fields is rapidly developed, and the composition comprises cell-related applications, tissue engineering, drug delivery, immune regulation, wound healing and the like.
In 2016, Bacho et al obtained a 100-fold stretchable self-healing elastomer at room temperature for 48 hours by introducing a cross-linking complex into a Polydimethylsiloxane (PDMS) chain (A highly stretchable self-healing elastomer, nat. chem.2016, 8, 618-. The crosslinking complex used consists of a 2, 6-pyridinediamide ligand which coordinates to the Fe (III) center by three different interactions.
The prior art has the defect that the monomer or low molecular polymer for preparing the supermolecular polymer is difficult to obtain (needs to be made by self). Therefore, the preparation of supramolecular polymers with excellent properties using the currently known compounds is a technical problem to be solved by the present invention.
Disclosure of Invention
The inventors of the present invention have found, through extensive and intensive studies: lipoic acid or its derivative as monomer, cross-linking agent and Fe ion source in certain amount are mixed and hot melted to obtain supermolecular polymer without solvent. The obtained supermolecular polymer has the advantages of high extensibility of more than 150 times and capability of being subjected to ultrafast self-repairing (not more than one minute) under the condition of room temperature.
It is an object of the present invention to provide a supramolecular polymer based on lipoic acid or/and derivatives thereof.
The supramolecular polymer is prepared by the preparation method mainly comprising the following steps:
under the condition of no solvent, the lipoic acid or/and the derivatives thereof, the cross-linking agent and the iron source are subjected to hot melting and mixing to obtain a target object;
wherein, the mol ratio of the lipoic acid or/and the derivatives thereof, the cross-linking agent and the iron source is 2 (0.1-1.5) to (0.01-1), (the mol number of the iron source is the mol number of iron ions);
the lipoic acid or/and derivatives thereof is selected from: one or more than two (including two) mixtures of the compounds shown in the formula I;
the crosslinking agent is a hydrocarbon compound containing carbon-carbon unsaturated bonds, and the iron source consists of iron salt and an organic solvent capable of dissolving the iron salt;
in the formula I, R1Is hydrogen or C1～C4Straight or branched alkyl, R2Is hydrogen or carboxyl (-COOH), and n is an integer of 1-5.
It is another object of the present invention to provide a process for the preparation of the supramolecular polymer described above.
The method mainly comprises the following steps: under the condition of no solvent, the lipoic acid or/and the derivatives thereof are placed in a reaction vessel with a stirring device, stirred and heated, after the lipoic acid or/and the derivatives thereof are melted, the cross-linking agent and the iron source are sequentially added into the reaction vessel according to the molar ratio, stirred for at least 3 minutes, the heating is stopped, and the target product is obtained after cooling.
Drawings
FIG. 1 is an appearance diagram of a supramolecular polymer prepared in example 1 of the present invention;
FIG. 2 is a graph of the rheological properties of supramolecular polymers prepared in example 2 of the present invention;
FIG. 3 is a structural representation of supramolecular polymers prepared in example 3 of the present invention;
wherein A is a structural schematic diagram of the polymer, B is an infrared spectrogram of the polymer, and C is a Raman spectrogram of the polymer;
FIG. 4 is a diagram illustrating the self-healing performance of the supramolecular polymer prepared in example 4 of the present invention;
wherein, A is a self-healing microscopic image of the supramolecular polymer, and B is a stretching curve of the supramolecular polymer after initial and self-healing;
FIG. 5 is a diagram of the underwater self-healing performance of the supramolecular polymer prepared in example 5 of the invention;
wherein, A is a cutting graph of the supramolecular polymer, and B is an underwater self-healing performance representation graph of the supramolecular polymer.
Fig. 6 is a graph of the tensile and rebound properties of supramolecular polymers prepared in example 6 of the invention:
wherein, A is an initial diagram of the supramolecular polymer, B is a drawing diagram of the supramolecular polymer, C is a diagram of the release of the supramolecular polymer after being drawn, D is a drawing performance curve of the supramolecular polymer, and E is a rebound performance curve of the supramolecular polymer.
Detailed Description
In a preferable technical scheme of the invention, the lipoic acid or/and the derivatives thereof are compounds shown in formula I, wherein n is an integer of 1-3.
In another preferred embodiment of the present invention, the crosslinking agent is a substituted benzene, the substituent of which is vinyl or C1～C3An alkyl-substituted vinyl group;
the preferred crosslinking agents used in the present invention are styrene, divinylbenzene or 1, 3-bis (1-methylvinyl) benzene (DIB).
In another preferred embodiment of the present invention, the iron salt may be iron sulfate, iron chloride, iron nitrate or/and iron stearate; the organic solvent is acetone, ethanol or methanol.
The invention provides a method for preparing the supermolecular polymer, which mainly comprises the following steps: under the condition of no solvent, the lipoic acid or/and the derivatives thereof are placed in a reaction vessel with a stirring device, stirred and heated (the oil bath temperature is 70-200 ℃), after the lipoic acid or/and the derivatives thereof are melted, the cross-linking agent is added into the reaction vessel according to the molar ratio, after the completion, the stirring is continued for 5-8 minutes, the iron source is added into the reaction vessel according to the molar ratio, after the completion, the stirring is continued for 3-5 minutes, the heating is stopped, and the target product is obtained after cooling.
The invention has the following characteristics:
1. the raw materials used in the invention are beneficial to human body, are biocompatible, have wide sources, are cheap and easily available, and have industrial feasibility;
2. the invention adopts a method of directly heating and melting raw materials, does not need solvent, has quick reaction, simple and safe process and does not produce industrial pollution such as waste water, waste residue and the like. The whole preparation process is simple, the production cost is low, the yield is quantitative, and the requirements of green chemistry are met;
3. the supermolecule polymer provided by the invention has room-temperature and underwater self-healing performance, high stretchability (capable of being stretched by more than 150 times) and excellent thermal responsiveness (capable of being subjected to solid-liquid conversion for more than 10 times under thermal stimulation).
In addition, the supramolecular polymer provided by the invention has good biocompatibility (and does not contain solvent), and has wide application prospect in the field of biological medical treatment.
The invention is further illustrated by the following examples, which are intended only for a better understanding of the contents of the invention. The examples given therefore do not limit the scope of protection of the invention.
Preparation of supramolecular polymers
Example 1
10g of lipoic acid powder is placed in a reactor with a stirring device, heated in an oil bath until the lipoic acid powder is melted, and stirred. Then 6g (60 wt%) of 1, 3-bis (1-methylvinyl) benzene (DIB) was added to the reactor, and heating and stirring were continued for 5 minutes. And adding 0.1g of ferric chloride acetone solution into the reactor, continuously heating and stirring for 3 minutes, stopping heating, and cooling to room temperature to obtain the supramolecular polymer-1.
Examples 2 to 8
The procedure and conditions were the same as in example 1 except that the kinds of the monomer and the crosslinking agent and the molar ratio of the monomer, the crosslinking agent and the iron source were changed to obtain different supramolecular polymers, respectively, as detailed in table 1.
TABLE 1
The appearance of the supramolecular polymer provided by the invention (taking supramolecular polymer-1 as an example) is shown in figure 1; the rheological property curve of the supramolecular polymer (taking supramolecular polymer-2 as an example) is shown in figure 2; and the structural characterization of the supramolecular polymer provided (taking supramolecular polymer-3 as an example) is shown in fig. 3.
Test of self-healing (healing) property, tensile property and thermal response property of supramolecular polymer
Example 9
1. Testing of self-healing (healing) performance
(1) Taking a section of strip-shaped supramolecular polymer (supramolecular polymer-4 is taken as an example), cutting the supramolecular polymer into two sections by using scissors, closely placing the two sections together, placing the two sections on a glass slide, recording an image of the damaged polymer by using a 100 × -time microscope, observing the self-healing performance of the damaged polymer by using a 100 × -time microscope again after 50 hours, and recording;
taking a section of strip-shaped supramolecular polymer (supramolecular polymer-4 is taken as an example), cutting the supramolecular polymer into two sections by using scissors, closely placing the two sections together, standing for 1 minute, placing the two sections of the polymer on a clamp of a drawing machine, drawing at the speed of 100mm/min, and observing the tensile property of the two sections of the polymer.
FIG. 4, wherein A is the self-healing microscopic image (1 min) of supramolecular polymer-4 and B is the initial and post-self-healing tensile curve of supramolecular polymer-4;
(2) taking a section of the supramolecular polymer (supramolecular polymer-5 is taken as an example) in a thick strip shape, cutting the supramolecular polymer into two sections by using scissors, putting the two sections into water and closely putting the two sections together, and observing the self-healing performance of the supramolecular polymer, wherein the self-healing performance is shown in detail in fig. 5 (wherein, A is a cutting graph of the supramolecular polymer, and B is an underwater self-healing performance representation graph of the supramolecular polymer).
The above experiments show that the supermolecule polymer-4 has excellent air and underwater self-healing (combination) performance.
2. Tensile Property test
A piece of the supramolecular polymer (taking supramolecular polymer-6 as an example) in a strip shape is taken, and the two pieces of the polymer are held by hands, so that the initial length of the polymer is 1 cm. Slowly and stably stretching the polymer, observing the stretching performance, slowly and stably releasing the polymer after stretching to more than 50cm, and observing the resilience performance;
taking a section of strip-shaped supramolecular polymer (taking supramolecular polymer-6 as an example), placing two sections of the polymer on a tension machine clamp, stretching at the speed of 100mm/min, and observing the stretching performance of the polymer;
taking a section of strip-shaped supramolecular polymer (taking supramolecular polymer-6 as an example), placing two sections of the polymer on a tension machine clamp, circularly stretching at the speed of 100mm/min, and observing the resilience performance of the polymer.
FIG. 6, where A is the initial diagram of supramolecular polymer-6, B is the drawing diagram of supramolecular polymer-6, C is the drawing diagram of the release of supramolecular polymer-6 after drawing, D is the drawing performance curve of supramolecular polymer-6, and E is the rebound performance curve of supramolecular polymer-6.
It is known from A that the initial length of the supramolecular polymer-6 is 1cm, and from B that the supramolecular polymer-6 is uniformly stretched to more than 50cm, and from C that the supramolecular polymer-6 after being released is 5 times of the initial length, and from D that the stretching ratio of the supramolecular polymer-6 can reach more than 15000%, and from E that the supramolecular polymer-6 can be repeatedly cycled at 200% stretching ratio, proving its excellent stretching and rebound elasticity.
3. Thermal responsiveness test
The supramolecular polymer of the present invention, which initially forms the elastomer, is melted under the heat of a 70 ℃ oil bath, then the heating is stopped and the cooling to room temperature is stopped and the polymer is again transformed from the molten state to the elastomeric state.
Therefore, the supramolecular polymer has excellent thermal responsiveness: i.e. solid-liquid conversion can be realized under thermal stimulation.
Claims (7)
1. A supramolecular polymer, characterized in that it is prepared by a preparation method essentially comprising the following steps:
under the condition of no solvent, the lipoic acid or/and the derivatives thereof, the cross-linking agent and the iron source are subjected to hot melting and mixing to obtain a target object;
wherein the molar ratio of the lipoic acid or/and the derivatives thereof, the cross-linking agent and the iron source is 2 (0.1-1.5) to 0.01-1;
the lipoic acid or/and derivatives thereof is selected from: one or a mixture of more than two of the compounds shown in the formula I;
the crosslinking agent is a hydrocarbon compound containing carbon-carbon unsaturated bonds, and the iron source consists of iron salt and an organic solvent capable of dissolving the iron salt;
in the formula I, R1Is hydrogen or C1～C4Straight or branched alkyl, R2Is hydrogen or carboxyl, and n is an integer of 1 to 5.
2. The supramolecular polymer in claim 1, wherein lipoic acid and/or derivatives thereof is a compound of formula I, wherein n is an integer from 1 to 3.
3. The supramolecular polymer as claimed in claim 1 or 2, wherein the cross-linking agent used is: substituted benzenes; the substituent of the substituted benzene is vinyl or C1～C3An alkyl-substituted vinyl group.
4. The supramolecular polymer as claimed in claim 3, wherein said cross-linking agent is: styrene, divinylbenzene or 1, 3-bis (1-methylvinyl) benzene.
5. The supramolecular polymer as claimed in claim 1 or 2, wherein the iron salt used is: iron sulfate, iron chloride, iron nitrate or/and iron stearate.
6. The supramolecular polymer as claimed in claim 1 or 2, wherein the organic solvent used is acetone, ethanol or methanol.
7. A process for the preparation of the supramolecular polymer as claimed in claim 1 or 2, comprising the main steps of: under the condition of no solvent, the lipoic acid or/and the derivatives thereof are placed in a reaction vessel with a stirring device, stirred and heated, after the lipoic acid or/and the derivatives thereof are melted, the cross-linking agent is added into the reaction vessel according to the molar ratio of claim 1 or 2, after the completion, the stirring is continued for 5 to 8 minutes, then the iron source is added into the reaction vessel according to the molar ratio of claim 1 or 2, after the completion, the stirring is continued for 3 to 5 minutes, the heating is stopped, and after the cooling, the target compound is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810232611.7A CN108484923B (en) | 2018-03-20 | 2018-03-20 | Supermolecular polymer based on thioctic acid compound and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810232611.7A CN108484923B (en) | 2018-03-20 | 2018-03-20 | Supermolecular polymer based on thioctic acid compound and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108484923A CN108484923A (en) | 2018-09-04 |
| CN108484923B true CN108484923B (en) | 2020-07-31 |
Family
ID=63318643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810232611.7A Active CN108484923B (en) | 2018-03-20 | 2018-03-20 | Supermolecular polymer based on thioctic acid compound and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484923B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109337043B (en) * | 2018-10-12 | 2021-03-26 | 泉州三欣新材料科技有限公司 | Solvent-free self-repairing polyurethane and preparation method thereof |
| CN109320723B (en) * | 2018-10-12 | 2021-05-04 | 佛山市十而立新材料有限公司 | Self-repairing organic silicon resin and preparation method thereof |
| CN111040119B (en) * | 2018-10-12 | 2021-12-24 | 三门大洋橡塑有限公司 | Self-repairing type organic silicon modified polyurethane and preparation method thereof |
| CN109233571B (en) * | 2018-10-12 | 2021-01-15 | 南宁本吉生物科技有限公司 | Solvent-free self-repairing epoxy resin and preparation method thereof |
| CN109401336B (en) * | 2018-10-25 | 2021-02-12 | 华东理工大学 | Preparation method of recyclable supramolecular polymer film with humidity response |
| CN109897200A (en) * | 2019-02-26 | 2019-06-18 | 哈尔滨工业大学 | The method of preparation method and the preparation of the utilization gel without interface walking gel robot of self-healing gel |
| CN109870174A (en) * | 2019-03-08 | 2019-06-11 | 华南协同创新研究院 | A kind of flexible electrode and preparation method thereof |
| CN112552725B (en) * | 2020-12-11 | 2022-03-29 | 中国科学院海洋研究所 | Underwater self-repairing organic silicon antifouling coating and preparation method thereof |
| CN113054193B (en) * | 2021-03-12 | 2022-05-24 | 广东工业大学 | Silicon-based negative electrode self-repairing polymer binder and preparation method and application thereof |
| CN113061263B (en) * | 2021-04-06 | 2021-12-17 | 华东理工大学 | Preparation method of photocrosslinking dynamic reversible supramolecular polymer adhesive based on lipoic acid micromolecular compound |
| CN113336957B (en) * | 2021-05-31 | 2023-05-23 | 深圳先进电子材料国际创新研究院 | Polymer material and preparation method and application thereof |
| CN113336960B (en) * | 2021-06-18 | 2022-12-06 | 华东理工大学 | Preparation method of supermolecular polymer with super-strong adhesive property in water |
| CN113214482B (en) * | 2021-06-25 | 2022-04-05 | 华东理工大学 | Preparation method of lipoic acid compound polymer |
| CN113621342B (en) * | 2021-08-27 | 2022-08-26 | 四川大学 | Solvent-free binder and preparation method and application thereof |
| CN114656616A (en) * | 2022-03-31 | 2022-06-24 | 深圳先进技术研究院 | Intrinsic self-repairing heat-conducting high polymer based on lipoic acid or/and lipoic acid derivatives, and preparation method and application thereof |
| CN115417998B (en) * | 2022-08-18 | 2023-05-05 | 广东工业大学 | Biodegradable self-repairing rubber elastomer and preparation method and application thereof |
| CN116444795A (en) * | 2023-03-15 | 2023-07-18 | 广东云曌医疗科技有限公司 | Self-healing elastomer and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156449A (en) * | 2006-12-22 | 2008-07-10 | Sumitomo Rubber Ind Ltd | Crosslinking agent, rubber composition comprising the same and tire manufactured using the rubber composition |
| CN105524272A (en) * | 2014-10-24 | 2016-04-27 | 江苏师范大学 | Preparation method and use of thioctic acid-modified polyethylene glycol-polyaminoacid block copolymer |
| WO2016066864A1 (en) * | 2014-10-30 | 2016-05-06 | Innovaciones Fisicas Y Quimicas Sostenibles, S.L. | Nanoparticles for the controlled release of active ingredients |
| CN106905478A (en) * | 2017-04-19 | 2017-06-30 | 贵州大学 | A kind of alpha lipoic acid molecularly imprinted polymer and preparation method thereof |
-
2018
- 2018-03-20 CN CN201810232611.7A patent/CN108484923B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156449A (en) * | 2006-12-22 | 2008-07-10 | Sumitomo Rubber Ind Ltd | Crosslinking agent, rubber composition comprising the same and tire manufactured using the rubber composition |
| CN105524272A (en) * | 2014-10-24 | 2016-04-27 | 江苏师范大学 | Preparation method and use of thioctic acid-modified polyethylene glycol-polyaminoacid block copolymer |
| WO2016066864A1 (en) * | 2014-10-30 | 2016-05-06 | Innovaciones Fisicas Y Quimicas Sostenibles, S.L. | Nanoparticles for the controlled release of active ingredients |
| CN106905478A (en) * | 2017-04-19 | 2017-06-30 | 贵州大学 | A kind of alpha lipoic acid molecularly imprinted polymer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Multi-responsive core-crosslinked poly (thiolether ester) micelles for》;Yanfang Hu et al;《polymer》;Elsevier;20171231;第110卷(第1期);第235-241页 * |
| 《抗氧化温敏型硫辛酸分子印迹聚合物的研究动态》;朱秋劲等;《食品安全质量检测学报》;20131231;第4卷(第6期);第1785-1788页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108484923A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108484923B (en) | Supermolecular polymer based on thioctic acid compound and preparation method thereof | |
| CN106633111B (en) | A kind of preparation method of high strength poly vinyl alcohol base double-network hydrogel | |
| CN110229374A (en) | A kind of preparation method and application of high intensity orientating type polyvinyl alcohol hydrogel | |
| CN113061263B (en) | Preparation method of photocrosslinking dynamic reversible supramolecular polymer adhesive based on lipoic acid micromolecular compound | |
| CN103102636A (en) | Shape memory material taken thermoplastic elastomer as matrix | |
| CN109503768B (en) | Preparation method of high-toughness adhesive weather-resistant polyvinyl alcohol-based double-network hydrogel | |
| CN106910854A (en) | Lithium ion battery separator polyethylene composition, lithium ion battery separator and preparation method thereof and lithium ion battery | |
| CN113871705B (en) | Self-repairing polyionic liquid-based electrolyte and preparation and application thereof | |
| CN114773756B (en) | Thermo-mechanical stable supermolecular elastomer material and preparation method thereof | |
| CN105949508A (en) | Heat stabilizer for PVC (polyvinyl chloride) and preparation method and application thereof | |
| CN114507409A (en) | Antibacterial agent, antibacterial PSU composite material and preparation method thereof | |
| Chernikova et al. | Controlled radical polymerization of acrylonitrile in the presence of trithiocarbonates as reversible addition-fragmentation chain transfer agents | |
| WO2010041876A3 (en) | Method of preparing organic solvent dispersion solution for conductive polymer using ionic polymer liquid and conductive polymer prepared thereby | |
| CN111944170A (en) | Preparation method of self-healing hydrogel | |
| CN114989332B (en) | Ionic elastomer, preparation method and application | |
| CN113831638B (en) | Anti-aging BOPP film and preparation method and application thereof | |
| CN111378158A (en) | Force-induced responsive polymer based on reversible free radical type force sensitive groups | |
| CN103044697B (en) | Method for preparing microphase structural latex film | |
| CN115141326A (en) | Modified wax powder and preparation method and application thereof | |
| CN104672386A (en) | Organic composite water-retaining agent and preparation method thereof | |
| Wang et al. | Multi-shape-changing interpenetrating networks with shape memory effect and adaptive plastic deformations | |
| CN105754040A (en) | High-liquidity heat-resistant PVC (polyvinyl chloride) resin and preparation method thereof | |
| CN109666163B (en) | Hybrid crosslinked dynamic polymer and application thereof | |
| CN101768316A (en) | Preparation method of polyaniline/P (MMA-BA-HEA) conductive composite material | |
| Liang et al. | “Cloth‐to‐Clothes‐Like” Fabrication of Soft Actuators |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |