CN106633811A - Shape memory plastic paper and preparation method and application thereof - Google Patents
Shape memory plastic paper and preparation method and application thereof Download PDFInfo
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- CN106633811A CN106633811A CN201610963422.8A CN201610963422A CN106633811A CN 106633811 A CN106633811 A CN 106633811A CN 201610963422 A CN201610963422 A CN 201610963422A CN 106633811 A CN106633811 A CN 106633811A
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- paper
- shape memory
- shape
- plastic paper
- plant fiber
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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
- C08L75/06—Polyurethanes from polyesters
-
- 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
-
- 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
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention is applicable to the field of composite materials and provides a shape memory plastic paper and preparation method and application thereof. The shape memory plastic paper contains a shape memory polymer, plant fiber paper and a surface active agent. The shape memory plastic paper has the advantages of large deformation amount based on the shape memory polymer, processing deformation, low cost, easily regulated shape recovery temperature and the like, the surface active agent is utilized to compound the shape memory polymer and the plant fiber paper, and accordingly the plant fiber paper has a corresponding shape memory function. The shape memory plastic paper has the function, a temporary shape can be fixed, and an initial shape can be also recovered under a certain outside stimulation condition.
Description
Technical field
The invention belongs to field of compound material, more particularly to a kind of shape memory plastic paper and its preparation method and application.
Background technology
Paper is domestic and international application in the important materials of writing record, commonly using for paper, not only promotes books document money
The rapid growth of material and the propagation of science and culture, and promote the development of calligraphy art, the transition of flourishing and Chinese character style.From ancient times
Since, mainly with recording, packing, wiping three zones, common paper does not have stimuli responsive characteristic to paper.
In recent years, functional paper, i.e., increase a kind of Novel paper of function on the basis of the original performance of paper, becomes a kind of weight
The lamellar new material wanted.People can by using methods such as functional fiber raw material, functional filler, paper conversion, printings, or
Paper deodorization, antibacterial, heat-resisting, conductive, catalysis are given using hard-core technologies such as nanotechnology, microcapsule technology, microflow control techniques
Etc. function.Therefore, functional paper has caused the wide of the fields such as medical treatment, biology, the energy, electronic technology as a kind of new material
General concern, while also penetrating into the various aspects of people's life.
However, not studies have reported that the functional paper with shape memory function in the functional paper of research at present.
The content of the invention
The technical problem to be solved is to provide a kind of shape memory plastic paper and its preparation method and application,
A kind of functional paper with shape memory function, the range of application of expanding function paper are aimed to provide, while improve shape memory gathering
The performance of compound, enriches the species of shape memory polymer material.
The present invention is achieved in that a kind of shape memory plastic paper, and the shape memory plastic paper includes shape memory
Polymer, plant fiber paper and surfactant.
Further, the mass ratio of the shape-memory polymer, plant fiber paper and surfactant is 10～50:10
～50:1～10.
Further, the shape-memory polymer includes at least one in polyurethane, DMAPS-co-AA copolymers.
Further, the surfactant is that ionic surfactant is anionic surfactant, cation
Type surfactant or zwitterionic surfactant.
Further, the thickness of the shape memory plastic paper is 0.05～0.2mm.
Present invention also offers a kind of preparation method of above-mentioned shape memory plastic paper, comprises the following steps：
Prepare shape-memory polymer solution and aqueous surfactant solution；
Plant fiber paper is placed in the aqueous surfactant solution and is soaked 10～30 minutes, and dried；
Plant fiber paper after drying is soaked 10～30 minutes in the shape-memory polymer solution；
Plant fiber paper after immersion treatment is taken out, is struck off, the liquid absorption for controlling the plant fiber paper is 10wt%
～200wt%, is then dried.
Further, the mass concentration of the shape-memory polymer solution is 1～20wt%.
Further, the mass concentration of the aqueous surfactant solution is 1～10wt%.
Further, the temperature of the drying and the drying is 50～80 DEG C.
Present invention also offers a kind of application of above-mentioned shape memory plastic paper, the application is by the shape memory
Plastic paper is used to prepare textile, toy, medical supplies or stationery.
Compared with prior art, beneficial effect is the present invention：Shape memory plastic paper provided in an embodiment of the present invention, be
The composite of shape-memory polymer and plant fiber paper, according to the deflection of shape-memory polymer is big, machining deformation, into
The advantages of this is low, shape recovery temperature is easily dimmable, forms preferable absorption and makees using surface active agent ion and Plant fiber
With, and other end strand will form the preferable compatibility with polymer, and shape-memory polymer is combined with Plant fiber's matter
Together, the good absorption effect of shape-memory polymer and Plant fiber is realized, so that plant fiber paper has accordingly
Shape memory function.This functional paper of shape memory plastic paper provided in an embodiment of the present invention, can fix temporary shapes, certain
Under the conditions of environmental stimuli, original shape can be returned to again.
Description of the drawings
Fig. 1 is the SEM figures of the shape memory plastic paper that the embodiment of the present invention 1 is provided；
Fig. 2 a are that the embodiment of the present invention 2 the shape memory plastic paper for providing and the plant fiber paper for not carrying out test operation exist
Mechanical property comparison schematic diagram on vertical ridge orientation, Fig. 2 b are that its mechanical property on horizontal ridge orientation compares signal
Figure；
Fig. 3 a are the original shape schematic diagrams of the multiple shape memory plastic paper that the embodiment of the present invention 3 is provided, Fig. 3 b be it
Schematic shapes after 80 DEG C of deformable foldings after 20 DEG C of coolings are fixed；
Fig. 4 be the embodiment of the present invention 3 provide shape memory plastic paper in temperature-rise period shape recovery process schematic diagram.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and
It is not used in the restriction present invention.
Embodiments provide a kind of shape memory plastic paper, the composite include shape-memory polymer,
Plant fiber paper and surfactant.
Shape memory plastic paper provided in an embodiment of the present invention, is the composite wood of shape-memory polymer and plant fiber paper
Material, according to the deflection of shape-memory polymer is big, machining deformation, low cost, easily dimmable shape recovery temperature the advantages of, profit
Preferable attraction function is formed with surface active agent ion and Plant fiber, and other end strand will be formed preferably with polymer
The compatibility, shape-memory polymer is combined with each other with Plant fiber's matter, realize shape-memory polymer and Plant fiber
Good absorption effect so that plant fiber paper has corresponding shape memory function.Shape provided in an embodiment of the present invention
Memory plastics paper this functional paper, can fix temporary shapes, under the conditions of certain environmental stimuli, original shape can be returned to again.
Specifically, the mass ratio of the shape-memory polymer, plant fiber paper and surfactant is 10～50:10～
50:1～10.In the inventive solutions, when shape-memory polymer content is more, the shape-memory properties of composite
And excellent in mechanical performance, dosage of surfactant improves and is conducive to the absorption of polymer.The shape-memory polymer includes poly-
Urethane, DMAPS-co-AA copolymer (DMAPS：N, N- dimethyl (methylacryoyloxyethyl) ammonium propane sulfonic acid inner salt, co：Altogether
It is poly-, AA：Acrylic acid) at least one.The surfactant is that anionic surfactant or cationic are lived
Property agent.
Specifically, the thickness of the shape memory plastic paper is 0.05～0.2mm.
The embodiment of the present invention additionally provides a kind of preparation method of above-mentioned shape memory plastic paper, comprises the following steps：
Prepare shape-memory polymer solution and aqueous surfactant solution；
Plant fiber paper is placed in the aqueous surfactant solution and is soaked 10～30 minutes, and dried；
Plant fiber paper after drying is soaked 10～30 minutes in the shape-memory polymer solution；
Plant fiber paper after immersion treatment is taken out, is struck off, the liquid absorption for controlling the plant fiber paper is 10wt%
～200wt%, is then dried.
Specifically, the solvent in the shape-memory polymer solution is dimethylformamide, tetrahydrofuran or dimethyl
Sulfoxide, the mass concentration of the solution is 1～20wt%.The mass concentration of the aqueous surfactant solution is 1～10wt%.
The temperature of the drying and the drying is 50～80 DEG C.The mass concentration of shape-memory polymer solution is too low, and paper is to poly-
The absorption amount of compound is less；Concentration is higher, and paper increases the absorption amount of polymer；Surfactant qualities concentration height is conducive to gathering
Compound adsorbs, and polymer absorption amount is more, and required surfactant concentration is bigger；Baking temperature with selected solvent it is different and not
Together.
The embodiment of the present invention additionally provides a kind of application of above-mentioned shape memory plastic paper, and the application is by the shape
Memory plastics paper is used to prepare textile, toy, medical supplies or stationery.
Embodiment 1
A kind of new shape memory polyurethane/paper composites, mainly by the shape memory polyurethane resin of 50 parts of weight,
The dodecylbenzene sodium sulfonate (SD) of the dust-free paper of 40 parts of weight and 10 parts of weight is compound to be prepared；The shape memory polyurethane is adopted
Poly adipate succinic acid ester with 65wt% weight fractions is soft section phase, and 35wt% weight fractions are by diphenylmethane diisocyanate
The hard section phase that ester and butanediol are constructed.Concrete preparation method is as follows：1) first shape memory polyurethane (SMPU) is dissolved in N, N-
The SMPU/DMF solution for standby of 10wt% is made in dimethylformamide (DMF) solvent；2) dust-free paper in 10wt% concentration ten
Soak 20 minutes in the aqueous solution of dialkyl benzene sulfonic acids sodium, and 80 DEG C of dry for standby；3) by the dust-free paper after drying in SMPU/
Soak 30 minutes in DMF solution；4) dust-free paper after immersion treatment is taken out, is struck off with Glass rod, control plant fiber paper
Liquid absorption；5) dust-free paper is dried in 80 DEG C of convection ovens, obtains final product the composite of SMPU/ paper, as shape memory plastic paper.
The special plant paper of the dust-free paper, loose, hole is more, and impurity is few.Dustless paper fiber (i.e. composite wood Jing after SMPU process
Material) surface SEM figures (electron scanning imaging figure) as shown in figure 1, compared with pristine fibre surface, can substantially observe polymerization
Thing is tightly adhered to fiber surface, defines the composite of firm SMPU/ paper.
Embodiment 2
A kind of new shape memory copolymer/paper composites, mainly by the shape memory polyurethane resin of 50 parts of weight,
The dodecylbenzene sodium sulfonate (SD) of the printing paper of 45 parts of weight and 5 parts of weight is compound to be prepared, shape memory copolymerization owner
Will adopt 80wt% weight fractions N, N- dimethyl (methylacryoyloxyethyl) ammonium propane sulfonic acid inner salt (DMAPS) and
Acrylic acid (AA) copolymerization of 20wt% weight fractions is formed.Concrete preparation method is as follows：1) it is first that DMAPS-co-AA copolymers is molten
Solution is made into the solution for standby of 10wt% in deionized water；2) printing paper is in the aqueous solution containing 10wt% dodecylbenzene sodium sulfonate
Middle immersion 20 minutes, and 50 DEG C of dry for standby；3) printing paper after drying is soaked in DMAPS-co-AA aqueous solutions 20 points
Clock；4) printing paper after immersion treatment is taken out, is struck off with Glass rod, control the liquid absorption of plant fiber paper；5) in 80 DEG C of drums
Printing paper is dried in wind baking oven, shape memory copolymer/paper composites, as shape memory plastic paper are obtained final product.Prepared
The Mechanics Performance Testing that shape memory copolymer/paper composites are contrasted with paper is as shown in Figure 2 a and 2 b.Without Jing shapes note
Recall elongation at break about 10% of the paper before polymer treatment in horizontal ridge orientation, and the fracture on vertical ridge orientation
Percentage elongation about 20%, Jing after the process of shape memory copolymer, the elongation at break of horizontal ridge orientation is promoted to 50%, and fracture is strong
Degree displays that raising；And the elongation at break of vertical ridge orientation is promoted to 40%.Mechanical experimental results show, polymer
After introducing, the mechanical strength and elongation at break of composite is significantly improved.
Embodiment 3
A kind of new type amphoteric ion shape memory polyurethane/paper composites, the main amphion comprising 50 parts of weight
Prepared by the neutral filter paper of shape memory polyurethane and 25 parts of weight, the amphion shape memory polyurethane is mainly by N- methyl
Diethanolamine (MDEA), hexamethylene diisocyanate (HDI), BDO (BDO), and 1,3- propyl sulfonic acid lactone
(PS) it is prepared from, content containing 50wt%MDEA-PS, 50wt%HDI-BDO contents.Amphion shape memory polyurethane/paper
The concrete preparation method of composite is as follows：1) first amphion shape memory polyurethane is dissolved in DMF and is made into 10wt%
Solution for standby；2) neutral filter paper soaks 15 minutes in amphion shape memory polyurethane solution；4) immersion treatment
Amphion shape memory polyurethane afterwards takes out, and is struck off with Glass rod, controls liquid absorption；5) dry in 80 DEG C of convection ovens
Neutral filter paper, obtains final product amphion shape memory polyurethane/paper composites, as shape memory plastic paper.From what is prepared
A rectangular specimens are cut in amphion shape memory polyurethane/paper composites, as shown in Figure 3 a；The 80 DEG C of changes of pattern bar
The shapes for obtaining as shown in Figure 3 b after shape folding after 20 DEG C of coolings are fixed, with preferable shape fixability energy.After fixation
The pattern bar of folding is placed on temperature higher than under 50 DEG C of environment, it can clearly be seen that pattern bar is raised with temperature, heat progressively occurs
Cause shape to recover, as shown in figure 4, original shape finally can be completely recovered under the conditions of 80 DEG C, show preferable shape and recover
Effect, shows that prepared amphion shape memory polyurethane/paper composites have preferable thermal shape memory performance.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of shape memory plastic paper, it is characterised in that the shape memory plastic paper includes shape-memory polymer, plant
Fibrous paper and surfactant.
2. shape memory plastic paper as claimed in claim 1, it is characterised in that the shape-memory polymer, Plant fiber
The mass ratio of paper and surfactant is 10～50:10～50:1～10.
3. shape memory plastic paper as claimed in claim 1, it is characterised in that the shape-memory polymer includes poly- ammonia
At least one in ester, DMAPS-co-AA copolymers.
4. shape memory plastic paper as claimed in claim 1, it is characterised in that the surfactant is that ion-type surface is lived
Property agent be anionic surfactant, cationic surface active agent or zwitterionic surfactant.
5. shape memory plastic paper as claimed in claim 1, it is characterised in that the thickness of the shape memory plastic paper is
0.05～0.2mm.
6. a kind of preparation method of the shape memory plastic paper as described in claim 1 to 5 any one, it is characterised in that bag
Include following steps：
Prepare shape-memory polymer solution and aqueous surfactant solution；
Plant fiber paper is placed in the aqueous surfactant solution and is soaked 10～30 minutes, and dried；
Plant fiber paper after drying is soaked 10～30 minutes in the shape-memory polymer solution；
Plant fiber paper after immersion treatment is taken out, is struck off, control the liquid absorption of the plant fiber paper for 10wt%～
200wt%, is then dried.
7. preparation method as claimed in claim 6, it is characterised in that the mass concentration of the shape-memory polymer solution is
1～20wt%.
8. preparation method as claimed in claim 6, it is characterised in that the mass concentration of the aqueous surfactant solution is 1
～10wt%.
9. preparation method as claimed in claim 6, it is characterised in that the temperature of the drying and the drying is 50～80
℃。
10. a kind of application of the shape memory plastic paper as described in claim 1 to 5 any one, it is characterised in that described to answer
With for by the shape memory plastic paper be used for prepare textile, toy, medical supplies or stationery.
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| CN201610963422.8A CN106633811B (en) | 2016-10-28 | 2016-10-28 | Shape memory plastic paper and preparation method and application thereof |
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| CN201610963422.8A CN106633811B (en) | 2016-10-28 | 2016-10-28 | Shape memory plastic paper and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018076278A1 (en) * | 2016-10-28 | 2018-05-03 | 深圳大学 | Shape memory plastic paper, preparation method therefor and application thereof |
| CN110563906A (en) * | 2019-08-15 | 2019-12-13 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0834067A (en) * | 1994-07-22 | 1996-02-06 | Shin Etsu Polymer Co Ltd | Shape memory paper |
| CN104193893A (en) * | 2014-07-24 | 2014-12-10 | 深圳大学 | Shape memory polymer based on betaine and preparation method of shape memory polymer |
| CN105524289A (en) * | 2015-11-26 | 2016-04-27 | 哈尔滨工业大学 | Preparation method and application of shape memory polyurethane film laminating solution |
-
2016
- 2016-10-28 CN CN201610963422.8A patent/CN106633811B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0834067A (en) * | 1994-07-22 | 1996-02-06 | Shin Etsu Polymer Co Ltd | Shape memory paper |
| CN104193893A (en) * | 2014-07-24 | 2014-12-10 | 深圳大学 | Shape memory polymer based on betaine and preparation method of shape memory polymer |
| CN105524289A (en) * | 2015-11-26 | 2016-04-27 | 哈尔滨工业大学 | Preparation method and application of shape memory polyurethane film laminating solution |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018076278A1 (en) * | 2016-10-28 | 2018-05-03 | 深圳大学 | Shape memory plastic paper, preparation method therefor and application thereof |
| CN110563906A (en) * | 2019-08-15 | 2019-12-13 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
| CN110563906B (en) * | 2019-08-15 | 2021-11-16 | 深圳大学 | Shape memory polyurethane and preparation method and application thereof |
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| CN106633811B (en) | 2020-06-12 |
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