CN105837778A - A preparing method of a shape-memory polymer cured through radiation - Google Patents
A preparing method of a shape-memory polymer cured through radiation Download PDFInfo
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- CN105837778A CN105837778A CN201610220623.9A CN201610220623A CN105837778A CN 105837778 A CN105837778 A CN 105837778A CN 201610220623 A CN201610220623 A CN 201610220623A CN 105837778 A CN105837778 A CN 105837778A
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- memory polymer
- shape memory
- diisocyanate
- caprolactone
- shape
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G2280/00—Compositions for creating shape memory
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a preparing method of a shape-memory polymer cured through radiation. The method includes steps of initiating epsilon-caprolactone ring opening polymerization through a polyol to obtain polycaprolactone polyol, reacting the polycaprolactone polyol, diisocyanate and hydroxyalkyl acrylate under actions of organic bismuth to obtain a polyurethaneacrylate prepolymer end groups of which are double bonds, adding a photoinitiator, pouring into a mold, and performing ultraviolet radiation curing to obtain the shape-memory polymer. Beneficial effects of the method are that crystalline polycaprolactone segments are introduced into a polyurethaneacrylate main chain, the melting point of the polymer is controlled through an external temperature so as to make the structural form changed, shape memory is liable to achieve, a transition temperature is close to the human body temperature, the polyurethaneacrylate is prepared through an ultraviolet radiation curing, the method is simple in process, time-saving and labor-saving, the shape-memory polymer is biodegradable, a degradation product is nontoxic, and the shape-memory polymer can be used for microtraumatic operations and medicine releasing.
Description
Technical field
The invention belongs to biomedical materials field, relate to the system of a kind of radiation curing shape memory polymer
Preparation Method.
Background technology
Shape memory polymer material has lightweight, Large strain/recovery of shape ability.So-called shape memory,
Refer to have the goods of original shape (playing primary state) after (deformation states) is fixed in deformation, by light, heat, electricity,
The process of the outside stimulus means such as acid-base value (pH value), phase in version reaction can recover again the characteristic of its original shape,
Thus complete the cyclic process of " remembered primary state → fixed deformation state → recovered primary state " shape memory.Shape
Shape memory material has self-regeneration, temperature, pH sensing effect.
Temperature is a critically important factor in human physiological environment, thermotropic shape memory polymer, with
Temperature reaches stimulating responsive, typically has two phase structure, can remember original shape fixing phase and with
Temperature can reversible solidification and softening can anti-phase.Can anti-phase be physical crosslinking structure, such as glass transition temperature
Relatively low glassy state, its effect is to make goods be deformed and fix this shape.Fixing phase can be physical crosslinking
Structure, crystalline state as higher in fusing point, or be mutually wound around between the macromolecular chain of high molecular, it is possible to for changing
Learning cross-linked structure, its effect is the memory for moulded products original-shape and reply.For polycaprolactone type
Thermotropic shape memory polymer, it depends on the crystal property of system, meets biodegradable, so
Polycaprolactone is frequently used to research.Its preparation method is studied by the most many scholars, the most molten
Agent casting, phase separation method, supercritical CO 2 foaming etc..But the preparation method complex process of these foams,
Production efficiency is low, relatively costly, wayward.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, and the present invention provides a kind of radiation curing shape
The preparation method of shape Memorability polymer.
The present invention solves the technical scheme that its technical problem used: a kind of radiation curing shape memory
The preparation method of property polymer, comprises the following steps:
A, synthesize crystallizable polycaprolactone polyol: initiator polyhydric alcohol causes 6-caprolactone ring-opening polymerisation,
Obtain polycaprolactone polyol, precipitation, it is dried；
B, prepare shape memory polymer: polycaprolactone polyol, diisocyanate and hydroxyalkyl acrylate
Under organo-bismuth effect, reaction obtains the polyurethane acrylate prepolymer that end group is double bond, adds light trigger,
Pour in mould, cured with ultraviolet radiation, obtain shape memory polymer.
Further, in step a, the molecular weight of polycaprolactone polyol is 2000～4000.
Further, the detailed process synthesizing crystallizable polycaprolactone polyol in step a is: reaction is held
Device is sequentially added into initiator polyhydric alcohol, 6-caprolactone and catalyst, is passed through nitrogen, be warming up to 130～
150 DEG C, react 12～24h, product is poured into excess cold diethyl ether in centrifugation, 50 DEG C of dry 24h,
Standby.
Further, in step a, polyhydric alcohol is ethylene glycol, BDO, glycerol, tetramethylolmethane or poly-
Ethylene glycol 400, catalyst is stannous octoate, dibutyl tin laurate, triethylenediamine, two acetic acid two
One or more in methyl stannum, dibutyl tin maleate or zinc octoate, 6-caprolactone needs hydrogenated calcium
It is dried decompression distillation after 24h.
Further, in step a, ethylene glycol is 1:31.3～63.5 with the mass ratio of 6-caprolactone, Isosorbide-5-Nitrae-fourth
Glycol is 1:21.2～43.4 with the mass ratio of 6-caprolactone, and glycerol is 1 with the mass ratio of 6-caprolactone:
20.7～42.5, the mass ratio of tetramethylolmethane and 6-caprolactone is 1:13.7～28.4, PEG400 with
The mass ratio of 6-caprolactone is 1:4～9, and catalyst accounts for polyhydric alcohol and the 3 of 6-caprolactone gross mass～5 ‰.
Further, the detailed process preparing shape memory polymer in step b is: by polycaprolactone polyol
Alcohol, the toluene solution of diisocyanate and organo-bismuth are sequentially added in reaction vessel, under nitrogen protection, 70～
80 DEG C of reaction 3h, are cooled to 45 DEG C by reaction system, add hydroxyalkyl acrylate and continue 70 DEG C of reactions, infrared
In detection reaction system, NCO peak disappears i.e. to react and terminates, and obtains polyurethane acrylate prepolymer；By polyurethane
Acrylic ester prepolymer adds light trigger mix homogeneously, pours dumbbell shape mould medium ultraviolet radiation curing into, then
Put into baking oven and dry 3～4h；Taking-up is immersed in 12h in acetone, moves to 50 DEG C of vacuum drying ovens and is dried to constant weight,
Obtain shape memory polymer.
Further, in step b diisocyanate be tetramethylene isocyanates, hexa-methylene isocyanates,
Isophorone diisocyanate diisocyanate, methyl diphenylene diisocyanate or 4,4 ＇-dicyclohexyl methyl hydride
Diisocyanate, hydroxyalkyl acrylate is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methacrylate second
Ester, Hydroxypropyl methacrylate or hy-droxybutyl, light trigger is 1-hydroxycyclohexyl phenyl ketone.
Further, in step b polycaprolactone polyol, diisocyanate and hydroxyalkyl acrylate mole
Ratio is 1:2:2, and organo-bismuth accounts for polycaprolactone polyol and the 0.1 of diisocyanate gross mass～0.2%, light
Initiator accounts for the 0.5～1% of polyurethane acrylate prepolymer quality, cured with ultraviolet radiation time 5～20min.
The invention has the beneficial effects as follows: in urethane acrylate main chain, introduce crystallinity polycaprolactone segment,
Can control its fusing point by additional temperature makes its configuration change, it is easy to accomplish shape memory,
The temperature changed is near human body temperature；The method using cured with ultraviolet radiation obtains urethane acrylate,
Technique is simple, laborsaving during joint；Shape memory polymer is biodegradable, and catabolite is nontoxic, permissible
It is applied to Minimally Invasive Surgery and drug release.
Accompanying drawing explanation
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is polycaprolactone polyol structural characterization figure prepared by various embodiments of the present invention, and figure (a) is right
Answer embodiment 1, the corresponding embodiment 2 and 3 of figure (b)；
Fig. 2 is the configuration figure of shape memory polymer prepared by various embodiments of the present invention, wherein,
A, b and c corresponding embodiment 1,2 and 3 respectively.
Detailed description of the invention
Presently in connection with specific embodiment, the invention will be further described, and following example are intended to the present invention is described
Rather than limitation of the invention further.
Embodiment 1
(1) synthesis polycaprolactone polyol: be sequentially added into 1,4-butanediol in the round-bottomed flask of 100mL
1.00g, 6-caprolactone 21.22g, octoate catalyst stannous 0.0667g, be passed through N2It is warming up to 130 DEG C, instead
Answer 24h, stopped reaction.The product obtained is poured into centrifugation in the cold diethyl ether of excess, is placed on 50 DEG C very
Empty drying baker is dried 24h, moves into drying tower standby.
(2) preparation of shape memory polymer: by 0.01mol polycaprolactone polyol, 0.02mol six
Methylene diisocyanate, 4mL toluene solution and 0.0700g catalyst organo-bismuth are sequentially added the circle of 100mL
End flask, 70～80 DEG C of reaction 3h, are cooled to 45 DEG C by reaction system under nitrogen protection, add 0.02mol
Hydroxyethyl methylacrylate continues 70 DEG C of reactions, and in infrared detection reaction system, NCO peak disappears i.e. to react and terminates,
Vinyl is connected on the two ends of prepolymer；The polyurethane acrylate prepolymer obtained is added 0.10g light-initiated
Agent mix homogeneously, pours dumbbell shape mould medium ultraviolet radiation curing 20min into, places into baking oven 3～4h；Take out
It is immersed in 12h in acetone, moves to 50 DEG C of vacuum drying ovens and be dried to constant weight, shape memory polymerization will be obtained
Thing.
Embodiment 2
(1) synthesis polycaprolactone polyol: be sequentially added in the round-bottomed flask of 100mL PEG400 5.00g,
6-caprolactone 20.00g, octoate catalyst stannous 0.0750g, be passed through N2It is warming up to 130 DEG C, reacts 24h,
Stopped reaction.The product obtained is poured into centrifugation in the cold diethyl ether of excess, is placed on 50 DEG C of vacuum drying ovens
In be dried 24h, move into drying tower standby.
(2) preparation of shape memory polymer: by 0.005mol polycaprolactone polyol, 0.01mol six Asia
Methyl diisocyanate, 4mL toluene solution and 0.0590g catalyst organo-bismuth are sequentially added the round bottom of 100mL and burn
Bottle, 70～80 DEG C of reaction 3h, are cooled to 45 DEG C by reaction system under nitrogen protection, add 0.01mol methyl
2-(Acryloyloxy)ethanol continues 70 DEG C of reactions, and in infrared detection reaction system, NCO peak disappears i.e. to react and terminates, ethylene
Base is connected on the two ends of prepolymer；The polyurethane acrylate prepolymer obtained is added the mixing of 0.06g light trigger
Uniformly, pour dumbbell shape mould medium ultraviolet radiation curing 20min into, place into baking oven 3～4h；Taking-up is immersed in
12h in acetone, moves to 50 DEG C of vacuum drying ovens and is dried to constant weight, will obtain shape memory polymer.
Embodiment 3
(1) synthesis polycaprolactone polyol: be sequentially added in the round-bottomed flask of 100mL PEG400 4.00g,
6-caprolactone 26.00g, octoate catalyst stannous 0.0900g, be passed through N2It is warming up to 130 DEG C, reacts 24h,
Stopped reaction.The product obtained is poured into centrifugation in the cold diethyl ether of excess, is placed on 50 DEG C of vacuum drying ovens
In be dried 24h, move into drying tower standby.
(2) preparation of shape memory polymer: by different to 0.005mol polycaprolactone polyol, 0.01mol
Isophorone diisocyanate, 4mL toluene solution and 0.0607g catalyst organo-bismuth are sequentially added the circle of 100mL
End flask, 70～80 DEG C of reaction 3h, are cooled to 45 DEG C by reaction system under nitrogen protection, add 0.01mol
Hydroxyethyl methylacrylate continues 70 DEG C of reactions, and in infrared detection reaction system, NCO peak disappears i.e. to react and terminates,
Vinyl is connected on the two ends of prepolymer；The polyurethane acrylate prepolymer obtained is added 0.06g light-initiated
Agent mix homogeneously, pours dumbbell shape mould medium ultraviolet radiation curing 20min into, places into baking oven 3～4h；Take out
It is immersed in 12h in acetone, moves to 50 DEG C of vacuum drying ovens and be dried to constant weight, shape memory polymerization will be obtained
Thing.
1, the structural characterization of polycaprolactone polyol
Nuclear magnetic resonance analyser (1H-NMR) (AVANCE III-400, Bruker company of Germany) is used for testing gathers in oneself
The structure of ester polyol, solvent deuterochloroform.
Fig. 1 is the structural characterization of the polycaprolactone polyol that embodiment 1～3 prepares, and wherein, figure (a) is right
Answer embodiment 1, the corresponding embodiment 2 and 3 of figure (b).Structure correspondence NMR of polycaprolactone polyol in figure
Proton uptake peak, can be with the structure of qualitative polycaprolactone, it is also possible to by the molecule of the quantitative polycaprolactone of NMR
Amount.
2, the composition structure of shape memory polymer and the performance parameter of form see table:
3, shape memory polymer morphology characterizes
Use DSC800 differential scanning calorimeter that the Tg of shape memory polymer is tested.Take 5～10mg PU
Sample is placed in solid crucible, N2Atmosphere, removes after thermal history (with the speed of 20K/min from-75 DEG C of intensifications
To 100 DEG C, then 20K/min is cooled to-75 DEG C from 100 DEG C, it is therefore an objective to remove polymer in preparation process
Thermal environment impact), be warming up to 100 DEG C with the speed of 10K/min from-75 DEG C.
Fig. 2 is the Morphological Characterization of the shape polymer that embodiment 1～3 prepares, and wherein, a, b, c are the most right
Answer embodiment 1,2,3.Figure can be seen that the fusing point of shape polymer and the glass transition temperature of low temperature.
The fixing mutually for the glass transition temperature of material with temperature energy reversible solidification, softening of original shape can be remembered
Can the crystal region of polycaprolactone of anti-phase.When material be shaped as the deformation of 100% after, additional temperature
After exceeding the fusing point of material, the thawing of its crystalline segment is moved, and can recover shape, has thermotropic shape
Shape Memorability.
The thermotropic shape memory polymer of the present invention, its operation principle is to it at low temperature (0～15 DEG C)
Stretch so that it is deformation 100%, and be fixed 30～60min, being fixed of the shape of material.Will
Material is placed in water or the air of 37 DEG C, and the shape of material can quickly return to former state in 10～60s.
Change the shape of material by changing temperature, it depends on crystallizable polycaprolactone segment in system.Material
Material reinstatement is after temperature is higher than fusing point, the thawing of crystal region, the movement of segment.
With the above-mentioned desirable embodiment according to the present invention for enlightenment, by above-mentioned description, related work
Personnel can carry out various change and amendment completely in the range of without departing from this invention technological thought.
The content that the technical scope of this invention is not limited in description, it is necessary to according to right
Determine its technical scope.
Claims (8)
1. a preparation method for radiation curing shape memory polymer, is characterized in that: comprise the following steps:
A, synthesize crystallizable polycaprolactone polyol: initiator polyhydric alcohol causes 6-caprolactone ring-opening polymerisation,
Obtain polycaprolactone polyol, precipitation, it is dried；
B, prepare shape memory polymer: polycaprolactone polyol, diisocyanate and hydroxyalkyl acrylate
Under organo-bismuth effect, reaction obtains the polyurethane acrylate prepolymer that end group is double bond, adds light trigger,
Pour in mould, cured with ultraviolet radiation, obtain shape memory polymer.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 1, its
Feature is: in described step a, the molecular weight of polycaprolactone polyol is 2000～4000.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 1, its
Feature is: the detailed process synthesizing crystallizable polycaprolactone polyol in described step a is: reaction is held
Device is sequentially added into initiator polyhydric alcohol, 6-caprolactone and catalyst, is passed through nitrogen, be warming up to 130～
150 DEG C, react 12～24h, product is poured into excess cold diethyl ether in centrifugation, 50 DEG C of dry 24h,
Standby.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 3, its
Feature is: in described step a, polyhydric alcohol is ethylene glycol, 1,4-butanediol, glycerol, tetramethylolmethane or poly-
Ethylene glycol 400, catalyst is stannous octoate, dibutyl tin laurate, triethylenediamine, two acetic acid two
One or more in methyl stannum, dibutyl tin maleate or zinc octoate, 6-caprolactone needs hydrogenated calcium
It is dried decompression distillation after 24h.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 3, its
Feature is: in described step a, ethylene glycol is 1:31.3～63.5 with the mass ratio of 6-caprolactone, Isosorbide-5-Nitrae-fourth
Glycol is 1:21.2～43.4 with the mass ratio of 6-caprolactone, and glycerol is 1 with the mass ratio of 6-caprolactone:
20.7～42.5, the mass ratio of tetramethylolmethane and 6-caprolactone is 1:13.7～28.4, PEG400 with
The mass ratio of 6-caprolactone is 1:4～9, and catalyst accounts for polyhydric alcohol and the 3 of 6-caprolactone gross mass～5 ‰.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 1, its
Feature is: the detailed process preparing shape memory polymer in described step b is: by polycaprolactone polyol
Alcohol, the toluene solution of diisocyanate and organo-bismuth are sequentially added in reaction vessel, under nitrogen protection, 70～
80 DEG C of reaction 3h, are cooled to 45 DEG C by reaction system, add hydroxyalkyl acrylate and continue 70 DEG C of reactions, infrared
In detection reaction system, NCO peak disappears i.e. to react and terminates, and obtains polyurethane acrylate prepolymer；By polyurethane
Acrylic ester prepolymer adds light trigger mix homogeneously, pours dumbbell shape mould medium ultraviolet radiation curing into, then
Put into baking oven and dry 3～4h；Taking-up is immersed in 12h in acetone, moves to 50 DEG C of vacuum drying ovens and is dried to constant weight,
Obtain shape memory polymer.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 1, its
Feature is: in described step b diisocyanate be tetramethylene isocyanates, hexa-methylene isocyanates,
Isophorone diisocyanate diisocyanate, methyl diphenylene diisocyanate or 4,4 ＇-dicyclohexyl methyl hydride
Diisocyanate, hydroxyalkyl acrylate is 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methacrylate second
Ester, Hydroxypropyl methacrylate or hy-droxybutyl, light trigger is 1-hydroxycyclohexyl phenyl ketone.
The preparation method of a kind of radiation curing shape memory polymer the most according to claim 1, its
Feature is: in described step b polycaprolactone polyol, diisocyanate and hydroxyalkyl acrylate mole
Ratio is 1:2:2, and organo-bismuth accounts for polycaprolactone polyol and the 0.1 of diisocyanate gross mass～0.2%, light
Initiator accounts for the 0.5～1% of polyurethane acrylate prepolymer quality, cured with ultraviolet radiation time 5～20min.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928671A (en) * | 2017-03-01 | 2017-07-07 | 广州新诚生物科技有限公司 | A kind of high-strength shape memory 3D printing biological plastics and preparation method |
| CN108129645A (en) * | 2017-12-06 | 2018-06-08 | 广东博兴新材料科技有限公司 | A kind of radiation-curable polycaprolactone diols and its preparation method and application |
| WO2019006694A1 (en) * | 2017-07-05 | 2019-01-10 | 深圳大学 | Method for preparing shape memory polyurethane |
| CN110483699A (en) * | 2019-09-27 | 2019-11-22 | 常州大学 | A kind of multiple response shape memory polyurethane acrylate copolymer and preparation method thereof |
| CN111269373A (en) * | 2020-02-12 | 2020-06-12 | 浙江大学衢州研究院 | Preparation method of remodelable shape memory elastomer based on eutectic |
| CN111690111A (en) * | 2020-07-30 | 2020-09-22 | 中国科学院兰州化学物理研究所 | Comb type polymer and preparation method and application thereof |
| CN113956432A (en) * | 2021-11-16 | 2022-01-21 | 广东十辰十新材料有限公司 | Degradable UV resin and degradable UV pressure-sensitive adhesive based on same |
| CN114292400A (en) * | 2021-12-03 | 2022-04-08 | 中国科学院深圳先进技术研究院 | Bidirectional actuating shape memory polymer and preparation method thereof |
| CN114806063A (en) * | 2022-05-09 | 2022-07-29 | 江苏大学 | Composite material with electric conduction, heat conduction and shape memory performance and preparation method thereof |
| CN115627071A (en) * | 2022-10-24 | 2023-01-20 | 中国科学院兰州化学物理研究所 | 4D printing photo-curing cyanate ester ink, preparation method thereof and shape memory cyanate ester material |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928671A (en) * | 2017-03-01 | 2017-07-07 | 广州新诚生物科技有限公司 | A kind of high-strength shape memory 3D printing biological plastics and preparation method |
| WO2019006694A1 (en) * | 2017-07-05 | 2019-01-10 | 深圳大学 | Method for preparing shape memory polyurethane |
| CN108129645A (en) * | 2017-12-06 | 2018-06-08 | 广东博兴新材料科技有限公司 | A kind of radiation-curable polycaprolactone diols and its preparation method and application |
| CN110483699A (en) * | 2019-09-27 | 2019-11-22 | 常州大学 | A kind of multiple response shape memory polyurethane acrylate copolymer and preparation method thereof |
| CN111269373A (en) * | 2020-02-12 | 2020-06-12 | 浙江大学衢州研究院 | Preparation method of remodelable shape memory elastomer based on eutectic |
| CN111690111A (en) * | 2020-07-30 | 2020-09-22 | 中国科学院兰州化学物理研究所 | Comb type polymer and preparation method and application thereof |
| CN113956432A (en) * | 2021-11-16 | 2022-01-21 | 广东十辰十新材料有限公司 | Degradable UV resin and degradable UV pressure-sensitive adhesive based on same |
| CN114292400A (en) * | 2021-12-03 | 2022-04-08 | 中国科学院深圳先进技术研究院 | Bidirectional actuating shape memory polymer and preparation method thereof |
| CN114292400B (en) * | 2021-12-03 | 2023-10-24 | 中国科学院深圳先进技术研究院 | Two-way actuation shape memory polymer and preparation method thereof |
| CN114806063A (en) * | 2022-05-09 | 2022-07-29 | 江苏大学 | Composite material with electric conduction, heat conduction and shape memory performance and preparation method thereof |
| CN114806063B (en) * | 2022-05-09 | 2024-01-05 | 江苏大学 | Composite material with electric conduction, heat conduction and shape memory properties and preparation method thereof |
| CN115627071A (en) * | 2022-10-24 | 2023-01-20 | 中国科学院兰州化学物理研究所 | 4D printing photo-curing cyanate ester ink, preparation method thereof and shape memory cyanate ester material |
| CN115627071B (en) * | 2022-10-24 | 2023-11-24 | 中国科学院兰州化学物理研究所 | 4D printing photo-curing cyanate ink, preparation method thereof and shape memory cyanate material |
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