CN106633811B - 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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- CN106633811B CN106633811B CN201610963422.8A CN201610963422A CN106633811B CN 106633811 B CN106633811 B CN 106633811B CN 201610963422 A CN201610963422 A CN 201610963422A CN 106633811 B CN106633811 B CN 106633811B
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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
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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
- 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
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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
Abstract
The invention is applicable to the field of composite materials, and provides shape memory plastic paper, a preparation method and application thereof. According to the advantages of large deformation amount, processing deformation, low cost, easy regulation of shape recovery temperature and the like of the shape memory polymer, the shape memory plastic paper provided by the invention utilizes the surfactant to compound the shape memory polymer and the plant fiber together, so that the plant fiber paper has a corresponding shape memory function. The functional paper of the shape memory plastic paper provided by the invention can fix a temporary shape and recover to an original shape under a certain external stimulation condition.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to shape memory plastic paper and a preparation method and application thereof.
Background
The paper is an important material applied to character recording at home and abroad, and the common use of the paper not only promotes the rapid growth of book literature and data and the spread of scientific culture, but also promotes the development and prosperity of calligraphy and art and the change of Chinese character fonts. Since ancient times, paper mainly has three functions of recording, packaging and wiping, and ordinary paper does not have stimulus response characteristics.
In recent years, functional paper, i.e., a new paper with added functions on the basis of the original performance of paper, has become an important new material in sheet form. People can endow paper with functions of deodorization, antibiosis, heat resistance, electric conduction, catalysis and the like by using methods of functional fiber raw materials, functional fillers, paper processing, printing and the like or by utilizing advanced technologies such as nanotechnology, microcapsule technology, microfluidic technology and the like. Therefore, functional paper has attracted extensive attention as a new material in the fields of medical treatment, biology, energy, electronics, and the like, and has also penetrated various aspects of people's lives.
However, no functional paper having a shape memory function has been reported in the currently studied functional papers.
Disclosure of Invention
The invention aims to provide shape memory plastic paper and a preparation method and application thereof, and aims to provide functional paper with a shape memory function, expand the application range of the functional paper, improve the performance of a shape memory polymer and enrich the types of shape memory polymer materials.
The shape memory plastic paper comprises shape memory polymer, plant fiber paper and surfactant.
Further, the mass ratio of the shape memory polymer to the plant fiber paper to the surfactant is 10-50: 1-10.
Further, the shape memory polymer comprises at least one of polyurethane and DMAPS-co-AA copolymer.
Further, the surfactant is an ionic surfactant which is an anionic surfactant, a cationic surfactant or a zwitterionic surfactant.
Further, the thickness of the shape memory plastic paper is 0.05-0.2 mm.
The invention also provides a preparation method of the shape memory plastic paper, which comprises the following steps:
preparing a shape memory polymer solution and a surfactant aqueous solution;
soaking the plant fiber paper in the surfactant aqueous solution for 10-30 minutes, and drying;
soaking the dried plant fiber paper in the shape memory polymer solution for 10-30 minutes;
taking out the plant fiber paper after the soaking treatment, strickling, controlling the liquid absorption of the plant fiber paper to be 10-200 wt%, and then drying.
Further, the mass concentration of the shape memory polymer solution is 1-20 wt%.
Further, the mass concentration of the surfactant aqueous solution is 1-10 wt%.
Further, the drying temperature and the drying temperature are both 50-80 ℃.
The invention also provides an application of the shape memory plastic paper, and the application is that the shape memory plastic paper is used for preparing textiles, toys, medical supplies or stationery.
Compared with the prior art, the invention has the beneficial effects that: the shape memory plastic paper provided by the embodiment of the invention is a composite material of the shape memory polymer and the plant fiber paper, and according to the advantages of large deformation amount, processing deformation, low cost, easy adjustment of shape recovery temperature and the like of the shape memory polymer, a better adsorption effect is formed by surfactant ions and plant fibers, a better compatibility is formed by molecular chains at the other end and the polymer, the shape memory polymer and the plant fibers are compounded together, and a good adsorption effect of the shape memory polymer and the plant fibers is realized, so that the plant fiber paper has a corresponding shape memory function. The functional paper of the shape memory plastic paper provided by the embodiment of the invention can fix the temporary shape and recover to the original shape under a certain external stimulation condition.
Drawings
FIG. 1 is an SEM image of a shape memory plastic paper provided in example 1 of the present invention;
fig. 2a is a schematic diagram showing the comparison of mechanical properties of the shape memory plastic paper provided in example 2 of the present invention and the plant fiber paper without experimental operation in the vertical grain direction, and fig. 2b is a schematic diagram showing the comparison of mechanical properties in the horizontal grain direction;
fig. 3a is a schematic view of the original shape of the multiple shape memory plastic paper provided in embodiment 3 of the present invention, and fig. 3b is a schematic view of the shape after being cooled and fixed at 20 ℃ after being deformed and folded at 80 ℃;
fig. 4 is a schematic diagram of the shape recovery process of the shape memory plastic paper provided in embodiment 3 of the present invention during the temperature rising process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides shape memory plastic paper, and the composite material comprises a shape memory polymer, plant fiber paper and a surfactant.
The shape memory plastic paper provided by the embodiment of the invention is a composite material of the shape memory polymer and the plant fiber paper, and according to the advantages of large deformation amount, processing deformation, low cost, easy adjustment of shape recovery temperature and the like of the shape memory polymer, a better adsorption effect is formed by surfactant ions and plant fibers, a better compatibility is formed by molecular chains at the other end and the polymer, the shape memory polymer and the plant fibers are compounded together, and a good adsorption effect of the shape memory polymer and the plant fibers is realized, so that the plant fiber paper has a corresponding shape memory function. The functional paper of the shape memory plastic paper provided by the embodiment of the invention can fix the temporary shape and recover to the original shape under a certain external stimulation condition.
Specifically, the mass ratio of the shape memory polymer to the plant fiber paper to the surfactant is 10-50: 1-10. In the technical scheme of the invention, when the content of the shape memory polymer is high, the shape memory performance and the mechanical property of the composite material are excellent, and the use amount of the surfactant is increased, which is beneficial to the adsorption of the polymer. The shape memory polymer comprises at least one of polyurethane and DMAPS-co-AA copolymer (DMAPS: N, N-dimethyl (methacryloyloxyethyl) ammonio propanesulfonate inner salt, co: copolymerization, AA: acrylic acid). The surfactant is an anionic surfactant or a cationic surfactant.
Specifically, the thickness of the shape memory plastic paper is 0.05-0.2 mm.
The embodiment of the invention also provides a preparation method of the shape memory plastic paper, which comprises the following steps:
preparing a shape memory polymer solution and a surfactant aqueous solution;
soaking the plant fiber paper in the surfactant aqueous solution for 10-30 minutes, and drying; will be provided with
Soaking the dried plant fiber paper in the shape memory polymer solution for 10-30 minutes; soaking in water
Taking out the plant fiber paper after the soaking treatment, strickling, controlling the liquid absorption of the plant fiber paper to be 10-200 wt%, and then drying.
Specifically, the solvent in the shape memory polymer solution is dimethylformamide, tetrahydrofuran or dimethyl sulfoxide, and the mass concentration of the solution is 1-20 wt%. The mass concentration of the surfactant aqueous solution is 1-10 wt%. The drying temperature and the drying temperature are both 50-80 ℃. The mass concentration of the shape memory polymer solution is too low, and the adsorption amount of the paper to the polymer is less; the concentration is higher, and the adsorption amount of the polymer by the paper is increased; the high mass concentration of the surfactant is beneficial to polymer adsorption, and the more the polymer adsorption amount is, the higher the required surfactant concentration is; the drying temperature varies depending on the solvent selected.
The embodiment of the invention also provides an application of the shape memory plastic paper, and the application is to use the shape memory plastic paper for preparing textiles, toys, medical supplies or stationery.
Example 1
A novel shape memory polyurethane/paper composite material is mainly prepared by compounding 50 parts by weight of shape memory polyurethane resin, 40 parts by weight of dust-free paper and 10 parts by weight of sodium dodecyl benzene Sulfonate (SD); the shape memory polyurethane adopts 65 wt% of polybutylene adipate as a soft segment phase and 35 wt% of a hard segment phase constructed by diphenylmethane diisocyanate and butanediol. The preparation method comprises the following steps: 1)
firstly, dissolving Shape Memory Polyurethane (SMPU) in N, N-Dimethylformamide (DMF) solvent to prepare 10 wt% of SMPU/DMF solution for later use; 2) soaking the dust-free paper in a 10 wt% aqueous solution of sodium dodecyl benzene sulfonate for 20 minutes, and drying at 80 ℃ for later use; 3) soaking the dried dust-free paper in an SMPU/DMF solution for 30 minutes; 4) taking out the soaked dust-free paper, and strickling the dust-free paper by using a glass rod to control the liquid absorption amount of the plant fiber paper; 5) and drying the dust-free paper in a blast oven at the temperature of 80 ℃ to obtain the SMPU/paper composite material, namely the shape memory plastic paper. The special plant paper for the dust-free paper is loose, has many holes and is few in impurities. SEM images (electron scanning micrographs) of the surface of the SMPU-treated airlaid paper fibers (i.e., composite) as shown in fig. 1, it was clearly observed that the polymer adhered firmly to the fiber surface, forming a robust SMPU/paper composite, compared to the original fiber surface.
Example 2
A novel shape memory copolymer/paper composite material is mainly prepared by compounding 50 parts by weight of a shape memory copolymer, 45 parts by weight of printing paper and 5 parts by weight of sodium dodecyl benzene Sulfonate (SD), wherein the shape memory copolymer is mainly prepared by copolymerizing 80 wt% of N, N-dimethyl (methacryloyloxyethyl) ammonium propane sulfonic acid inner salt (DMAPS) and 20 wt% of Acrylic Acid (AA). The preparation method comprises the following steps: 1) firstly, dissolving DMAPS-co-AA copolymer in deionized water to prepare 10 wt% solution for later use; 2) soaking the printing paper in an aqueous solution containing 10 wt% of sodium dodecyl benzene sulfonate for 20 minutes, and drying the printing paper at 50 ℃ for later use; 3) soaking the dried printing paper in DMAPS-co-AA aqueous solution for 20 minutes; 4) taking out the printing paper after soaking treatment, and strickling the printing paper by using a glass rod to control the liquid absorption amount of the plant fiber paper; 5) and drying the printing paper in a forced air oven at 80 ℃ to obtain the shape memory copolymer/paper composite material, namely the shape memory plastic paper. The mechanical properties of the prepared shape memory copolymer/paper composite are tested in comparison with paper as shown in fig. 2a and 2 b. The elongation at break of the paper before being treated by the shape memory polymer in the horizontal grain direction is about 10 percent, the elongation at break of the paper before being treated by the shape memory polymer in the vertical grain direction is about 20 percent, the elongation at break of the paper in the horizontal grain direction is improved to 50 percent after being treated by the shape memory polymer, and the strength at break is also improved; and the elongation at break in the direction perpendicular to the grain direction is increased to 40%. The mechanical property test result shows that the mechanical strength and the elongation at break of the composite material are obviously improved after the polymer is introduced.
Example 3
A novel zwitterionic shape memory polyurethane/paper composite material mainly comprises 50 parts by weight of zwitterionic shape memory polyurethane and 25 parts by weight of neutral filter paper, wherein the zwitterionic shape memory polyurethane is mainly prepared from N-Methyldiethanolamine (MDEA), Hexamethylene Diisocyanate (HDI), 1, 4-Butanediol (BDO) and 1, 3-Propyl Sultone (PS) and contains 50 wt% of MDEA-PS and 50 wt% of HDI-BDO. The specific preparation method of the zwitterionic shape memory polyurethane/paper composite material comprises the following steps: 1) firstly, dissolving zwitter-ion shape memory polyurethane in DMF to prepare 10 wt% solution for standby; 2) soaking the neutral filter paper in a zwitter-ion shape memory polyurethane solution for 15 minutes; 4) taking out the soaked zwitter-ion shape memory polyurethane, leveling the polyurethane by using a glass rod, and controlling the liquid absorption amount; 5) and drying the neutral filter paper in a blast oven at the temperature of 80 ℃ to obtain the zwitter-ion shape memory polyurethane/paper composite material, namely the shape memory plastic paper. Cutting a rectangular sample strip from the prepared zwitterion shape memory polyurethane/paper composite material, as shown in fig. 3 a; the paper sample strip is cooled and fixed at 20 ℃ after being deformed and folded at 80 ℃ to obtain the shape shown in figure 3b, and has better shape fixing performance. The fixed folded paper sample strip is placed in an environment with the temperature higher than 50 ℃, so that the paper sample strip can be obviously subjected to thermal shape recovery gradually along with the temperature rise, as shown in figure 4, and finally can be completely recovered to the initial shape at 80 ℃, so that a good shape recovery effect is shown, and the prepared zwitterion shape memory polyurethane/paper composite material has good thermal shape memory performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The preparation method of the shape memory plastic paper is characterized in that the shape memory plastic paper comprises a shape memory polymer, plant fiber paper and a surfactant, wherein the mass ratio of the shape memory polymer to the plant fiber paper to the surfactant is 10-50: 1-10; the shape memory polymer comprises DMAPS-co-AA copolymer (DMAPS: N, N-dimethyl (methacryloyloxyethyl) ammonio propanesulfonic acid inner salt, co: copolymerization, AA: acrylic acid); the surfactant is an anionic surfactant, a cationic surfactant or a zwitterionic surfactant;
the preparation method comprises the following steps:
preparing a shape memory polymer solution and a surfactant aqueous solution;
soaking the plant fiber paper in the surfactant aqueous solution for 10-30 minutes, and drying;
soaking the dried plant fiber paper in the shape memory polymer solution for 10-30 minutes;
taking out the plant fiber paper after the soaking treatment, strickling, controlling the liquid absorption of the plant fiber paper to be 10-200 wt%, and then drying.
2. The method according to claim 1, wherein the shape memory polymer solution has a mass concentration of 1 to 20 wt%.
3. The method according to claim 1, wherein the surfactant aqueous solution has a mass concentration of 1 to 10 wt%.
4. The method according to claim 1, wherein the drying temperature and the drying temperature are both 50-80 ℃.
5. The method of claim 1, wherein the shape-memory plastic paper has a thickness of 0.05 to 0.2 mm.
6. Use of the shape memory plastic paper prepared by the method for preparing the shape memory plastic paper according to any one of claims 1 to 5, characterized in that the shape memory plastic paper is used for preparing textiles, toys, medical supplies or stationery.
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| WO2018076278A1 (en) * | 2016-10-28 | 2018-05-03 | 深圳大学 | Shape memory plastic paper, preparation method therefor and application thereof |
| CN110563906B (en) * | 2019-08-15 | 2021-11-16 | 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 |
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- 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 |
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