CN108219370A - A kind of preparation method of thermotropic shape-memory polymer - Google Patents
A kind of preparation method of thermotropic shape-memory polymer Download PDFInfo
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- CN108219370A CN108219370A CN201711414922.7A CN201711414922A CN108219370A CN 108219370 A CN108219370 A CN 108219370A CN 201711414922 A CN201711414922 A CN 201711414922A CN 108219370 A CN108219370 A CN 108219370A
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- shape
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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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
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C08L2201/00—Properties
- C08L2201/12—Shape memory
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to high-performance shape-memory polymer applied technical fields, are related to a kind of preparation method of thermotropic shape-memory polymer.Thermotropic shape-memory polymer is made of conducting polymer and thermoset shape memory resin, and content of the conducting polymer in thermotropic shape-memory polymer is 15wt% 60wt%, and conducting polymer is Polyaniline and its derivative etc.；Thermoset shape memory resin is shape memory resin.The present invention is modified thermoset shape memory polymer using conducting polymer, the characteristics of heat being generated using conducting polymer energization, it can make the thermally equivalent of shape-memory polymer under conditions of energization, realize the thermal drivers deformation of thermoset shape memory polymer.Shape-memory polymer in the present invention has the good moulded manufacturability of former thermosetting resin itself, the preparation that composite material mainstream moulding process realizes composite material of shape memory can be used to be molded, be a kind of resin matrix of high performance structures function integration composite material of shape memory.
Description
Technical field
The invention belongs to high-performance shape-memory polymer applied technical fields, are related to a kind of thermotropic shape memory polymers
The preparation method of object.
Background technology
Shape-memory polymer is a kind of new functional macromolecule material of stimulation-induction type, and having can be by the external world
Change the characteristic of its shape under stimulate the reaction, be a kind of novel intelligent material.For marmem, shape memory
Polymer have the advantages that it is incomparable, including density is low, shape recovery rate is high, recovery temperature is wide for memory, deformation quantity is big, can add
The advantages that work is good and at low cost.For thermoplasticity shape-memory polymer, thermoset shape memory polymer heat tool
There is the features such as higher mechanical property, high-temperature resistant grade, good weatherability, good moulding processability, intelligent variant can be used as to fly
Resin matrix of the large corporation with composite material of shape memory structural member can be independently unfolded in device and space.
With the development of aerospace field technology, higher requirement is proposed to material.Both there is certain carrying
Ability, but with specific function structure-function integrated composite become advanced aerospace composite element must
Right demand.And the performance of thermoset shape memory polymeric matrix directly determines the shape of thermoset shape memory composite material
Memory function, temperature resistant grade and mechanical property.Therefore, high-performance shape memory resin polymer becomes aerospace composite wood
Expect the integrated deciding factor of structure-function.
The mode of heating of shape-memory polymer is mainly using the external heating such as resistance wire (or sheet material), heater box at present
Method heats material by external calandria, realizes the function of shape-memory polymer.Another is relatively conventional
Thermal drivers mode is that conducting particles is distributed to inside shape-memory polymer, is driven by way of being powered and heating.Often
Electric conductor has carbon nanotube, carbon black, nickel powder, chopped carbon fiber etc..
The prior art is primarily present problems with：
(1) using resistance wire (or sheet material) when calandrias heat shape-memory polymer, calandria needs external
To the surface of material, process for making is relative complex, and more difficult precise control of temperature, is caused by local temperature in temperature-rise period
It is excessively high and generate material shape memory performance and mechanical property damage phenomenon.In addition, since calandria is compound with shape memory
Material thermal expansion coefficient mismatches, and calandria easily isolates and falls off.
(2) it is distributed to inside shape-memory polymer using conducting particles, is driven by way of being powered and heating
Deficiency is that conducting particles is more difficult to be uniformly dispersed in shape-memory polymer, when energization cause material local temperature excessively high or
It is too low, so as to influence the performance of shape-memory polymer.In addition, conducting particles generally belongs to inorganic material, with polymer
Interfacial combined function is poor, and a degree of reduction can occur for the mechanical property of shape-memory polymer.
Invention content
The purpose of the present invention is being directed to the deficiencies in the prior art, a kind of thermotropic shape-memory polymer is proposed
Preparation method.
The technical scheme is that：Thermotropic shape-memory polymer is by conducting polymer and thermoset shape memory tree
Fat form, content of the conducting polymer in thermotropic shape-memory polymer be 15wt%-60wt%, conducting polymer be with
The combination of lower one or more：Polyaniline and its derivative, polyacetylene and its derivative, polythiophene and its derivative, polyphenyl sulphur
Acid and its derivative gather to azophenlyene and its derivative, polyfluorene and its derivative, polypyrrole and its derivative, polybenzazole and its spread out
Biology；Thermoset shape memory resin is the combination of following one or more：Shape memory epoxy resin, shape memory span come
Imide resin, shape memory cyanate resin, shape memory polyimide resin, shape memory phenolic resin, shape memory
Unsaturated polyester resin, shape memory acrylic resin.
The present invention has the advantage that and advantageous effect：
The present invention is modified thermoset shape memory polymer using conducting polymer, is powered using conducting polymer
The characteristics of generating heat can make the thermally equivalent of shape-memory polymer under conditions of energization, realize thermoset shape memory
The thermal drivers deformation of polymer.Conducting polymer proposed by the present invention has backbone, and polymerize with thermoset shape memory
Object has good interface performance, can improve the mechanical property of modified shape-memory polymer.Shape memory in the present invention
Polymer has the good moulded manufacturability of former thermosetting resin itself, and composite material mainstream moulding process can be used and realize shape
The preparation molding of memory composite material is a kind of resin matrix of high performance structures-function integration composite material of shape memory.
The shape-memory polymer prepared using the present invention can improve the mechanics of fiber-reinforced shape memory polymer matrix composites as matrix
Performance, and realize the heating excitation deformation of its direct-electrifying, so as to fulfill not only there is bearing capacity, but also there is shape memory function
Structure-function integrated composite, can be widely used in space flight large size can independently unfolding mechanism, deformation spacecraft, variant fly
The aerospace fields such as row device.
Specific embodiment
The design and technology of preparing of the present invention are described in further details, but the technology of the present invention side below by embodiment
Case is not limited to act specific embodiment set forth below.
Using conducting polymer and thermoset shape memory polymer as raw material, a certain amount of conducting polymer is surpassed
Fine grained is evenly spread in thermoset shape memory polymer, obtains thermotropic shape-memory polymer.
The conducting polymer is at least a kind of following resin：Polyaniline and its derivative, polyacetylene and its derivative,
Polythiophene and its derivative, gathers to azophenlyene and its derivative, polyfluorene and its derivative, polypyrrole polyphenyl sulfonic acid and its derivative
And its derivative, Polyindole derivatives.
The thermoset shape memory polymer is at least following a kind of：Shape memory epoxy resin, shape memory are double
Maleimide resin, shape memory cyanate resin, shape memory polyimide resin, shape memory phenolic resin, shape
Remember two or more mixture of unsaturated polyester resin, shape memory acrylic resin or more resin.
A kind of preparation method of thermotropic shape-memory polymer, including step：Conducting polymer is remembered in thermotropic shape
It is 15wt%-60wt% to recall the content in polymer.
(1) 100 parts by weight thermoset shape memory resins are heated to 40-120 DEG C, in 1000-1500 revs/min of rotating speed
Lower carry out mechanical agitation, it is spare after stirring 10-30 minutes；
(2) into resin obtained by step (1), 1-30 parts of conducting polymer is added in, under 1000-1500 revs/min of rotating speed
Mechanical agitation is carried out, it is spare after stirring 10-30 minutes；
(3) mixture obtained by step (2) is transferred in three-roll mill and milled, conducting polymer is made to remember in shape
Recall in resin uniformly disperse after take out it is spare.
Embodiment 1
100 grams of shape memory epoxy resins are added in the beaker equipped with mechanical agitation, thermometer, stirs and begins to warm up
To after 60 DEG C, 20 grams of polyaniline conductive polymers are added in, and stir evenly, form suspension.Obtained suspension is transferred to
Three-roll mill is taken out after milling repeatedly 5 times, and refrigeration is spare.
Embodiment 2
100 grams of shape memory bimaleimide resins are added in the beaker equipped with mechanical agitation, thermometer, stirring is simultaneously
After beginning heat to 90 DEG C, 30 grams of polythiophene conductive macromolecules are added in, and stir evenly, form suspension.It is suspended by what is obtained
Liquid is transferred to three-roll mill, is taken out after milling repeatedly 5 times, and refrigeration is spare.
Embodiment 3
100 grams of shape memory cyanate resins are added in the beaker equipped with mechanical agitation, thermometer, stir and start to add
Heat adds in 30 grams of polyfluorene conducting polymers, and stir evenly to after 90 DEG C, forms suspension.Obtained suspension is transferred to
Three-roll mill is taken out after milling repeatedly 5 times, and refrigeration is spare.
Embodiment 4
100 grams of shape memory cyanate resins are added in the beaker equipped with mechanical agitation, thermometer, stir and start to add
Heat adds in 30 grams of polyfluorene conducting polymers, and stir evenly to after 90 DEG C, forms suspension.Obtained suspension is transferred to
Three-roll mill is taken out after milling repeatedly 5 times, and refrigeration is spare.
Embodiment 5
100 grams of shape memory polyimide resins are added in the beaker equipped with mechanical agitation, thermometer, stirs and starts
After being heated to 120 DEG C, 30 grams of polypyrrole conducting polymers are added in, and stir evenly, form suspension.Obtained suspension is turned
Three-roll mill is moved on to, is taken out after milling repeatedly 5 times, refrigeration is spare.
Claims (1)
1. a kind of preparation method of thermotropic shape-memory polymer, which is characterized in that thermotropic shape-memory polymer is by leading
Electric macromolecule and thermoset shape memory resin composition, content of the conducting polymer in thermotropic shape-memory polymer are
15wt%-60wt%, conducting polymer are the combination of following one or more：Polyaniline and its derivative, polyacetylene and its spread out
Biology, polythiophene and its derivative, polyphenyl sulfonic acid and its derivative gather to azophenlyene and its derivative, polyfluorene and its derivative, gather
Pyrroles and its derivative, Polyindole derivatives；Thermoset shape memory resin is the combination of following one or more：Shape
Remember epoxy resin, shape memory bimaleimide resin, shape memory cyanate resin, shape memory polyimides tree
Fat, shape memory phenolic resin, shape memory unsaturated polyester resin, shape memory acrylic resin.
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| CN201711414922.7A CN108219370A (en) | 2017-12-22 | 2017-12-22 | A kind of preparation method of thermotropic shape-memory polymer |
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| CN201711414922.7A CN108219370A (en) | 2017-12-22 | 2017-12-22 | A kind of preparation method of thermotropic shape-memory polymer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109943071A (en) * | 2019-03-29 | 2019-06-28 | 中南大学 | A kind of polysiloxane-modified cyanate resin base shape-memory material and preparation method thereof with high glass-transition temperature |
| CN110753442A (en) * | 2018-07-23 | 2020-02-04 | 浙江清华柔性电子技术研究院 | Circuit conversion unit, electronic device and temperature control equipment |
| WO2021018100A1 (en) * | 2019-07-30 | 2021-02-04 | 苏州大学 | Remoldable shape memory bismaleimide resin and use thereof |
| CN113896918A (en) * | 2021-10-22 | 2022-01-07 | 海南大学 | Rapid film forming method of polyaniline-based excitation response film |
| CN114015202A (en) * | 2021-10-29 | 2022-02-08 | 航天材料及工艺研究所 | Temperature response shape memory epoxy resin, composite material and preparation method |
| CN115536816A (en) * | 2022-10-28 | 2022-12-30 | 中国科学院兰州化学物理研究所 | Thermosetting epoxy resin shape memory polymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786777A (en) * | 2012-08-06 | 2012-11-21 | 江苏大学 | Intrinsic conduction shape memory polymer and preparation method thereof |
| CN105802188A (en) * | 2014-12-29 | 2016-07-27 | 中航复合材料有限责任公司 | Thermotropic type shape memory composite material |
-
2017
- 2017-12-22 CN CN201711414922.7A patent/CN108219370A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786777A (en) * | 2012-08-06 | 2012-11-21 | 江苏大学 | Intrinsic conduction shape memory polymer and preparation method thereof |
| CN105802188A (en) * | 2014-12-29 | 2016-07-27 | 中航复合材料有限责任公司 | Thermotropic type shape memory composite material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110753442A (en) * | 2018-07-23 | 2020-02-04 | 浙江清华柔性电子技术研究院 | Circuit conversion unit, electronic device and temperature control equipment |
| CN110753442B (en) * | 2018-07-23 | 2022-03-08 | 浙江清华柔性电子技术研究院 | Circuit conversion unit, electronic device and temperature control equipment |
| CN109943071A (en) * | 2019-03-29 | 2019-06-28 | 中南大学 | A kind of polysiloxane-modified cyanate resin base shape-memory material and preparation method thereof with high glass-transition temperature |
| WO2021018100A1 (en) * | 2019-07-30 | 2021-02-04 | 苏州大学 | Remoldable shape memory bismaleimide resin and use thereof |
| CN113896918A (en) * | 2021-10-22 | 2022-01-07 | 海南大学 | Rapid film forming method of polyaniline-based excitation response film |
| CN114015202A (en) * | 2021-10-29 | 2022-02-08 | 航天材料及工艺研究所 | Temperature response shape memory epoxy resin, composite material and preparation method |
| CN115536816A (en) * | 2022-10-28 | 2022-12-30 | 中国科学院兰州化学物理研究所 | Thermosetting epoxy resin shape memory polymer and preparation method thereof |
| CN115536816B (en) * | 2022-10-28 | 2024-02-20 | 中国科学院兰州化学物理研究所 | Thermosetting epoxy resin shape memory polymer and preparation method thereof |
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Application publication date: 20180629 |