CN113621212A - Liquid crystal polymer composite material doped with carbon nano tube and preparation method thereof - Google Patents

Liquid crystal polymer composite material doped with carbon nano tube and preparation method thereof Download PDF

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CN113621212A
CN113621212A CN202111035421.4A CN202111035421A CN113621212A CN 113621212 A CN113621212 A CN 113621212A CN 202111035421 A CN202111035421 A CN 202111035421A CN 113621212 A CN113621212 A CN 113621212A
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liquid crystal
crystal polymer
composite material
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张东宝
于冉
徐良
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Ningxia Qingyan Polymer New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory

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Abstract

The invention discloses a liquid crystal polymer composite material doped with carbon nanotubes and a preparation method thereof, wherein the liquid crystal polymer composite material doped with the carbon nanotubes comprises the carbon nanotubes, liquid crystal polymers, an SBS elastomer and a solubilizer, wherein the liquid crystal polymers are crustacean-type liquid crystal polymers. The liquid crystal polymer composite material doped with the carbon nano tube prepared by the invention has excellent shape memory performance and better mechanical property, and can meet the requirement of the biomedical field on the shape memory performance of the material.

Description

Liquid crystal polymer composite material doped with carbon nano tube and preparation method thereof
Technical Field
The invention relates to the field of liquid crystal polymers, in particular to a liquid crystal polymer composite material doped with carbon nanotubes and a preparation method thereof.
Background
The mesogen-jacketed liquid crystal polymer is a liquid crystal polymer which is connected with a polymer main chain at the gravity center position (or waist) through a covalent bond or a very short spacer, and can be divided into the following types according to the structure of a central bond bridge thereof: mesogen-jacketed liquid crystal polymers based on vinyl hydroquinone, mesogen-jacketed liquid crystal polymers based on vinyl p-phenylenediamine, mesogen-jacketed liquid crystal polymers based on vinyl p-aminophenol and mesogen-jacketed liquid crystal polymers based on vinyl terephthalic acid, wherein the mesogen-jacketed liquid crystal polymers based on vinyl terephthalic acid have attracted attention from researchers because of their relatively short synthesis cycles.
With the development of the biomedical field, the requirements on the biological material are higher and higher, and in some environments, the biological material is required to have excellent shape memory performance, namely, the biological material can recover to the original shape under the external stimulation (such as heating, electrification, magnetic field, illumination, PH change and the like), while the shape memory performance of the existing liquid crystal polymer material cannot meet the requirements of the biomedical field.
Accordingly, there is still a need for advancement and development of the prior art.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a liquid crystal polymer composite doped with carbon nanotubes and a method for preparing the same, which aims to improve the shape memory property of the liquid crystal polymer material.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a liquid crystal polymer composite material doped with carbon nanotubes comprises the carbon nanotubes, liquid crystal polymers, an SBS elastomer and a solubilizer, wherein the liquid crystal polymers are mesogen-jacketed liquid crystal polymers.
The liquid crystal polymer composite material doped with the carbon nano tube is characterized in that the liquid crystal polymer is 25-58% by weight, the SBS elastomer is 40-70% by weight, the carbon nano tube is 1-2% by weight, and the solubilizer is 1-3% by weight.
The liquid crystal polymer composite material doped with the carbon nano tube is characterized in that the liquid crystal polymer is 35-45% by weight, the SBS elastomer is 50-60% by weight, the carbon nano tube is 2% by weight, and the solubilizer is 3% by weight.
The liquid crystal polymer composite material doped with the carbon nano tube is characterized in that the liquid crystal polymer is 40% in parts by weight, the SBS elastomer is 55% in parts by weight, the carbon nano tube is 2% in parts by weight, and the solubilizer is 3% in parts by weight.
The liquid crystal polymer composite material doped with the carbon nano tube is characterized in that the crustacean-type liquid crystal polymer is vinyl terephthalic acid crustacean-type liquid crystal polymer.
The carbon nanotube-doped liquid crystal polymer composite material is characterized in that the vinyl terephthalic acid crustacean-type liquid crystal polymer is one of polyvinyl terephthalic acid di (p-butoxyphenyl) ester or polyvinyl terephthalic acid dicyclohexyl ester.
The carbon nanotube-doped liquid crystal polymer composite material is characterized in that the solubilizer is a copolymer of maleic anhydride and polypropylene.
In addition, the invention also provides a preparation method of the liquid crystal polymer composite material doped with the carbon nanotubes, which is used for preparing the liquid crystal polymer composite material doped with the carbon nanotubes, wherein the preparation method comprises the following steps:
grinding liquid crystal macromolecules into powder, and mixing the powder with an SBS elastomer to obtain a mixture;
dissolving the mixture in an organic solvent, and performing ultrasonic dispersion to obtain a mixed solution A;
adding carbon nano tubes and a solubilizer into the mixed solution A, and performing ultrasonic dispersion to obtain a mixed solution B;
and spreading the mixed solution B on a template, and removing the organic solvent to obtain the carbon nanotube-doped liquid crystal polymer composite material.
The preparation method of the liquid crystal polymer composite material doped with the carbon nano tube is characterized in that the organic solvent is trichloromethane.
The preparation method of the liquid crystal polymer composite material doped with the carbon nano tube comprises the step of preparing a template, wherein the template is a glass vessel.
Has the advantages that: according to the liquid crystal polymer composite material doped with the carbon nano tubes, the SBS elastomer and the carbon nano tubes are doped in the liquid crystal polymer, wherein the SBS elastomer can reduce the storage modulus of the composite material at normal temperature and increase the flexibility of the composite material, so that the shape memory performance of the composite material can be improved, and meanwhile, the added carbon nano tubes can improve the mechanical property of the composite material, so that the prepared composite material can meet the requirements of the biomedical field.
Detailed Description
The present invention provides a liquid crystal polymer composite material doped with carbon nanotubes and a preparation method thereof, and the present invention is further described in detail below in order to make the objects, technical schemes, and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The liquid crystal polymer is a novel material with an anisotropic structure, and has wide development prospects in the chemical fields of nonlinear photoelectric materials, tunable diffraction gratings, heat-insulating materials, high-performance Kevlar fibers and the like. The concept of mesogen-jacketed liquid crystal polymer, which is a liquid crystal polymer with mesogens connected to the main chain of the polymer at the center of gravity (or waist) only by a covalent bond or a short spacer, was proposed in 1987, the mesogen-jacketed liquid crystal polymer shows a certain rigidity due to the strong interaction between the side group and the main chain, which is similar to the main chain type liquid crystal polymer, and these characteristics make the mesogen-jacketed liquid crystal polymer a third type of liquid crystal polymer different from the main chain type and the side chain type.
Based on the technical problems of high energy storage modulus of the mesogen-jacketed liquid crystal polymer at normal temperature, hard and brittle materials and small shape memory recovery stress, the invention can reduce the energy storage modulus of the composite material at normal temperature and increase the flexibility of the composite material by blending the synthesized mesogen-jacketed liquid crystal polymer and SBS (styrene-butadiene-styrene block copolymer) elastomer, thereby improving the shape memory performance of the composite material.
Further, in the invention, the carbon nanotubes are added into the composite material, so that the liquid crystal polymer composite material doped with the carbon nanotubes is prepared, wherein the added carbon nanotubes can further improve the mechanical property of the liquid crystal polymer composite material doped with the carbon nanotubes while maintaining the good shape memory property of the liquid crystal polymer composite material doped with the carbon nanotubes, so that the prepared liquid crystal polymer composite material doped with the carbon nanotubes can meet the use requirements in the field of biomedical science.
In the invention, the prepared liquid crystal polymer composite material doped with the carbon nano tube comprises: 25-58% of liquid crystal polymer, 40-70% of SBS elastomer, 1-2% of carbon nano tube and 1-3% of solubilizer.
It should be noted that, due to poor compatibility between the SBS elastomer and the liquid crystal polymer, if the mass fraction of the SBS elastomer is too low during the preparation process, the shape memory property of the prepared liquid crystal polymer composite material doped with carbon nanotubes is poor, and if the mass fraction of the SBS elastomer is too high, the stability of the prepared liquid crystal polymer composite material doped with carbon nanotubes is low, so that the mass fraction of the SBS elastomer is preferably controlled to 50-60%, and the mass fraction of the liquid crystal polymer is preferably controlled to 35-45%. Preferably, the mass portion of the liquid crystal polymer is 40%, the mass portion of the SBS elastomer is 55%, the mass portion of the carbon nanotube is 2%, and the mass portion of the solubilizer is 3%.
In the present invention, the crustacean-type liquid crystal polymer is a vinyl terephthalic acid crustacean-type liquid crystal polymer, and preferably, the vinyl terephthalic acid crustacean-type liquid crystal polymer is one of polyvinyl terephthalic acid di (p-butoxyphenyl) ester or polyvinyl terephthalic acid dicyclohexyl ester. Among them, poly (p-butoxyphenyl) terephthalate and poly (vinylcyclohexyl terephthalate) are prepared by esterification of vinylterephthalic acid with 4-butoxyphenol and cyclohexanol, respectively, to obtain the corresponding monomer M1 and monomer M2, and thereafter, by radical polymerization of monomer M1 and monomer M2, the corresponding polymers poly (p-butoxyphenyl) terephthalate and poly (vinylcyclohexyl terephthalate), respectively.
Wherein the free radical polymerization reaction of the monomer M1 comprises the following steps: putting a monomer M1 in a vacuum drying oven, drying for 24h under the vacuum state at 50 ℃, adding a monomer M1 and an initiator (azobisisobutyronitrile) into a polymerization tube according to the molar ratio of 200:1 under the protection of nitrogen, wherein the azobisisobutyronitrile is dissolved in tetrahydrofuran, injecting the tetrahydrofuran into the polymerization tube through a needle tube, freezing the polymerization tube for 5-10min under the environment of liquid nitrogen, vacuumizing, and reacting for 8h at 70 ℃ after the temperature is recovered to the room temperature to obtain the polyvinyl bis (p-butoxyphenyl) terephthalate.
Wherein the free radical polymerization reaction of the monomer M2 comprises the following steps: putting a monomer M2 in a vacuum drying oven, drying for 24h at 50 ℃ in a vacuum state, adding a monomer M2 and an initiator (azobisisobutyronitrile) into a polymerization tube according to a molar ratio of 200:1 under the protection of nitrogen, wherein the azobisisobutyronitrile is dissolved in tetrahydrofuran and injected into the polymerization tube through a needle tube, freezing the polymerization tube for 5-10min in a liquid nitrogen environment, vacuumizing, and reacting for 8h at 70 ℃ after the temperature is recovered to room temperature to obtain the polycyclohexyl polythylterephthalate.
In the invention, the shape memory performance of the prepared liquid crystal polymer composite material doped with the carbon nano tube is quantitatively characterized by adopting a dynamic mechanical thermal analyzer, wherein the specific operation steps are as follows:
1) fixing the sample, wherein the effective length of the sample is L, heating to 70 ℃ at a heating rate of 5 ℃/min, stabilizing for 10min, and recording the strain at the moment as epsilon0；
2) Applying an external force, simultaneously cooling to 35 ℃ at a cooling rate of 5 ℃/min, and recording the maximum strain reached in the cooling process as epsilon1；
3) Removing the external force and recording the strain at that time asε2；
4) Heating to 30 deg.C above the glass transition temperature of the material at a heating rate of 5 deg.C/min, maintaining for 30min, recovering shape, and recording the strain at the time as epsilon3；
5) Repeating steps 2) to 4).
Wherein the shape memory fixation rate (R)f) And shape memory recovery ratio (R)r) Calculating according to the formula:
Rf＝(ε2-ε0)/(ε1-ε0)
Rr＝(ε1-ε3)/(ε1-ε0)。
in the invention, the shape memory performance of the prepared liquid crystal polymer composite material doped with the carbon nano tube is evaluated mainly through the shape memory fixation rate and the shape memory recovery rate.
The following is a further explanation of the liquid crystal polymer composite doped with carbon nanotubes according to the present invention by specific examples:
example 1
The mass portion of the polyvinyl terephthalic acid di (p-butoxyphenyl) ester is 35%, the mass portion of the SBS elastomer is 60%, the mass portion of the carbon nano tube is 2%, and the mass portion of the solubilizer is 3%.
Grinding the polyvinyl terephthalic acid di (p-butoxy benzene) ester into powder, mixing the powder with SBS elastomer, dissolving the powder by using trichloromethane to obtain a mixed solution, adding the carbon nano tubes and a solubilizer into the mixed solution, performing ultrasonic dispersion, and uniformly spreading the mixed solution after ultrasonic treatment on a glass dish to obtain the liquid crystal polymer composite film doped with the carbon nano tubes.
Example 2
The mass portion of the polyvinyl terephthalic acid di (p-butoxyphenyl) ester is 40%, the mass portion of the SBS elastomer is 55%, the mass portion of the carbon nano tube is 2%, and the mass portion of the solubilizer is 3%.
Grinding the polyvinyl terephthalic acid di (p-butoxy benzene) ester into powder, mixing the powder with SBS elastomer, dissolving the powder by using trichloromethane to obtain a mixed solution, adding the carbon nano tubes and a solubilizer into the mixed solution, performing ultrasonic dispersion, and uniformly spreading the mixed solution after ultrasonic treatment on a glass dish to obtain the liquid crystal polymer composite film doped with the carbon nano tubes.
Example 3
The mass portion of the polyvinyl terephthalic acid di (p-butoxyphenyl) ester is 45%, the mass portion of the SBS elastomer is 50%, the mass portion of the carbon nano tube is 2%, and the mass portion of the solubilizer is 3%.
Grinding the polyvinyl terephthalic acid di (p-butoxy benzene) ester into powder, mixing the powder with SBS elastomer, dissolving the powder by using trichloromethane to obtain a mixed solution, adding the carbon nano tubes and a solubilizer into the mixed solution, performing ultrasonic dispersion, and uniformly spreading the mixed solution after ultrasonic treatment on a glass dish to obtain the liquid crystal polymer composite film doped with the carbon nano tubes.
Example 4
35% of polyvinyl dicyclohexyl terephthalate, 60% of SBS elastomer, 2% of carbon nano tube and 3% of solubilizer.
Grinding the polyvinyl dicyclohexyl terephthalate into powder, mixing the powder with SBS elastomer, dissolving the powder with trichloromethane to obtain a mixed solution, adding the carbon nano tubes and the solubilizer into the mixed solution, performing ultrasonic dispersion, and uniformly spreading the mixed solution after ultrasonic dispersion on a glass dish to obtain the liquid crystal polymer composite film doped with the carbon nano tubes.
Example 5
40% of polyvinyl dicyclohexyl terephthalate, 55% of SBS elastomer, 2% of carbon nano tube and 3% of solubilizer.
Grinding the polyvinyl dicyclohexyl terephthalate into powder, mixing the powder with SBS elastomer, dissolving the powder with trichloromethane to obtain a mixed solution, adding the carbon nano tubes and the solubilizer into the mixed solution, performing ultrasonic dispersion, and uniformly spreading the mixed solution after ultrasonic dispersion on a glass dish to obtain the liquid crystal polymer composite film doped with the carbon nano tubes.
Example 6
45% of polyvinyl dicyclohexyl terephthalate, 50% of SBS elastomer, 2% of carbon nano tube and 3% of solubilizer.
Grinding the polyvinyl dicyclohexyl terephthalate into powder, mixing the powder with SBS elastomer, dissolving the powder with trichloromethane to obtain a mixed solution, adding the carbon nano tubes and the solubilizer into the mixed solution, performing ultrasonic dispersion, and uniformly spreading the mixed solution after ultrasonic dispersion on a glass dish to obtain the liquid crystal polymer composite film doped with the carbon nano tubes.
Further, the shape memory properties of the sheets prepared in examples 1 to 6 were examined in the present invention, and the results are shown in the following table:
Figure BDA0003243728070000081
in the above table, R isfIs the shape memory fixation rate, RrFor the shape memory recovery rate, it can be seen from the data in the above table that the liquid crystal polymer composite material doped with carbon nanotubes prepared by the present invention has better shape memory performance, wherein, when the mesogen-jacketed liquid crystal polymer is poly (p-butoxyphenyl) terephthalate, the shape memory performance of the composite material is better than that of the composite material when the mesogen-jacketed liquid crystal polymer is poly (vinylcyclohexyl terephthalate).
Further, the mechanical properties of the prepared liquid crystal polymer composite material doped with carbon nanotubes were tested, and the results are shown in the following table:
Figure BDA0003243728070000082
Figure BDA0003243728070000091
it should be noted that the comparison group in the table is a poly (p-butoxyphenyl) terephthalate example for comparison, and the samples of the examples 1 to 6 are prepared in advance into long strips according to the relevant detection standards for testing, and it can be seen from the data in the table that the liquid crystal polymer composite material doped with carbon nanotubes prepared by the present invention has better mechanical properties, and the mechanical properties are significantly improved compared with the liquid crystal polymer material used as the comparison.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. The liquid crystal polymer composite material doped with the carbon nano tubes is characterized by comprising the carbon nano tubes, liquid crystal polymers, an SBS elastomer and a solubilizer, wherein the liquid crystal polymers are crustacean-type liquid crystal polymers.
2. The carbon nanotube-doped liquid crystal polymer composite material according to claim 1, wherein the liquid crystal polymer comprises 25 to 58 mass%, the SBS elastomer comprises 40 to 70 mass%, the carbon nanotube comprises 1 to 2 mass%, and the solubilizer comprises 1 to 3 mass%.
3. The carbon nanotube-doped liquid crystal polymer composite material according to claim 2, wherein the liquid crystal polymer comprises 35 to 45 mass%, the SBS elastomer comprises 50 to 60 mass%, the carbon nanotube comprises 2 mass%, and the solubilizer comprises 3 mass%.
4. The carbon nanotube-doped liquid crystal polymer composite material according to claim 3, wherein the liquid crystal polymer comprises 40% by weight, the SBS elastomer comprises 55% by weight, the carbon nanotubes comprise 2% by weight, and the solubilizer comprises 3% by weight.
5. The carbon nanotube-doped liquid crystal polymer composite according to claim 1, wherein the mesogen-jacketed liquid crystal polymer is a vinyl terephthalic acid mesogen-jacketed liquid crystal polymer.
6. The carbon nanotube-doped liquid crystal polymer composite according to claim 5, wherein the vinyl terephthalic acid-based crustacean-type liquid crystal polymer is one of poly (p-butoxyphenyl) terephthalate or poly (dicyclohexyl terephthalate).
7. The carbon nanotube-doped liquid crystal polymer composite according to claim 1, wherein the solubilizer is a copolymer of maleic anhydride polypropylene.
8. A method for preparing a liquid crystal polymer composite material doped with carbon nanotubes, which is used for preparing the liquid crystal polymer composite material doped with carbon nanotubes in any one of claims 1 to 7, wherein the method comprises the following steps:
grinding liquid crystal macromolecules into powder, and mixing the powder with an SBS elastomer to obtain a mixture;
dissolving the mixture in an organic solvent, and performing ultrasonic dispersion to obtain a mixed solution A;
adding carbon nano tubes and a solubilizer into the mixed solution A, and performing ultrasonic dispersion to obtain a mixed solution B;
and spreading the mixed solution B on a template, and removing the organic solvent to obtain the liquid crystal polymer composite material doped with the carbon nano tube.
9. The method of claim 8, wherein the organic solvent is chloroform.
10. The method of claim 8, wherein the template is a glass dish.
CN202111035421.4A 2021-09-02 2021-09-02 Liquid crystal polymer composite material doped with carbon nano tube and preparation method thereof Pending CN113621212A (en)

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Citations (2)

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Publication number Priority date Publication date Assignee Title
US20080234424A1 (en) * 2006-11-17 2008-09-25 Lee Hang-Woo Carbon nanotube composite and method of preparing the same, carbon nanotube composite thin film prepared from the carbon nanotube composite and method of preparing the carbon nanotube composite thin film
CN108424587A (en) * 2018-04-25 2018-08-21 张云伟 A kind of preparation method of shape memory liquid crystal new material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080234424A1 (en) * 2006-11-17 2008-09-25 Lee Hang-Woo Carbon nanotube composite and method of preparing the same, carbon nanotube composite thin film prepared from the carbon nanotube composite and method of preparing the carbon nanotube composite thin film
CN108424587A (en) * 2018-04-25 2018-08-21 张云伟 A kind of preparation method of shape memory liquid crystal new material

Non-Patent Citations (2)

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万里鹰等: ""SBS改性甲壳型液晶高分子的力学性能与形状记忆行为"", 《高分子材料科学与工程》 *
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Application publication date: 20211109