CN105504474B - A kind of shape memory macromolecule composite material and preparation method thereof - Google Patents
A kind of shape memory macromolecule composite material and preparation method thereof Download PDFInfo
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- CN105504474B CN105504474B CN201610011240.0A CN201610011240A CN105504474B CN 105504474 B CN105504474 B CN 105504474B CN 201610011240 A CN201610011240 A CN 201610011240A CN 105504474 B CN105504474 B CN 105504474B
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
The present invention relates to a kind of shape memory macromolecule composite material and preparation method thereof.The composite material is mainly made of random copolymer elastomer and organic molecule crystalline material, can also include other auxiliary agents, and raw material is fully blended using double screw extruder and directly obtains thin film shape memory, the product such as sheet material, fiber.Random copolymer elastomer has good entropic elasticity, plays restorer original-shape；Small molecule organic compound plays fixed and releasing material temporary shapes by the way that crystallization and melting transition occurs；Both synergistic effects, make material have excellent shape-memory properties.Raw material of the present invention is generally easy to get and cheap；Double screw extrusion method is a kind of continuous preparation process, realizes the step preparation by raw material to shape memory product, efficient, product stability is good, environmental-friendly without using any solvent.The strong cost for reducing shape memory high molecule material of the invention, significantly improves its preparation efficiency.
Description
Technical field
The present invention relates to shape-memory material field, and in particular to a kind of shape using random copolymer elastomer as matrix
Remember polymer composite and preparation method thereof.
Background technology
Shape memory high molecule material is a kind of intellectual material that response can be produced to external condition, they " can remember
Recall " shape of setting（Original-shape）, then it is molded the shapes of various needs（Temporary shapes）, when extraneous temperature
When reaching specified conditions, they can automatically revert to original shape for degree, magnetic field, humidity, illumination.Shape memory high molecule material
Material have figuration easily, soft, deformation quantity is big, response condition is adjustable, triggering mode is various, printable, light weight, cost are low etc.
Plurality of advantages, before there is wide application in fields such as biologic medical, aerospace, intelligence weaving, sensor and selfreparings
Scape.Traditional temperature response type shape memory high molecule material is mainly to have soft segment and hard section knot by prepared by polymerisation
The copolymer material of structure, the building-up process of this kind of shape memory copolymer material is extremely complex, and cost is higher, low yield, at the same time
Since it is desired that using a large amount of inflammable and organic solvents of toxicity, environment is polluted, is difficult to realize large-scale production.It is and later
The shape memory blend material of development is to be prepared by reply gathering compound and stationary phase polymer by way of physical mixed
Form, although avoiding the building-up process of complexity, simplify preparation process, only when the two kinds of polymer being mutually mixed is formed
During the phase structure of co-continuous, that is, only when the component ratio for the two kinds of polymer being mutually mixed is 50:When near 50, just have
Preferable shape-memory properties.In addition, shape memory high molecule blend material can be in original-shape and various temporary shapes
Between one of the basic principle changed be that the fixation of its temporary shapes and releasing can be by crystalline polymers（As stationary phase）Phase
State changes（Crystalline state changes with molten state）Realized to control, this transition temperature is referred to as the transfer of shapes temperature of material
（T sw）.However, transfer of shapes temperature is fewer and fewer in the crystalline polymer of near room temperature, only has polycaprolactone（PCL）, polyoxy
Change ethene（PEO）It is available and expensive Deng a small number of polymer, it strongly limit shape memory high molecule blend material
The development and application of material.
Chinese patent CN 103224682 and CN 103102636 utilizes more block structure polymer, such as styrene-fourth
Styrene（SBS）Block copolymer and olefin block copolymers（OBCs）, and small-molecule substance is raw material, use is molten
Liquid blending, be kneaded or the method for immersion prepares shape-memory material.Inventing reduces the production cost of material, but more blocks
The polymer of structure needs in solution blending preparation process to use a large amount of organic solvents than relatively limited, and after mixing
Removing solvent is also evaporated, has pollution to environment.In addition, either solution blending, immersion or mixing in patent, it is obtained
Mixture also to wait post forming process to use by compressing again, therefore be all intermittent preparation process, exist
Preparation efficiency is low, can not continuous production the problem of.So selecting raw material that is cheap and being easy to get, realize shape-memory material from original
The continuous preparation for expecting finished product is the key technical problem of field development.
The content of the invention
The present invention proposes a kind of shape memory for the problems of existing shape memory high molecule material preparation method
Polymer composite and preparation method thereof.The present invention selects the random copolymer elastomer of extensive commercialization to be used as and replys phase,
Cheap and miscellaneous organic molecule crystalline material is selected continuously to be squeezed by efficient double screw extruder as stationary phase
Go out to prepare shape memory macromolecule composite material, by using different extrusion neck ring molds, realize that a step directly obtains shape memory
The products such as film, sheet material, plate, club-shaped material or fiber.Random copolymer elastomer in material has good entropic elasticity,
Play the role of restorer original-shape；Organic molecule crystalline material in material is risen by the way that crystallization and melting transition occurs
To fixed and releasing material temporary shapes effects；Both synergistic effects, make material have excellent shape-memory properties.This hair
It is bright to significantly improve the flexibility for preparing shape-memory material, the cost for preparing shape-memory material is greatly reduced, is realized
Prepared by a step of raw material to shape memory product and continuous production, it is easy to operate, efficient, product stability is good, and not
It is environmental-friendly using any organic solvent, it is particularly suitable for producing in enormous quantities.
A kind of shape memory macromolecule composite material proposed by the present invention, mainly by random copolymer elastomer and in room temperature
The organic molecule crystalline material in crystalline state is formed down, also comprising other adjuvant components.Random copolymer elastomer plays
The effect of restorer original-shape, organic molecule crystalline material play the role of fixed material temporary shapes, composite material
Transfer of shapes temperature by organic molecule crystalline material fusing point（T m1）Determine, random copolymer elastomer, organic molecule
Crystalline material and other auxiliary agent quality parts ratios for example under：
100 parts of random copolymer elastomer, in terms of mass number；
10-150 parts of organic molecule crystalline material, in terms of mass number；
Other adjuvant component 0-100 parts, in terms of mass number.
In the present invention, the fusing point of the random copolymer elastomer（T m2）Higher than the fusing point of organic molecule crystalline material
（T m1）More than 10 DEG C, work as temperature（T）T m1＜T＜T m2During scope, the characteristic of elastomer is presented in composite material, shows as variable
Shape and recovery of shape, you can composite material is deformed into required shape and size；Work as temperature（T）It is down toT＜T m1Model
When enclosing, the characteristic of crystalline solid is presented in composite material, shows as hardness and shape stability, you can consolidated the deformation of composite material
Live calmly；When composite material needs to be returned to original-shape, composite material is reheated toT m1＜T＜T m2Scope, deformation
Body automatically reverts to original-shape again under the driving of internal stress, forms shape memory effect；So move in circles, pass through control
Environment temperature residing for composite material achieves that the Shape memory behavior of material.
In the present invention, using the good plasticizing of double screw extruder and immixture, realize random copolymer elastomer and
Organic molecule crystalline material is sufficiently mixed.By selecting the random copolymer elastomer of different melting points and having for different melting points
Machine small molecule crystalline material is next for composite, and acquisition has different response temperature ranges（T m1-T m2）Shape-memory material.
In the present invention, by varying the component of random copolymer elastomer and organic molecule crystalline material in composite material
Ratio, adjusts the mechanical property and shape-memory properties of material.
In the present invention, selected random copolymer elastomer includes but not limited to ethylene-alpha-olefin random copolymer elasticity
Body（POE）Or any of propylene-alpha olefin random copolymer elastomer or its blend.
In the present invention, selected organic molecule crystalline material includes but not limited to saturated fatty acid, saturated fatty acid
Any of ester, saturated fat amine or paraffin or its blend.
In the present invention, other adjuvant components for any of antioxidant, colouring agent, various modifying agent or filler etc. or
It is several.
The preparation method of shape memory macromolecule composite material proposed by the present invention, comprises the following steps that：
The random copolymer elastomer, organic molecule crystalline material and other auxiliary agents of selection are proportionally added into double spiral shells
In the barrel of bar extruder, material is flowed out by mouth mold through double screw extruder fusion plastification and being sufficiently mixed, then through cooling and
Shape memory macromolecule composite material is made in winding；It is 60-300 DEG C to control each section of temperature of double screw extruder.
In the present invention, the film of composite material, piece can be prepared by using different mouth molds in double screw extruder
The products such as material, plate, club-shaped material or fiber.
The Shape memory behavior principle of shape memory macromolecule composite material proposed by the present invention is random copolymer elasticity
The fusing point of body（T m2）Higher than the fusing point of organic molecule crystalline material（T m1）More than 10 DEG C.It is heated to when composite materialT m1＜T
＜T m2During scope, the organic molecule crystalline material in material switchs to molten state, and material integrally just shows random copolymer bullet
The rubber elastic behavior of property body, material can under the effect of external force be stretched, distort, and the change of size and/or shape occurs,
Obtain an interim shape.Then T ＜ are cooled toT m1Scope, the small molecule organic compound in material will be crystallized and fixed
This interim shape.When temperature is raised again toT m1＜ T ＜T m2During scope, organic molecule crystalline material melts again, material
Material will automatically return to original shape under the effect of the entropic elasticity of random copolymer elastomer, realize Shape memory behavior.
The present invention according to following test method to the shape-memory properties of the shape memory macromolecule composite material of preparation into
Row detection：
The both ends of strip composite sample are fixed on to the folder of the electronic universal tester equipped with temperature-controlled box at room temperature
On tool, length at this time is defined asl 0.It is warming up to and is higher than organic molecule crystalline material fusing point（T m1）5 DEG C of temperature, waits 5 points
Clock reaches equalized temperature.Sample is stretched 50% by service-test machine, and length at this time is defined asl 1.Cool the temperature to room temperature,
Keep sample both ends to fix, wait 5 minutes.One end of sample is unclamped, its length is measured, is defined asl 2.It is warming up to and is higher than again
Organic molecule crystalline material fusing point（T m1）5 DEG C of temperature, waits 5 minutes, makes sample occur fully to reply.Sample is taken out, is surveyed
Its length is measured, is defined asl 3。
Shape recovery rate=
Shape fixed rate=
The beneficial effects of the present invention are：
1. the present invention prepares composite material of shape memory using random copolymer elastomer and organic molecule crystalline material,
The flexibility for preparing shape-memory material is significantly improved, while greatly reduces the cost for preparing shape-memory material.
2. the present invention is realized by double screw extruder method and is prepared and connected by a step of raw material to shape memory product
Continuous production, it is easy to operate, efficient, product stability is good, it is particularly suitable for producing in enormous quantities.
3. the present invention in preparation process without using any organic solvent, it is environmental-friendly.
4. preparation method proposed by the present invention can obtain thin film shape memory, sheet material, plate club-shaped material or fiber etc.
Different products.
5. shape memory macromolecule composite material proposed by the present invention and preparation method thereof is by selecting the nothings of different melting points
The organic molecule crystalline material of rule copolymer elastomer and different melting points is arranged in pairs or groups, and can be obtained and to be remembered with different shape
Recall the composite material of shape memory of response temperature range.
6. shape memory macromolecule composite material proposed by the present invention and preparation method thereof can be adjusted in wide range
The ratio of two kinds of key components, so that the performance of controlled material.
The shape memory macromolecule composite material excellent performance and controllable scope that the present invention obtains are wide.It is proposed by the present invention
Preparation method strong applicability, can prepare shape-memory material, significantly drop using the raw material of a large amount of cheap commercializations
Low production cost.Whole preparation process is without using any organic solvent, and easy to operate, environmental-friendly, efficient, a step obtains
Final product, is particularly suitable for large-scale continuous production, application easy to spread, has very high commercial application prospect.
Embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiments are served only for
The present invention is described further, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art according to
The invention described above content makes the present invention some nonessential modifications and adaptations, still falls within protection scope of the present invention.
Embodiment 1
POE (ENGAGE 8450) and stearic acid（Fusing point is 70 DEG C or so）Proportionally added after 90 parts and 10 parts mixing
Into twin-screw extruder barrel, each section of temperature control of double screw extruder is between 100-180 DEG C.Material is in twin-screw extrusion
Fusion plastification and it is sufficiently mixed in machine, is flowed out by flat mouth mold, thin film shape memory material is made after cooling and winding.Institute
Between the shape memory response temperature for obtaining material is 70-90 DEG C, the shape recovery rate of material is 90-92%, and the shape of material is fixed
Rate is 92-93%.
Embodiment 2
The other the same as in Example 1, circular hole mouth mold is changed to by the flat mouth mold of double screw extruder, and the bar-shaped material of shape memory is made
Material.Between the shape memory response temperature of resulting materials is 70-90 DEG C, the shape recovery rate of material is 90-92%, the shape of material
Shape fixed rate is 92-93%.
Embodiment 3
The other the same as in Example 1,70 parts and 30 parts are changed to by POE (ENGAGE 8450) and stearic acid ratio, resulting materials
Between shape memory response temperature is 70-90 DEG C, the shape recovery rate of material is 88-90%, and the shape fixed rate of material is 95-
97%。
Embodiment 4
The other the same as in Example 1,50 parts and 50 parts are changed to by POE (ENGAGE 8450) and stearic acid ratio, resulting materials
Between shape memory response temperature is 70-90 DEG C, the shape recovery rate of material is 82-84%, and the shape of material is fixed as 96-
97%。
Embodiment 5
POE (ENGAGE HM7280) and stearic acid are proportionally added to double screw extruder after 90 parts and 10 parts mixing
In barrel, each section of temperature control of double screw extruder is between 120-200 DEG C.Fusion plastification is simultaneously in double screw extruder for material
It is sufficiently mixed, is flowed out by flat mouth mold, thin film shape memory material is made after cooling and winding.The shape note of resulting materials
Recall response temperature be 70-110 DEG C between, the shape recovery rate of material is 90-94%, and the shape fixed rate of material is 93-95%.
Embodiment 6
The other the same as in Example 5, circular hole mouth mold is changed to by the flat mouth mold of double screw extruder, and the bar-shaped material of shape memory is made
Material.Between the shape memory response temperature of resulting materials is 70-110 DEG C, the shape recovery rate of material is 90-94%, the shape of material
Shape fixed rate is 93-95%.
Embodiment 7
The other the same as in Example 5,70 parts and 30 parts, resulting materials are changed to by POE (ENGAGE HM7280) and stearic acid ratio
Shape memory response temperature be 70-110 DEG C between, the shape recovery rate of material is 80-86%, and the shape fixed rate of material is
96-97%。
Embodiment 8
The other the same as in Example 5,50 parts and 50 parts, resulting materials are changed to by POE (ENGAGE HM7280) and stearic acid ratio
Shape memory response temperature be 70-110 DEG C between, the shape recovery rate of material is 75-80%, and the shape fixed rate of material is
97-98%。
Embodiment 9
POE (ENGAGE 8200) and paraffin（Fusing point is 40 DEG C or so）Proportionally it is added to after 70 parts and 30 parts mixing
In twin-screw extruder barrel, each section of temperature control of double screw extruder is between 80-160 DEG C.Material is in double screw extruder
Middle fusion plastification is simultaneously sufficiently mixed, and is flowed out by flat mouth mold, and thin film shape memory material is made after cooling and winding.Gained
Between the shape memory response temperature of material is 40-60 DEG C, the shape recovery rate of material is 91-93%, the shape fixed rate of material
For 95-96%.
Embodiment 10
Other same embodiments 9, porous mouth mold is changed to by the flat mouth mold of double screw extruder, and uses rotation winding at a high speed
Device, is made shape memory fiber material.The shape-memory properties of resulting materials are substantially the same manner as Example 9.
Embodiment 11
The other the same as in Example 3, in addition adds 20 parts of calcium carbonate, the shape recovery rate and shape fixed rate of resulting materials compare
It is more satisfactory.
Embodiment 12
The other the same as in Example 3, in addition adds 15 parts of carbon blacks, the shape recovery rate and shape fixed rate of resulting materials compare
It is preferable.
Embodiment 13
The other the same as in Example 3, in addition adds 0.5 part of antioxidant, shape-memory properties and 3 base of embodiment of resulting materials
This is identical.
Claims (7)
1. a kind of shape memory macromolecule composite material, it is characterised in that mainly by random copolymer elastomer and at room temperature
Formed in the organic molecule crystalline material of crystalline state, also play recovery comprising other adjuvant components, random copolymer elastomer
The effect of material original-shape, organic molecule crystalline material play the role of fixed material temporary shapes, the shape of composite material
Shape transition temperature by organic molecule crystalline material fusing point（Tm1）Determine, random copolymer elastomer, organic molecule crystallization
Material and other auxiliary agent quality parts ratios for example under：100 parts of random copolymer elastomer, in terms of mass number；Organic molecule knot
10-150 parts of eutectic substance, in terms of mass number；Other adjuvant component 0-100 parts, in terms of mass number；
The random copolymer elastomer includes ethylene-alpha-olefin random copolymer elastomer（POE）Or propylene-alpha olefin is randomly common
Any of copolymer elastomers or its blend；
The fusing point of the random copolymer elastomer（Tm2）Higher than the fusing point of the organic molecule crystalline material（Tm1）10 DEG C with
On；By selecting the random copolymer elastomer of different melting points and the organic molecule crystalline material of different melting points to be answered
Close, acquisition has different response temperature ranges（Tm1-Tm2）Shape-memory material.
2. shape memory macromolecule composite material according to claim 1, it is characterised in that work as temperature（T）In Tm1＜ T ＜
Tm2During scope, the characteristic of elastomer is presented in composite material, shows as deformability and recovery of shape, you can become composite material
Shape is to required shape and size；Work as temperature（T）It is down to T ＜ Tm1During scope, the characteristic of crystalline solid, performance is presented in composite material
For hardness and shape stability, you can be fixed the deformation of composite material；When composite material needs to be returned to original-shape
When, composite material is reheated to Tm1＜ T ＜ Tm2Scope, deformable body automatically revert to original again under the driving of internal stress
Shape, forms shape memory effect；So move in circles, by controlling the environment temperature residing for composite material to achieve that material
Shape memory behavior.
3. shape memory macromolecule composite material according to claim 1 or 2, it is characterised in that by varying composite wood
The component ratio of random copolymer elastomer and organic molecule crystalline material in material, adjusts the mechanical property and shape note of material
Recall performance.
4. shape memory macromolecule composite material according to claim 1, it is characterised in that selected organic molecule
Crystalline material includes but not limited to any of saturated fatty acid, polyunsaturated fatty acid ester, saturated fat amine or paraffin or it is common
Mixed thing.
5. shape memory macromolecule composite material according to claim 1, it is characterised in that other adjuvant components are antioxygen
Any of agent, colouring agent, various modifying agent or filler are several.
A kind of 6. preparation method of shape memory macromolecule composite material as claimed in claim 1, it is characterised in that specific step
It is rapid as follows：The random copolymer elastomer, organic molecule crystalline material and other auxiliary agents of selection are proportionally added into double spiral shells
In the barrel of bar extruder, material is flowed out by mouth mold through double screw extruder fusion plastification and being sufficiently mixed, then through cooling and
Shape memory macromolecule composite material is made in winding；It is 60-300 DEG C to control each section of temperature of double screw extruder.
7. the preparation method of shape memory macromolecule composite material according to claim 6, it is characterised in that twin-screw squeezes
Go out machine to produce the film of composite material, sheet material, plate, club-shaped material or fiber is prepared by using different mouth molds
Product.
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| CN106620808A (en) * | 2016-11-16 | 2017-05-10 | 同济大学 | Medical fixed shape memory high-molecular composite material and preparation method thereof |
| CN110256760B (en) * | 2019-06-21 | 2021-04-13 | 四川大学 | Reversible shape memory material with photoelectric responsiveness and preparation method and application thereof |
| CN110368161B (en) * | 2019-07-22 | 2021-03-26 | 北京化工大学 | Rehabilitation/exercise protection tool and preparation method and use method thereof |
| CN110372922B (en) * | 2019-07-22 | 2021-06-01 | 北京化工大学 | Polymer material with triple shape memory effect and preparation and application thereof |
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| CN103224682A (en) * | 2013-04-19 | 2013-07-31 | 复旦大学 | Shape memory material based on olefin block copolymers |
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