CN111303569A - Preparation method of tough polymer film - Google Patents
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- CN111303569A CN111303569A CN202010024399.2A CN202010024399A CN111303569A CN 111303569 A CN111303569 A CN 111303569A CN 202010024399 A CN202010024399 A CN 202010024399A CN 111303569 A CN111303569 A CN 111303569A
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- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
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Abstract
The invention discloses a preparation method of a tough polymer film, which comprises the following steps of firstly, carrying out electrostatic self-assembly on cellulose nanocrystals modified by polyethyleneimine and montmorillonite nanosheets to obtain a CNC and MMT supermolecule assembly, then dispersing the CNC and MMT supermolecule assembly into a polyvinyl alcohol aqueous solution, uniformly stirring and pouring the assembly into a culture dish, and forming a film by using a solvent evaporation method to obtain a composite film with synchronously increased tensile strength and elongation at break, so that a tough material with balanced performance is obtained, the stress transfer efficiency is improved, the tensile strength of fibers is effectively increased, the elongation at break is increased by using multiple weak interactions, and the defect that the elongation at break is neglected when the breaking strength is improved in the conventional method for enhancing the mechanical property of a polymer matrix by using nanofillers is overcome.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a preparation method of a tough polymer film.
Background
The two-dimensional material is a novel crystal material with atomic-scale thickness, and the unique electronic confinement effect endows the material with unique physical and chemical properties and rich scientific connotation, thereby having important application prospects in numerous fields, in particular to the aspects of electronic devices, photoelectric devices and the like. The premise of researching the properties of the materials and putting the materials into large-scale application is the preparation and accurate and effective integration of high-quality two-dimensional materials; the flaky calcium carbonate is assembled on biological macromolecules layer by accurately regulating and controlling shells in the nature to form a brick mud structure, and a great amount of weak interaction exists between interfaces to endow the pearl layer with super-strong strength and toughness. However, the artificially synthesized material cannot precisely control the structural elements through a large amount of interaction like natural materials (shells, bones and the like), so that stress cannot be effectively transferred when each structural element is stressed, and the material is broken. The former work of reinforcing polymer films by utilizing nano filling materials has obvious improvement on tensile strength, but the elongation at break is not changed greatly or even reduced, so that the toughness enhancement of the composite film is limited, and the reason is that the interaction force which can be used as sacrificial bonding between structural elements is less, and the stress transmission efficiency is also reduced. Under the background that flexible electronic equipment, tough composite materials and application thereof are increasingly valued at home and abroad, the development of methods such as reinforcing and toughening of the composite materials is necessary and urgent, and the method has important scientific significance and social value.
At present, the existing technology of utilizing nano reinforced polymer film has the disadvantages that although the tensile strength of the composite film is improved, the improvement of the elongation at break is not obvious, even the elongation at break is reduced, and the practicability is not good. Accordingly, one skilled in the art provides a method for preparing a tough polymer film to solve the above problems in the background art.
Disclosure of Invention
The invention aims to provide a preparation method of a tough polymer film, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a tough polymer film, comprising the steps of:
1) adding 10mL of PEI aqueous solution with the concentration of 3.0 wt% into 5mL of CNC suspension with the concentration of 3.0 wt%, continuously stirring for 1h at room temperature, then adjusting the pH of the mixed solution to 1.3 by using concentrated hydrochloric acid to enhance the ionic interaction between CNC and PEI, continuously stirring for ten minutes, centrifuging the mixed solution at a high speed for 20min by a 13000rpm rotary speed centrifuge, discarding supernatant, washing precipitates for three times by using ultrapure water, removing free PEI molecules without the interaction, finally re-dispersing the precipitates in water, centrifuging at a low speed for 5min, removing the CNC aggregates, collecting the supernatant to obtain mono-dispersed CNC suspension with the concentration of 1.0 wt%, and naming the suspension as PCNC suspension for later use;
2) adding 2g of montmorillonite powder into 500mL of ultrapure water, continuously dissolving and stirring for one week, centrifuging for 5min by a centrifuge, discarding the precipitate, collecting supernatant to obtain fully stripped MMT nanosheets for later use, wherein the concentration is 0.7 wt%;
3) mixing the PCNC suspension liquid prepared in the step 1 with the MMT suspension liquid prepared in the step 2 to prepare a PCNC and MMT assembly;
4) and (3) mixing the PCNC and MMT assembly prepared in the step three with a certain amount of PVA solution, uniformly stirring at normal temperature, and airing to form a film to prepare the PCNC, MMT and PVA composite film.
As a further scheme of the invention: in the step 2), the rotating speed of the centrifuge is set to 8000rmp when the centrifuge works for 5 min.
As a still further scheme of the invention: in the step 3), the mass ratio of the PCNC to the MMT in the prepared PCNC and MMT assembly is 1: 2.
As a still further scheme of the invention: in the step 3), the mass ratio of the PCNC and MMT assembly to the PVA is 1: 9.
As a still further scheme of the invention: in the step 4), the stirring time is at least 24 hours at normal temperature.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, each structural element with excellent mechanical properties is self-assembled, the mechanical properties of the polymer matrix are enhanced by using the assembly, the assembly contains a large amount of weak interaction, and the assembly serves as a sacrificial bond when being stretched by stress, so that the stress transmission efficiency is improved, the tensile strength of the fiber is effectively increased, and the elongation at break is increased by using multiple weak interaction, thereby obtaining a tough material with balanced properties, and solving the defect that the elongation at break is neglected in improving the strength at break in the existing method for enhancing the mechanical properties of the polymer matrix by using the nano filler.
Drawings
FIG. 1 is a transmission electron microscope topography of the PCNC and MMT assembly prepared by the invention.
FIG. 2 is a scanning electron microscope topography of the PCNC, MMT and PVA composite film prepared by the invention.
FIG. 3 is a diagram showing the mechanical properties of the PCNC, MMT and PVA composite film prepared by the present invention.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to specific embodiments.
Example 1: a method for preparing a tough polymer film, comprising the steps of:
1) adding 10mL of PEI aqueous solution with the concentration of 3.0 wt% into 5mL of CNC suspension with the concentration of 3.0 wt%, continuously stirring for 1h at room temperature, then adjusting the pH of the mixed solution to 1.3 by using concentrated hydrochloric acid to enhance the ionic interaction between CNC and PEI, continuously stirring for ten minutes, centrifuging the mixed solution at a high speed for 20min by a 13000rpm rotary speed centrifuge, discarding supernatant, washing precipitates for three times by using ultrapure water, removing free PEI molecules without the interaction, finally re-dispersing the precipitates in water, centrifuging at a low speed for 5min, removing the CNC aggregates, collecting the supernatant to obtain mono-dispersed CNC suspension with the concentration of 1.0 wt%, and naming the suspension as PCNC suspension for later use;
2) adding 2g of montmorillonite powder into 500mL of ultrapure water, continuously dissolving and stirring for one week, centrifuging for 5min by a centrifuge, discarding the precipitate, collecting supernatant to obtain fully stripped MMT nanosheets for later use, wherein the concentration is 0.7 wt%;
3) mixing the PCNC suspension liquid prepared in the step 1 with the MMT suspension liquid prepared in the step 2 to prepare a PCNC and MMT assembly;
4) and (3) mixing the PCNC and MMT assembly prepared in the step three with a certain amount of PVA solution, uniformly stirring at normal temperature, and airing to form a film to prepare the PCNC, MMT and PVA composite film.
In the step 2), the rotating speed of the centrifuge is set to 8000rmp when the centrifuge works for 5 min.
In the step 3), the mass ratio of the PCNC to the MMT in the prepared PCNC and MMT assembly is 1: 2.
In the step 3), the mass ratio of the PCNC and MMT assembly to the PVA is 1: 9.
In the step 4), the stirring time is at least 24 hours at normal temperature.
Example 2: a method for preparing a tough polymer film, comprising the steps of:
1) adding 10mL of PEI aqueous solution with the concentration of 3.0 wt% into 5mL of CNC suspension with the concentration of 3.0 wt%, continuously stirring for 1h at room temperature, then adjusting the pH of the mixed solution to 1.3 by using concentrated hydrochloric acid to enhance the ionic interaction between CNC and PEI, continuously stirring for ten minutes, centrifuging the mixed solution at a high speed for 20min by a 13000rpm rotary speed centrifuge, discarding supernatant, washing precipitates for three times by using ultrapure water, removing free PEI molecules without the interaction, finally re-dispersing the precipitates in water, centrifuging at a low speed for 5min, removing the CNC aggregates, collecting the supernatant to obtain mono-dispersed CNC suspension with the concentration of 1.0 wt%, and naming the suspension as PCNC suspension for later use;
2) adding 2g of montmorillonite powder into 500mL of ultrapure water, continuously dissolving and stirring for one week, centrifuging for 5min by a centrifuge, discarding the precipitate, collecting supernatant to obtain fully stripped MMT nanosheets for later use, wherein the concentration is 0.7 wt%;
3) mixing the PCNC suspension liquid prepared in the step 1 with the MMT suspension liquid prepared in the step 2 to prepare a PCNC and MMT assembly;
4) and (3) mixing the PCNC and MMT assembly prepared in the step three with a certain amount of PVA solution, uniformly stirring at normal temperature, and airing to form a film to prepare the PCNC, MMT and PVA composite film.
In the step 2), the rotating speed of the centrifuge is set to 8000rmp when the centrifuge works for 5 min.
In the step 3), the mass ratio of the PCNC to the MMT in the prepared PCNC and MMT assembly is 1: 1.
In the step 3), the mass ratio of the PCNC and MMT assembly to the PVA is 1: 9.
In the step 4), the stirring time is at least 24 hours at normal temperature.
Compared with a pure PVA film, the tensile strength of the composite film of the embodiment is improved by 206 percent, and the elongation at break is improved by 125 percent.
Example 3: a method for preparing a tough polymer film, comprising the steps of:
1) adding 10mL of PEI aqueous solution with the concentration of 3.0 wt% into 5mL of CNC suspension with the concentration of 3.0 wt%, continuously stirring for 1h at room temperature, then adjusting the pH of the mixed solution to 1.3 by using concentrated hydrochloric acid to enhance the ionic interaction between CNC and PEI, continuously stirring for ten minutes, centrifuging the mixed solution at a high speed for 20min by a 13000rpm rotary speed centrifuge, discarding supernatant, washing precipitates for three times by using ultrapure water, removing free PEI molecules without the interaction, finally re-dispersing the precipitates in water, centrifuging at a low speed for 5min, removing the CNC aggregates, collecting the supernatant to obtain mono-dispersed CNC suspension with the concentration of 1.0 wt%, and naming the suspension as PCNC suspension for later use;
2) adding 2g of montmorillonite powder into 500mL of ultrapure water, continuously dissolving and stirring for one week, centrifuging for 5min by a centrifuge, discarding the precipitate, collecting supernatant to obtain fully stripped MMT nanosheets for later use, wherein the concentration is 0.7 wt%;
3) mixing the PCNC suspension liquid prepared in the step 1 with the MMT suspension liquid prepared in the step 2 to prepare a PCNC and MMT assembly;
4) and (3) mixing the PCNC and MMT assembly prepared in the step three with a certain amount of PVA solution, uniformly stirring at normal temperature, and airing to form a film to prepare the PCNC, MMT and PVA composite film.
In the step 2), the rotating speed of the centrifuge is set to 8000rmp when the centrifuge works for 5 min.
In the step 3), the mass ratio of the PCNC to the MMT in the prepared PCNC and MMT assembly is 1: 4.
In the step 3), the mass ratio of the PCNC and MMT assembly to the PVA is 1: 9.
In the step 4), the stirring time is at least 24 hours at normal temperature.
Compared with a pure PVA film, the tensile strength of the composite film of the embodiment is improved by 103 percent, and the elongation at break is improved by 110 percent.
Example 4: a method for preparing a tough polymer film, comprising the steps of:
1) adding 10mL of PEI aqueous solution with the concentration of 3.0 wt% into 5mL of acidified Carbon Nanotube (CNT) suspension with the concentration of 3.0 wt%, continuously stirring for 1h at room temperature, then adjusting the pH of the mixed solution to 1.3 by using concentrated hydrochloric acid to enhance the ionic interaction between the CNT and the PEI, continuously stirring for ten minutes, centrifuging the mixed solution at a high speed for 20min by a centrifugal machine with the rotating speed of 13000rpm, discarding the supernatant, washing the precipitate for three times by using ultrapure water, removing free PEI molecules which do not interact with each other, finally re-dispersing the precipitate in water, centrifuging at a low speed for 5min, removing the CNT aggregate, collecting the supernatant to obtain a mono-dispersed CNT suspension with the concentration of 1.0 wt%, and naming the mono-dispersed CNT suspension as PCNT suspension for later use;
2) adding 2g of montmorillonite powder into 500mL of ultrapure water, continuously dissolving and stirring for one week, centrifuging for 5min by a centrifuge, discarding the precipitate, collecting supernatant to obtain fully stripped MMT nanosheets for later use, wherein the concentration is 0.7 wt%;
3) mixing the PCNT suspension prepared in the step 1 with the MMT suspension prepared in the step 2 to prepare a PCNT and MMT assembly;
4) and (3) mixing the PCNT and MMT assembly prepared in the step three with a certain amount of PVA solution, uniformly stirring at normal temperature, and airing to form a film to prepare the PCNT, MMT and PVA composite film.
In the step 2), the rotating speed of the centrifuge is set to 8000rmp when the centrifuge works for 5 min.
In the step 3), the mass ratio of the PCNT to the MMT in the prepared PCNT and MMT assembly is 1: 5.
In the step 3), the mass ratio of the PCNT and MMT assembly to PVA is 3: 7.
In the step 4), the stirring time is at least 24 hours at normal temperature.
Compared with a pure PVA film, the tensile strength of the composite film is improved by 37 percent, the elongation at break is improved by 114 percent, and the working principle of the invention is as follows:
the invention provides a preparation method of a tough polymer film, which comprises the steps of firstly, carrying out electrostatic self-assembly on Cellulose Nanocrystalline (CNC) modified by Polyethyleneimine (PEI) and montmorillonite nanosheet (MMT) to obtain a CNC and MMT supermolecule assembly, then dispersing the CNC and MMT supermolecule assembly into a polyvinyl alcohol (PVA) aqueous solution, uniformly stirring the assembly and pouring the assembly into a culture dish, forming a film by using a solvent evaporation method, and obtaining the composite film with synchronously increased tensile strength and elongation at break. Thereby obtaining a tough material with balanced performance, and solving the defect that the breaking strength is improved and the elongation at break is neglected in the existing method for enhancing the mechanical property of the polymer matrix by the nano filler; the transmission electron microscope appearance of the PCNC and MMT assembly prepared by the invention is shown in figure 1, wherein the PCNC nano rod is attached to the surface and the edge of the MMT nano plate, the orientation is different, a dense PCNC layer is formed on the surface of the MMT, the size of an assembly body depends on the sizes of the original MMT and the original PCNC, the scanning electron microscope appearance of the PCNC, the MMT and the PVA composite film prepared by the invention is shown in figure 2, it can be seen that the film has smooth surface, the cross section is in a layered structure, the layered structure is formed by stacking assemblies, PVA molecular interlayers are arranged between the layers of the assemblies, the mechanical property representation of the PCNC, MMT and PVA composite film prepared by the invention is shown in figure 3, it can be seen that the PVA film reinforced by the assembly body has obviously improved mechanical property, wherein the tensile strength is improved by 132 percent, the elongation at break is improved by 300 percent, and the effectiveness of the scheme is proved.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (5)
1. The preparation method of the tough polymer film is characterized by comprising the following steps:
1) adding 10mL of PEI aqueous solution with the concentration of 3.0 wt% into 5mL of CNC suspension with the concentration of 3.0 wt%, continuously stirring for 1h at room temperature, then adjusting the pH of the mixed solution to 1.3 by using concentrated hydrochloric acid to enhance the ionic interaction between CNC and PEI, continuously stirring for ten minutes, centrifuging the mixed solution at a high speed for 20min by a 13000rpm rotary speed centrifuge, discarding supernatant, washing precipitates for three times by using ultrapure water, removing free PEI molecules without the interaction, finally re-dispersing the precipitates in water, centrifuging at a low speed for 5min, removing the CNC aggregates, collecting the supernatant to obtain mono-dispersed CNC suspension with the concentration of 1.0 wt%, and naming the suspension as PCNC suspension for later use;
2) adding 2g of montmorillonite powder into 500mL of ultrapure water, continuously dissolving and stirring for one week, centrifuging for 5min by a centrifuge, discarding the precipitate, collecting supernatant to obtain fully stripped MMT nanosheets for later use, wherein the concentration is 0.7 wt%;
3) mixing the PCNC suspension liquid prepared in the step 1 with the MMT suspension liquid prepared in the step 2 to prepare a PCNC and MMT assembly;
4) and (3) mixing the PCNC and MMT assembly prepared in the step three with a certain amount of PVA solution, uniformly stirring at normal temperature, and airing to form a film to prepare the PCNC, MMT and PVA composite film.
2. The method for preparing a tough polymer film according to claim 1, wherein in the step 2), the rotation speed of the centrifuge during 5min of centrifugation is set to 8000 rmp.
3. The method for preparing the tough polymer film according to claim 1, wherein in the step 3), the mass ratio of the PCNC to the MMT in the prepared PCNC and MMT assembly is 1: 2.
4. The method for preparing the tough polymer film according to claim 1, wherein in the step 3), the mass ratio of the PCNC and MMT assembly to the PVA is 1: 9.
5. The method for preparing a tough polymer film according to claim 1, wherein in the step 4), the stirring time at normal temperature is at least 24 hours.
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| CN113550509A (en) * | 2021-07-17 | 2021-10-26 | 廉江市第三建筑工程有限公司 | Construction method of anti-cracking protective layer of roof structure |
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Non-Patent Citations (1)
| Title |
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| 赵肖娟: "一维多级结构复合材料的构筑研究", 《工程科技Ⅰ辑》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113550509A (en) * | 2021-07-17 | 2021-10-26 | 廉江市第三建筑工程有限公司 | Construction method of anti-cracking protective layer of roof structure |
| CN113550509B (en) * | 2021-07-17 | 2022-05-17 | 廉江市第三建筑工程有限公司 | Construction method of anti-cracking protective layer of roof structure |
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Application publication date: 20200619 |