CN106832879A - A kind of TEMP conductive polymer composite based on bidirectional shape memory - Google Patents
A kind of TEMP conductive polymer composite based on bidirectional shape memory Download PDFInfo
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- CN106832879A CN106832879A CN201710025710.3A CN201710025710A CN106832879A CN 106832879 A CN106832879 A CN 106832879A CN 201710025710 A CN201710025710 A CN 201710025710A CN 106832879 A CN106832879 A CN 106832879A
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
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- C08L2201/00—Properties
- C08L2201/12—Shape memory
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Abstract
The present invention provides a kind of TEMP polymer composite based on bidirectional shape memory that can realize bidirectional inductive, can realize deforming at a temperature of, particularly under a continuous disturbances, film is stretched to balance when first temperature is raised, solid shape electric signal drops to balance after cooling, then (fuel factor is avoided) under low-voltage, when temperature is raised, the composite can realize that different degrees of shape rises, electrical conductivity also rises therewith, when removing stimulation, composite drops to balance, and electrical conductivity is also slowly drop down to balance therewith.Technical scheme is：A kind of TEMP polymer composite with bidirectional shape memory, is made up of following component and mass percent：Nanometer conductive material, consumption is 1% 2%；Elastic network structure shape memory high molecule material, consumption is 39% 99%；The PCL materials of reversible crystalline phase, consumption is 0% 59%.
Description
Technical field
The present invention provides a kind of two-way (two-way) shape memory macromolecule composite material and conductive material field mechanism,
Specifically related to a kind of conducting metal nano wire with conductive network structure and the TEMP function with two-way function are answered
Condensation material and preparation method.
Background introduction
Scientific research recent years scholar constantly obtains new progress in shape memory high molecule material field.Its shape
Memory macromolecule (Shape memory polymer) material be a class have change of external conditions (such as temperature, humidity, light,
Electromagnetism etc.) stimulation under so as to produce perception.Particularly after its original shape is deformed upon, under extra stimulation, do
Going out corresponding adjustment makes its final recovery to original-shape.Shape memory high molecule its have big deformation quantity, easy figuration, processing hold
Easily, many advantages, such as response can adjust, light weight, cheap, species are enriched, therefore such material is in intelligent sensing, biology
The fields such as medical treatment, space flight and aviation, intelligence weaving, selfreparing have broad application prospects.
This patent is based on shape memory high molecule material, discloses a kind of TEMP based on bidirectional shape memory conductive
Macromolecule.Fax sense shape-memory properties two-way under heat triggering now, refer specifically to deformation recovery when temperature is raised in fact,
Shorten, electrical conductivity rises；Elongated electrical conductivity declines during temperature reduction.Therefore the present invention provides a kind of bidirectional shape memory of preparing
The high molecular preparation method of TEMP and represent mechanical means in this function.Realize passing through macromolecule and nanometer for the first time
The conductive material converse mechanism cold drawn to show pyrocondensation.
The content of the invention
The problem to be solved in the present invention is to provide a kind of temperature based on bidirectional shape memory that can realize bidirectional inductive
Sensing polymer composite, can realize deforming at a temperature of, particularly under a continuous disturbances, when first temperature is raised
Film is stretched to balance, and solid shape electric signal drops to balance after cooling, then (avoids fuel factor) under low-voltage, temperature liter
Gao Shi, the composite can realize that different degrees of shape rises, and electrical conductivity also rises therewith, when removing stimulation, composite wood
Material drops to balance, and electrical conductivity is also slowly drop down to balance therewith.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of TEMP polymer composite with bidirectional shape memory, its component includes elastic network structure shape
Shape remembers the PCL materials and nanometer conductive material of macromolecular material and reversible crystalline phase.
Two-way shape polymer composite with multiple stimulation response of the invention,
It is made up of following component and mass percent：
1. nanometer conductive material, consumption is 1%-2%
2. elastic network structure shape memory high molecule material, consumption is 39%-99%
3. PCL materials of reversible crystalline phase, consumption is 0%-59%
The PCL materials and elastic network structure shape memory high molecule material of described reversible crystalline phase are thermoplastic poly-
Caprolactone (PCL) (Mn=80000) and polyurethane (SMPU) macromolecule.
Nano-silver thread, the nanometer powder that described nanometer conductive material is such as (copper nanoparticle, nano-silver powder) have height
The conductive materials of electric conductivity.
The invention provides the preparation side for preparing the above-mentioned TEMP polymer composite with bidirectional shape memory
Method.Specifically comprise the following steps：With shape memory polyurethane as matrix, thermoplastic polycaprolactone is added, then macromolecule is answered
The blend solution drop coating of condensation material is obtained in nanometer conductive material matrix, the solvent for removing the blend solution on conducting base.
Preferably, shape-memory material polyurethane is the macromolecule matrix of body temp type, addition heat in described preparation technology
Plasticity polycaprolactone, mass percent scope is 0%-60%, is dissolved in organic solvent, and heating stirring ultrasound is uniform.Then it is sharp
One layer of conductive network of densification is obtained by methods such as drop coating or spin coatings on the glass substrate with the nano-silver thread of synthesis, will be prepared
Good blending macromolecular material drop coating is spread on electrical-conductive nanometer material surface, is first dried 12 hours at 70 DEG C -80 DEG C of baking oven,
Finally place into vacuum drying chamber left and right vacuum drying 24 hours at 70 DEG C.Obtain the TEMP with bidirectional shape memory
Conductive polymer composite
Above-mentioned organic solvent is N, N dimethyl acetamide, dimethyl sulfoxide (DMSO), N, N-dimethylformamide or tetrahydrochysene furan
One kind in muttering.
Compared with prior art, the present invention is provided with a kind of TEMP polymer composite of bidirectional shape memory
Preparation method, with following benefit：
The preparation process of the method is simple, easy to operate, and the selectivity of raw material is various.The two-way shape note for preparing
The TEMP polymer composite recalled possesses special pattern, while realizing the function of two-way fax sense.
Brief description of the drawings
Fig. 1 operation charts
Fig. 2 sterograms
The electric current of Fig. 3 conducting film two-way functions, temperature, depth map
The electron microscope of Fig. 4 films
Specific embodiment
In order that technological means of the invention, creation characteristic, reached purpose is readily apparent from effect, below by specific
Embodiment is described in further detail to the present invention.It is necessary to note that embodiment once is protection scope of the present invention.
Embodiment 1
1. the nano-silver thread of 1-3mg is dissolved in ethanol solution, stirred and ultrasound.By its drop coating or it is spin-coated on matrix
On.And dry.
2. thermoplastic polycaprolactone (PCL) is dissolved in N, N dimethyl second with the shape memory polyurethane SMPU of body temp type
In acid amides (DMAC), its ratio is PCL：SMPU=1:9.Heating stirring and ultrasound a period of time, make solution uniform.
3. mixed solution drop coating in above-mentioned 2 is heated 12 hours, after vacuum drying in after conductive material in drying box
Vacuum 24 hours in case.Obtain the two-way shape polymer composite of its multiple stimulation response.
4. a film of 40mm*5*0.05mm is cut into, is fixed in device, the gravity or puller system of counterweight are produced
Raw lasting external force is about 0.2N, and voltage is 0.01v, is applied on sample.
5. during testing herein.The length of its film falls before 15mm to balance, and electric current drops to 0.06mA.When plus
It is 6mm that length is replied when hot, and cooling afterwards returns back to Yuanping City's weighing apparatus.Its effect is 40%, and electric current is realized from 0.06mA to 0.096mA
Between circulate.Realize certain TEMP polymer composite effect based on bidirectional shape memory.
Embodiment 2
1. the nano-silver thread of 1-3mg is dissolved in ethanol solution, stirred and ultrasound.By its drop coating or it is spin-coated on matrix
On.And dry.
2. thermoplastic polycaprolactone (PCL) is dissolved in N, N dimethyl second with the shape memory polyurethane SMPU of body temp type
In acid amides (DMAC), its ratio is PCL：SMPU=1:4.Heating stirring and ultrasound a period of time, make solution uniform.
3. mixed solution drop coating in above-mentioned 2 is heated 12 hours, after vacuum drying in after conductive material in drying box
Vacuum 24 hours in case.Obtain the two-way shape polymer composite of its multiple stimulation response
4. a film of 40mm*5*0.05mm is cut into, is fixed in device, the gravity or puller system of counterweight are produced
Raw lasting external force is about 0.2N, and voltage is 0.01v, is applied on sample.
5. during testing herein, the length of its film falls before 16mm to balance, and electric current drops to 0.014mA.When
It is 7mm that length is replied during heating, and cooling afterwards returns back to Yuanping City's weighing apparatus.Its effect is 43%, and electric current realize from 0.014mA to
Circulated between 0.035mA.Realize certain TEMP polymer composite effect based on bidirectional shape memory.
Embodiment 3
1. the nano-silver thread of 1-3mg is dissolved in ethanol solution, stirred and ultrasound.By its drop coating or it is spin-coated on matrix
On.And dry.
2. thermoplastic polycaprolactone (PCL) is dissolved in N, N dimethyl second with the shape memory polyurethane SMPU of body temp type
In acid amides (DMAC), its ratio is PCL：SMPU=2:3.Heating stirring and ultrasound a period of time, make solution uniform.
3. mixed solution drop coating in above-mentioned 2 is heated 12 hours, after vacuum drying in after conductive material in drying box
Vacuum 24 hours in case.Obtain the two-way shape polymer composite of its multiple stimulation response
4. a film of 40mm*5*0.05mm is cut into, is fixed in device, the gravity or puller system of counterweight are produced
Raw lasting external force is about 0.2N, and voltage is 0.01v, is applied on sample.
5. during testing herein, the length of its film falls before 17mm to balance, and electric current drops to 0.024mA.When
It is 3mm that length is replied during heating, and cooling afterwards returns back to Yuanping City's weighing apparatus.Its effect is 17.6%, and electric current realize from 0.024mA to
Circulated between 0.030mA.Realize certain TEMP polymer composite effect based on bidirectional shape memory.
Claims (8)
1. a kind of TEMP polymer composite with bidirectional shape memory, it is characterised in that its component includes elasticity
Network structure shape remembers the PCL materials and nanometer conductive material of macromolecular material and reversible crystalline phase, and specific consumption is as follows：
Nanometer conductive material, consumption is 1%-2%
Elastic network structure shape memory high molecule material, consumption is 39%-99%
The PCL materials of reversible crystalline phase, consumption is 0%-59%.
2. composite according to claim 1, it is characterised in that：The PCL materials and elasticity of described reversible crystalline phase
Network structure shape memory macromolecular material is that thermoplastic polycaprolactone (PCL) (Mn=80000) and polyurethane (SMPU) are high
Molecule.
3. composite according to claim 1 and 2, it is characterised in that：The Nano Silver that described nanometer conductive material is
Line, the nanometer powder such as conductive materials of (copper nanoparticle, nano-silver powder) with high conductivity.
4. the preparation method of composite according to claim 3, it is characterised in that：Specifically comprise the following steps：With
Shape memory polyurethane is matrix, adds thermoplastic polycaprolactone, then the blend solution drop coating of polymer composite is being received
Rice conductive material substrates, the solvent for removing the blend solution on conducting base is obtained.
5. the preparation method of composite according to claim 4, it is characterised in that：Shape note in described preparation technology
Recall the macromolecule matrix that material polyurethane is body temp type, add thermoplastic polycaprolactone, mass percent scope is 0%-60%,
It is dissolved in organic solvent, heating stirring ultrasound is uniform.Then existed by methods such as drop coating or spin coatings using the nano-silver thread of synthesis
One layer of conductive network of densification is obtained in substrate of glass, the blending macromolecular material drop coating that will be prepared spreads over electrical-conductive nanometer material
On material surface, first dried 12 hours at 70 DEG C -80 DEG C of baking oven, finally place into vacuum drying chamber left and right vacuum at 70 DEG C and do
Dry 24 hours.Obtain the TEMP conductive polymer composite with bidirectional shape memory.
6. the preparation method of composite according to claim 5, it is characterised in that：Above-mentioned organic solvent is N, N diformazans
One kind in yl acetamide, dimethyl sulfoxide (DMSO), N, N-dimethylformamide or tetrahydrofuran.
7. the method for testing of the composite according to claim any one of 1-6, it is characterised in that be cut into certain
The film of width, is fixed in device, and the lasting external force that the gravity or puller system of counterweight are produced is about 0.1-0.2N/mm2, adjusts
Whole voltage is 0.01-0.1v, is applied on sample.
8. the method for testing of composite according to claim 7, it is characterised in that be under voltage, to directly heat
More than melting transition temperature, based on state change principle, electric signal rapid increase when temperature rises rapidly declines during cooling.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710025710.3A CN106832879A (en) | 2017-01-13 | 2017-01-13 | A kind of TEMP conductive polymer composite based on bidirectional shape memory |
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| CN201710025710.3A CN106832879A (en) | 2017-01-13 | 2017-01-13 | A kind of TEMP conductive polymer composite based on bidirectional shape memory |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107275121A (en) * | 2017-07-12 | 2017-10-20 | 广东工业大学 | A kind of ultracapacitor with self-healing and preparation method thereof |
| CN112538327A (en) * | 2020-12-08 | 2021-03-23 | 南开大学 | Temperature-control self-adhesive conductive composite material based on shape memory effect and preparation method and application thereof |
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| CN104371084A (en) * | 2014-10-28 | 2015-02-25 | 哈尔滨理工大学 | Shape memory polyurethane with high-temperature restorability |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587001A (en) * | 2004-09-08 | 2005-03-02 | 章一叶 | Anti-fake method for product package |
| CN104371084A (en) * | 2014-10-28 | 2015-02-25 | 哈尔滨理工大学 | Shape memory polyurethane with high-temperature restorability |
Non-Patent Citations (2)
| Title |
|---|
| LUO HONGSHENG 等: ""Shape memory-based tunable resistivity of polymer composites"", 《APPLIED SURFACE SCIENCE》 * |
| LUO HONGSHENG 等: ""Temperature sensing of conductive shape memory polymer composites"", 《MATERIALS LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107275121A (en) * | 2017-07-12 | 2017-10-20 | 广东工业大学 | A kind of ultracapacitor with self-healing and preparation method thereof |
| CN107275121B (en) * | 2017-07-12 | 2019-12-10 | 广东工业大学 | Self-healing super capacitor and preparation method thereof |
| CN112538327A (en) * | 2020-12-08 | 2021-03-23 | 南开大学 | Temperature-control self-adhesive conductive composite material based on shape memory effect and preparation method and application thereof |
| CN112538327B (en) * | 2020-12-08 | 2022-04-12 | 南开大学 | Temperature-control self-adhesive conductive composite material based on shape memory effect and preparation method and application thereof |
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Application publication date: 20170613 |