CN103224682A - Shape memory material based on olefin block copolymers - Google Patents
Shape memory material based on olefin block copolymers Download PDFInfo
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- CN103224682A CN103224682A CN2013101379186A CN201310137918A CN103224682A CN 103224682 A CN103224682 A CN 103224682A CN 2013101379186 A CN2013101379186 A CN 2013101379186A CN 201310137918 A CN201310137918 A CN 201310137918A CN 103224682 A CN103224682 A CN 103224682A
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Abstract
The invention belongs to the technical field of memory materials, and specifically relates to a shape memory material based on olefin block copolymers (OBCs). The material is composed of at least the following two components of OBCs and small molecular crystalline substances, and also may comprise other components. The material is characterized in that a permanent shape is determined by the OBCs and shape change is controlled by the small molecular crystalline substances. Polymer matrixes may the OBCs in various structures and compositions, and the small molecular crystalline substances may be small molecules having good compatibility with the OBCs and melting points lower than those of the OBCs. The method has the advantages that the OBCs are selected as the matrixes; the obtained modified materials have excellent mechanical properties and very large breaking elongation; the optional small molecular crystalline substances have various species; a transition temperature of the material can be controlled precisely by changing the species of the optional small molecular crystalline substances; and since the OBCs are produced in large scale and processing and shaping method for the OBCs are very mature, the shape memory composite material has possibility for large-scale production. The shape memory composite material has huge potential application values in intelligent textiles and thin film materials.
Description
Technical field
The invention belongs to the shape-memory material technical field, be specifically related to the composite material of shape memory of a kind of olefin block copolymers (OBCs) and paraffin, form by following two kinds of components at least: OBCs, small molecules crystal material, also can contain other component.These material modified characteristics are to determine permanent shape by OBCs, by small molecules crystalline material control change of shape.
Background technology
Shape-memory material is a kind of very important intelligent material, and it has the ability that some external environment of perception changes, and this material with responding ability is widely used in the smart material and structure field.To the shape-memory material of having finalized the design, under some particular environment condition (as heating, illumination or electromagnetic field inducing action etc.), the physical parameter of shape-memory material (as shape, volume or strain etc.) can be adjusted automatically; When removing or changing environmental factors, this adjusted state can be held; Yet once more shape-memory material is applied these particular environment conditions, it can reply or recover its original state again.What at first find shape memory characteristic is shape memory alloy: 1931, gold-cadmium alloy is found had shape memory effect, and 1962, most important and present most widely used nickel-titanium shape memory alloy was found.The scope of shape memory alloy has expanded to solid, film or even foam at present.The discovery of shape-memory polymer is then later, and Ota in 1981 finds that the polyethylene of radiation crosslinking has shape memory characteristic, and after this polymkeric substance such as urethane, Resins, epoxy also is found in succession and has shape memory.Shape-memory polymer all has boundless application prospect in fields such as wrapping material, textile industry, biomedicine, aerospace at present.
In the shape-memory polymer field, the thermoplasticity shape-memory material occupies critical role.The thermoplasticity shape-memory polymer is by T
mOr T
gHigher stationary phase and T
mOr T
gBut lower anti-phase constitutes.Under the stationary phase transition temperature, can form the physical crosslinking structure that molecule twines, thereby make material have entropy-elasticity, after the distortion recovery of shape can take place.But anti-phase the fixing of shape and is replied as on-off control, reduces to reversible phase transition temperature when following when temperature, and temporary transient shape can be fixed, and when temperature rises to this transition temperature when above once more, material can be replied permanent shape.Thermoplastic elastomer is mixed with the small molecules crystalline material, is the effective ways of preparation thermoplasticity shape-memory material.Small molecules in this mixture requires with polymeric matrix better consistency is arranged.Because the thermoplastic elastomer kind that itself possesses shape memory is less, but also limitation relatively of the transition temperature of anti-phase is subjected to very big restriction in actual applications.By adding the crystallization small molecules, can prepare various thermoplasticity shape-memory material, change the micromolecular fusing point of adding, the transition temperature of all right accuracy controlling shape-memory material makes material be suitable for specific applied environment.
2006, the scientist of Dow chemical company proposed the notion of " chain shuttle back and forth polymerization ", and has synthesized olefin block copolymers (OBCs) on this basis.This thermoplastic elastomer is made of soft section and hard section, and its main component is ethene/1-octene, and the 1-octene content is very low in the hard section, and the 1-octene content is higher relatively in soft section.The pattern that unique many block structures make OBCs present to be separated, the crystallizing field that wherein hard section is formed is a disperse phase, the non-crystalline region of soft section composition is an external phase.Because it is very unique that phase structure is compared traditional alkene, OBCs also has some very excellent mechanical properties, such as good compression tension set performance and elastic recovery performance, bigger elongation at break etc., these character make suitable textiles and the thin-film material etc. of being used as of OBCs.Because it is similar to straight-chain paraffin that the chain of OBCs is formed, both have good consistency, a large amount of paraffin can be stored in OBCs and arrange comparatively loose soft section, be in the external phase, therefore the crystallization and the fusion of paraffin can well change external phase segmental reactivity in the OBCs/ paraffin mixture, thus the fixing and answer of control shape.This patent reported method utilizes OBCs and small molecules crystalline material to make up shape memory composites first.It is matrix that the advantage of this method is to select for use OBCs, and the material modified mechanical property of gained is very excellent, and very big elongation at break is arranged.Available small molecules crystalline material is of a great variety, can carry out accuracy controlling to the transition temperature of material by changing its kind.Because OBCs large-scale production, its processing molding method are very ripe, so this shape memory composites possesses the possibility of scale operation.For the definite mixture of small molecules kind, OBCs and micromolecular adjustable ratio are very big, the mechanical property of material monolithic, comprise elongation at break, tensile strength etc., and shape memory character all can present corresponding variation with the change of material rate, thereby can obtain optimized mechanics and shape memory character by changing mass ratio.This type of shape-memory material has huge potential using value at intelligent textile and thin-film material field.
Summary of the invention
A kind of shape-memory material that this patent proposed based on OBCs, by forming by following two kinds of components at least: OBCs matrix, small molecules crystalline material, also can contain and other component.These material modified characteristics are to determine permanent shape by the OBCs matrix, by small molecules crystalline material control change of shape.
OBCs among the present invention, be to form polymkeric substance with many block structures by ethene and other alpha-olefin copolymer, many block structures of its uniqueness make it to present the form that is separated, the crystallizing field that wherein hard section is formed is a disperse phase, the non-crystalline region of soft section composition is an external phase, have the physical crosslinking structure, so have elasticity on the macroscopic view, after generation deformation, can automatically reply.The OBCs of various structures and composition comprises any chemical constitution (block length and sequence) and soft or hard section ratio, in principle can be as the matrix of this matrix material.Can be a kind of OBCs of the trade mark, also can be the mixture of different trade mark OBCs.
Small molecules crystalline material among the present invention can be to have better consistency and fusing point to be lower than the organic molecule of OBCs with the OBCs matrix, as in paraffin, lipid acid or the aliphatic amide of the various trades mark one or more etc.
In the material of the present invention, also can use various other auxiliary agents, as fire retardant, heat conduction properties-correcting agent, dispersion agent, oxidation inhibitor, tinting material, filler etc., not influence the performance of institute's invention material, and use according to practical situation.The composition of several main components (mass parts) is determined by the shape memory character that the consistency and the material of OBCs matrix and small molecules crystalline material will reach among the present invention.On the preparation method, the small molecules crystalline material is uniformly dispersed OBCs matrix and small molecule material thorough mixing in OBCs.When mixing, can adopt methods such as solution blending, melt blending or immersion.Melt blending does not need to use solvent, and OBCs directly mixes with the small molecules crystalline material can obtain shape-memory material; Solution blending need be selected suitable solvent for use, dissolves fully and mix back removing to desolvate, and obtains target material; Infusion method is about to place the sufficiently long time so that paraffin spreads evenly in the liquid after the OBCs particle is immersed in the paraffin fusion in OBCs, obtains target material.The working method that uses among the present invention is general macromolecule material product processing molding method, as mixing, mold pressing, injection etc., does not have particular requirement.
The ratio of quality and the number of copies of OBCs, small molecules crystalline material and other auxiliary agent is for example following:
100 parts of OBCs;
Crystallizable small molecules 25-200 part;
Other auxiliary agent 0-500 part.
Present method utilizes OBCs to determine permanent shape, by small molecules crystalline material control change of shape.It is matrix that its advantage is to select for use OBCs, and the material modified mechanical property of gained is very excellent, and very big elongation at break is arranged; Available small molecules crystalline material is of a great variety, can carry out accuracy controlling to the transition temperature of material by changing its kind; Because OBCs large-scale production, its processing molding method are very ripe, so this shape memory composites possesses the possibility of scale operation.For the definite mixture of small molecules kind, OBCs and micromolecular adjustable ratio are very big, the mechanical property of material monolithic, comprise elongation at break, tensile strength etc., and shape memory character all can present corresponding variation with the change of material rate, thereby can obtain optimized mechanics and shape memory character by changing mass ratio.This type of shape-memory material has huge potential using value at intelligent textile and thin-film material field.
Embodiment
Specifically by the following examples the present invention is further described, wherein form umber, content all by weight.
Embodiment 1
(fusing point is 30 with paraffin for OBC (LOT NO OBC-2)
oAbout C) dissolving fully in dimethylbenzene, wherein OBCs and paraffin ratio are 50 parts and 50 parts, and the material that obtains behind the solvent evaporate to dryness is molded into sheet, are cut into the rectangular specimen of the long 20mm of wide 4mm, test.The gained material shape is fixing all more satisfactory with the recovery of shape rate.
Embodiment 2
(fusing point is 10 to be positioned over n-Hexadecane for OBC (LOT NO OBC-3)
oAbout C) in the liquid, 80
oC places down 24h so that paraffin as far as possible diffusion evenly, wherein OBCs and n-Hexadecane ratio be 70 parts with 30 parts, adopt stretch mode to carry out shape memory and test, with material 60
oBe stretched to 100% under the C, in frozen water, carry out fixed in shape after, be warming up to 60 once more
oC, record answer situation, fixed in shape rate and response rate are all near 100%.
Embodiment 3
Other is with embodiment 2, and OBCs and n-Hexadecane ratio are 30 parts and 70 parts, and gained material shape fixed rate and response rate are all near 100%.
Embodiment 4
With OBCs (LOT NO OBC-1) and paraffin (fusing point 50
oAbout C) 160
OCMelt blending, wherein OBC and paraffin are each 100 parts, and the material that mixes is molded into sheet after taking out, and is cut into the rectangular specimen of the long 20mm of wide 4mm, tests.The gained material property is as follows: tensile strength is 6.3MPa, elongation at break 16.6.Adopt stretch mode to carry out the shape memory test, with material 60
oBe stretched to 100% under the C, in frozen water, carry out fixed in shape after, be warming up to 60 once more
oC, record answer situation.The material shape fixed rate is near 100%, and the recovery of shape rate is 97%.
Embodiment 5
Other is with embodiment 4, and wherein OBCs and paraffin ratio change 100 parts and 25 parts into, and the gained material property is as follows: tensile strength is 7.1MPa, elongation at break 19.3, and the fixed in shape rate is 95%, the recovery of shape rate is 98%.
Embodiment 6
(fusing point is 40 with paraffin for OBCs (LOT NO OBC-3)
oAbout C) 160
OCMelt blending, wherein OBCs and paraffin ratio are 70 parts and 30 parts, the material that mixes is molded into sheet after taking out, and is cut into the rectangular specimen of the long 20mm of wide 4mm, tests.The gained material property is as follows: tensile strength is 8.5MPa, elongation at break 15.5.Adopt stretch mode to carry out the shape memory test, with material 60
oBe stretched to 100% under the C, in frozen water, carry out fixed in shape after, be warming up to 60 once more
oC, record answer situation.The material shape fixed rate is 92%, and the recovery of shape rate is 88% in circulation for the first time, afterwards in the loop test near 100%, and more stable.
Embodiment 7
Other is with embodiment 6, and OBCs is 40 parts of 60 parts of ratios with the paraffin ratio, and the gained material property is as follows: tensile strength is 5.8MPa, elongation at break 15.2, fixed in shape rate are near 100%, and the recovery of shape rate is 90% in circulation for the first time, afterwards in the loop test near 100%, and more stable.
Embodiment 8
Other removes OBCs70 part, paraffin 30 especially with embodiment 6, adds 50 parts of lime carbonate, 5 parts of anti-agent, and gained material fixed rate and recovery of shape rate are all more satisfactory.
Embodiment 9
Other removes OBCs70 part, paraffin 30 especially with embodiment 8, changes 50 parts of lime carbonate into 50 parts of expanded graphites, and gained material fixed rate and recovery of shape rate are all more satisfactory.
Embodiment 10
Other is with embodiment 6, but matrix is not single OBCs, but the mixture that OBC-1 and OBC-2 form with 2:1, gained material fixed rate and recovery of shape rate are all more satisfactory.
Embodiment 11
Other is with embodiment 6, but matrix is not single OBCs, but the mixture that OBC-2 and OBC-3 form with 1:4, gained material fixed rate and recovery of shape rate are all more satisfactory.
Embodiment 12
Other is changed to stearylamine with embodiment 6 with paraffin, and gained material fixed rate and recovery of shape rate are all more satisfactory.
Embodiment 13
Other is changed to octadecyl acid with embodiment 12 with stearylamine, and gained material fixed rate and recovery of shape rate are all more satisfactory.
Claims (3)
1. shape memory composites based on olefin block copolymers OBCs, at least form by following two kinds of components: OBCs and various small molecules crystal material, also can contain other component, these material modified characteristics are to determine permanent shape by OBCs, by small molecules crystal material control change of shape
Wherein,
Described polymkeric substance OBCs is to form the polymkeric substance with many block structures by ethene and other alpha-olefin copolymer, and many block structures of its uniqueness make it to present the form that is separated, the crystallizing field that wherein hard section is formed is a disperse phase, the non-crystalline region of soft section composition is an external phase, has the physical crosslinking structure
The small molecules crystalline material, for having excellent compatibility and melt temperature to be lower than the various crystal materials of OBCs fusing point with OBCs,
Other component is fire retardant, heat conduction properties-correcting agent, dispersion agent, oxidation inhibitor, tinting material or filler,
The ratio of quality and the number of copies of OBCs, small molecules crystalline material and other auxiliary agent is for example following:
100 parts of OBCs;
Crystallizable small molecules 20-200 part;
Other auxiliary agent 0-500 part.
2. the shape memory composites based on olefin block copolymers OBCs according to claim 1, it is characterized in that described OBCs, the olefin block copolymers that comprises various structures or composition promptly comprises one or more the mixing of the OBCs of any block length, sequence and soft or hard section ratio.
3. the shape memory composites based on olefin block copolymers OBCs according to claim 1 is characterized in that described small molecules crystal material, is in paraffin, lipid acid or the aliphatic amide one or more.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504474A (en) * | 2016-01-08 | 2016-04-20 | 同济大学 | Shape memory polymer composite and preparation method thereof |
| CN109988412A (en) * | 2019-03-14 | 2019-07-09 | 同济大学 | It is a kind of with fatty acid salt be can anti-phase shape memory macromolecule composite material |
| CN113131038A (en) * | 2021-03-30 | 2021-07-16 | 暨南大学 | Battery system and assembly method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260220A (en) * | 2008-04-10 | 2008-09-10 | 复旦大学 | Blending polymer shape memory material and preparation method thereof |
| CN103102636A (en) * | 2013-02-19 | 2013-05-15 | 复旦大学 | Shape memory material taken thermoplastic elastomer as matrix |
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2013
- 2013-04-19 CN CN2013101379186A patent/CN103224682A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260220A (en) * | 2008-04-10 | 2008-09-10 | 复旦大学 | Blending polymer shape memory material and preparation method thereof |
| CN103102636A (en) * | 2013-02-19 | 2013-05-15 | 复旦大学 | Shape memory material taken thermoplastic elastomer as matrix |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504474A (en) * | 2016-01-08 | 2016-04-20 | 同济大学 | Shape memory polymer composite and preparation method thereof |
| CN105504474B (en) * | 2016-01-08 | 2018-04-17 | 同济大学 | A kind of shape memory macromolecule composite material and preparation method thereof |
| CN109988412A (en) * | 2019-03-14 | 2019-07-09 | 同济大学 | It is a kind of with fatty acid salt be can anti-phase shape memory macromolecule composite material |
| CN113131038A (en) * | 2021-03-30 | 2021-07-16 | 暨南大学 | Battery system and assembly method thereof |
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Application publication date: 20130731 |