CN112480581B - Preparation method of modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material - Google Patents
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Abstract
The invention provides a preparation method of a modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material, which comprises the following steps: adding polyvinyl alcohol into dimethyl sulfoxide, and heating to 40-80 ℃ to fully dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution; adding succinic anhydride and a catalyst into the polyvinyl alcohol solution, and stirring for 12-48 hours at room temperature to allow the mixture to react sufficiently to obtain a modified mixed solution; taking 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, a nano metal precursor aqueous solution, an amino-terminated hyperbranched polymer aqueous solution and the mixed solution obtained in the step S2 as raw materials to react to obtain a composite material solution; and (4) carrying out post-treatment on the composite material solution obtained in the step S3 to obtain the modified polyvinyl alcohol/nano metal composite flexible tensile strain film sensing material. The flexibility and elastic deformation performance of the material prepared by the invention are obviously improved.
Description
Technical Field
The invention relates to the field of sensor materials, in particular to a preparation method of a modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material.
Background
Polyvinyl alcohol (PVA) is a water-soluble polymer with excellent performance and wide application. The film prepared by the method has excellent oxygen resistance, oil resistance, wear resistance, tear resistance, transparency, antistatic property, chemical corrosion resistance and solvent selectivity. The long chain molecule contains a large amount of hydroxyl, but the side group (-OH) has small volume and can enter a crystallization point without causing stress, so the crystal has high crystallinity. Therefore, various materials prepared from polyvinyl alcohol have poor flexibility in the using process, almost have no tensile elasticity, and cannot be used as tensile deformation materials.
The hyperbranched polymer has a spheroidal molecular structure, is rich in a large number of end groups, and has high solubility, low viscosity and high activity. The amino-terminated hyperbranched polymer prepared by utilizing the synthesis of the monomer molecules with amino has a three-dimensional structure, a large number of primary amino groups are distributed on the surface, and imino and tertiary amino are contained in the polymer, so that the polymer has good solubility and dispersibility. The rheological property of the high polymer can be effectively improved by adding the hyperbranched polymer into the high polymer. Based on the three-dimensional structure of the hyperbranched polymer, a method is found for grafting the hyperbranched polymer to a polyvinyl alcohol molecular chain, so that the arrangement regularity of the polyvinyl alcohol molecular chain can be damaged, the molecular chain spacing is increased, the cross-linking and entanglement among the molecular chains are increased, the purpose of reducing a crystallization area is achieved, and the flexibility and elasticity of the material are effectively improved. In addition, metal ions can be captured inside the hyperbranched polymer through the complexing and adsorbing effects of the amino on the metal ions, then the metal ions are reduced into the metal nano-material by utilizing the reducing agent or the reducing effect of the amino, and meanwhile, the size of the generated metal nano-material can be controlled due to the protecting effect of the hyperbranched polymer, so that the generated nano-material has good dispersion stability. Therefore, based on the crosslinking modification effect of the amino-terminated hyperbranched polymer on the polyvinyl alcohol and the positioning regulation generation effect on the metal nano material, the flexible material with the positioned and doped metal nano material can be prepared by using the polyvinyl alcohol as the base material. Due to the conductivity of the metal material and the dispersibility of the nano material in the polyvinyl alcohol, when the material is in a stretching deformation process, the separation among the metal nano particles can cause the change of the conductivity of the material, so the material can be used as a good stretching strain sensor material and can be processed into various shapes such as films, fibers and the like.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention discloses a preparation method of a modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material, which has simple process, can graft hyperbranched polymers with a similar spherical molecular structure on linear chain high molecular polyvinyl alcohol, and cross-links polyvinyl alcohol molecules through the hyperbranched polymers, so that the structural regularity of the linear chain high molecular polyvinyl alcohol is reduced, and the elasticity is increased; the material prepared by the invention can be processed into various forms such as films, fibers and the like, has good elasticity and toughness, and the resistance of the material can be obviously changed in tensile strain, so that the material is a good base material for a tensile strain sensor. The specific technical scheme is as follows:
the invention provides a preparation method of a modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material, which comprises the following steps:
s1, adding polyvinyl alcohol into dimethyl sulfoxide, and heating to 40-80 ℃ to fully dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution;
s2, adding succinic anhydride and a catalyst into the polyvinyl alcohol solution, and stirring for 12-48 hours at room temperature to fully react to obtain a modified mixed solution;
s3, reacting 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, a nano metal precursor aqueous solution, an amino-terminated hyperbranched polymer aqueous solution and the mixed solution obtained in the step S2 as raw materials to obtain a composite material solution;
and S4, carrying out post-treatment on the composite material solution obtained in the step S3 to obtain the modified polyvinyl alcohol/nano metal composite flexible tensile strain film sensing material.
Further, in step S1, the concentration of the polyvinyl alcohol solution is 5-30 g/L.
Further, in the step S2, the molar ratio of succinic anhydride to hydroxyl groups on a polyvinyl alcohol molecular chain in the polyvinyl alcohol solution is 1: 20-1: 60, the catalyst is triethylamine, and the molar ratio of triethylamine to succinic anhydride is 1: 1-1: 20.
Further, step S3 specifically includes:
s31, dropwise adding the nano metal precursor water solution into the amino-terminated hyperbranched polymer water solution, and after dropwise adding, carrying out reduction reaction by heating high temperature reduction or adding a reducing agent to obtain an amino-terminated hyperbranched polymer/nano metal dispersion solution;
s32, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the modified mixed solution obtained in the step S2, and stirring and reacting at room temperature for 10-60 min;
s33, adding the amino-terminated hyperbranched polymer/nano-metal dispersion liquid obtained in the step S31 into the solution obtained in the step S32, and stirring and reacting at room temperature for 12-48 hours to obtain a composite material solution.
Further, in step S31, the nano metal precursor is silver nitrate or chloroauric acid, the concentration of the nano metal precursor aqueous solution is 0.01 to 0.5mol/L, the concentration of the amino-terminated hyperbranched polymer aqueous solution is 50 to 200g/L g/L, and the volume ratio of the nano metal precursor aqueous solution to the amino-terminated hyperbranched polymer aqueous solution is 1:1 to 1: 5.
Further, in step S31, the reduction reaction is heating high temperature reduction or reducing by adding reducing agent,
the heating high-temperature reduction is to heat the mixed solution obtained in the step S31 to 90-100 ℃, and the reaction time is 1-3 hours;
and the reducing agent is added into the mixed solution in the step S31, and the reducing agent is one or more of sodium borohydride, hydrazine hydrate, vitamin C, sodium citrate and ascorbic acid.
Further, the volume ratio of the amino-terminated hyperbranched polymer/nano-metal dispersion liquid obtained in the step S31 to the modified mixed solution obtained in the step S2 is 1: 2-1: 10;
in step S32, the molar ratio of the total amount of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide to the succinic anhydride is 1:10 to 1: 1.
Further, step S3 specifically includes:
s301, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the mixed solution obtained in the step S2, and stirring and reacting at room temperature for 10-60 min;
s302, adding an amino hyperbranched polymer aqueous solution into the mixed solution obtained in the step S301, and continuously stirring and reacting for 12-48 hours at room temperature;
and S303, dropwise adding the nano metal precursor aqueous solution into the mixed solution obtained in the step 302 while stirring, and reducing by heating at high temperature or adding a reducing agent after the dropwise adding is finished.
Further, in the step S301, the concentration of the amino-terminated hyperbranched polymer aqueous solution is 50-200 g/L;
in the step S302, the volume ratio of the added amount of the amino-terminated hyperbranched polymer aqueous solution to the mixed solution obtained in the step S301 is 1: 2-1: 10;
in the step S303, the nano metal precursor is silver nitrate or chloroauric acid, the concentration of the nano metal precursor aqueous solution is 0.01-0.5 mol/L, and the volume ratio of the dropwise added nano metal precursor aqueous solution to the mixed solution obtained in the step S302 is 1: 10-1: 30.
Further, in step S4, the post-processing includes: the composite material solution obtained in step S3 is placed in a polytetrafluoroethylene mold and dried, or,
and spinning the composite material solution obtained in the step S3.
The invention has the following beneficial effects:
(1) according to the preparation method, the linear polyvinyl alcohol macromolecules are modified by the hyperbranched polymer with the three-dimensional sphere-like structure, so that the crystallinity of the polyvinyl alcohol is obviously reduced, the flexibility of the material prepared by the hyperbranched polymer is improved, and the material has good elasticity and elastic recovery performance and can improve the flexibility and the elasticity of the substrate material.
(2) According to the preparation method, the assembly of metal nanoparticles can be formed on the grafting crosslinking point of the modified polyvinyl alcohol through the in-situ regulation generation and fixation effect of the amino-terminated hyperbranched polymer on the metal nanoparticles, and the separation and rearrangement of the metal nanoparticles are formed in the stretching deformation process, so that the resistance of the metal nanoparticles is obviously changed, and the metal nanoparticles are a good material for preparing the flexible stretching strain sensor.
(3) The preparation method of the invention can form continuous assembly and arrangement of the metal nano material on the molecular chain of the modified polyvinyl alcohol, which is the basis for ensuring the good induction performance of the metal nano material, and the traditional mechanical doping is often dispersed unevenly and has poor performance stability.
(4) The preparation method of the invention has simple and safe process and is beneficial to industrial production
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows X-ray diffraction patterns of polyvinyl alcohol (PVA) and amino-terminated hyperbranched polymer-modified polyvinyl alcohol according to the present invention;
FIG. 2 is a bar graph of tensile elongation at break for polyvinyl alcohol films and modified polyvinyl alcohol films;
fig. 3 is a graph of resistance change of the modified polyvinyl alcohol/nano silver composite flexible film under different elongation rates under one stretching cycle.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. In the present invention, unless otherwise expressly stated or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or may be connected through the interior of two elements or in interactive relation with one another. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The preparation method of the invention uses hyperbranched polymer with three-dimensional structure to modify polyvinyl alcohol to obtain polymer substrate with high flexibility and elasticity, and generates metal nano material through internal controllable positioning, or uses hyperbranched polymer to regulate and control in advance to generate metal nano material, and then uses hyperbranched polymer coated with metal nano material to graft modified polyvinyl alcohol, thereby obtaining organic/inorganic nano hybrid tensile strain sensor material.
Example 1
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.5g succinic anhydride (5mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step S1, then adding 0.10g triethylamine, and stirring at room temperature for 24h to enable full reaction.
S31, dropwise adding 10mL of silver nitrate aqueous solution with the concentration of 0.1mol/L into 30mL of amino-terminated hyperbranched polymer aqueous solution with the concentration of 100g/L, stirring while dropwise adding, heating to 95 ℃ after dropwise adding, stirring and reacting for 1h to obtain amino-terminated hyperbranched polymer nano-silver dispersion.
S32, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (5mmol) and 0.56g N-hydroxysuccinimide (5mmol) were added to the succinic anhydride modified polyvinyl alcohol solution of step S2, and the reaction was stirred at room temperature for 0.5 h.
S33, after the reaction in the step S32, adding the amino-terminated hyperbranched polymer nano-silver dispersion liquid obtained in the step S31 into the step S32, and continuously stirring and reacting for 24 hours at room temperature to obtain a composite material solution.
And S4, pouring the composite material solution obtained in the step S33 into a polytetrafluoroethylene mold, and drying and molding to obtain the modified polyvinyl alcohol/nano silver composite flexible tensile strain film sensing material.
Example 2
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.25g of succinic anhydride (2.5mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step S1, then adding 0.05g of triethylamine, and stirring at room temperature for 24h to enable full reaction.
S31, dropwise adding 10mL of silver nitrate aqueous solution with the concentration of 0.1mol/L into 30mL of amino-terminated hyperbranched polymer aqueous solution with the concentration of 50g/L, stirring while dropwise adding, heating to 95 ℃ after dropwise adding, stirring and reacting for 2h to obtain amino-terminated hyperbranched polymer nano-silver dispersion.
S32, 0.48g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2.5mmol) and 0.28g N-hydroxysuccinimide (2.5mmol) were added to the succinic anhydride modified polyvinyl alcohol solution of step S2, and the reaction was stirred at room temperature for 0.5 h.
And S33, after the reaction in the step S32 is finished, adding the amino-terminated hyperbranched polymer nano-silver dispersion liquid obtained in the step S31 into the step S32, and continuously stirring and reacting for 24 hours at room temperature.
And S4, pouring the mixed solution obtained in the step S33 into a polytetrafluoroethylene mold, and drying and molding to obtain the modified polyvinyl alcohol/nano silver composite flexible tensile strain film sensing material.
Example 3
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.20g of succinic anhydride (2mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step S1, then adding 0.04g of triethylamine, and stirring at room temperature for 24h to enable full reaction.
S31, dropwise adding 5mL of silver nitrate aqueous solution with the concentration of 0.1mol/L into 15mL of amino-terminated hyperbranched polymer aqueous solution with the concentration of 50g/L, stirring while dropwise adding, heating to 95 ℃ after dropwise adding, stirring and reacting for 2h to obtain amino-terminated hyperbranched polymer nano-silver dispersion.
S32, 0.384g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (2mmol) and 0.224g N-hydroxysuccinimide (2mmol) were added to the succinic anhydride modified polyvinyl alcohol solution of step S2, and the reaction was stirred at room temperature for 0.5 h.
And S33, after the reaction in the step S32 is finished, adding the amino-terminated hyperbranched polymer nano-silver dispersion liquid obtained in the step S31 into the step S32, and continuously stirring and reacting for 24 hours at room temperature.
And S4, spinning the mixed solution obtained in the step S33 to obtain the modified polyvinyl alcohol/nano silver composite flexible tensile strain fiber sensing material.
Example 4
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.5g succinic anhydride (5mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step 1, then adding 0.10g triethylamine, and stirring for 24h at room temperature to enable the mixture to fully react.
S31, dropwise adding 10mL of chloroauric acid aqueous solution with the concentration of 0.1mol/L into 30mL of amino-terminated hyperbranched polymer aqueous solution with the concentration of 100g/L, stirring while dropwise adding, heating to 95 ℃ after dropwise adding, stirring and reacting for 1h to obtain amino-terminated hyperbranched polymer nanogold dispersion.
S32, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (5mmol) and 0.56g N-hydroxysuccinimide (5mmol) were added to the succinic anhydride-modified polyvinyl alcohol solution obtained in step S2, and the reaction was stirred at room temperature for 0.5 h.
And S33, after the reaction in the step S32 is finished, adding the amino-terminated hyperbranched polymer nano-gold dispersion liquid obtained in the step S31 into the reaction liquid, and continuously stirring and reacting for 24 hours at room temperature.
And 4, pouring the mixed solution obtained in the step S33 into a polytetrafluoroethylene mold, and drying and molding to obtain the modified polyvinyl alcohol/nano-gold composite flexible tensile strain film sensing material.
Example 5
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.5g succinic anhydride (5mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step S1, then adding 0.10g triethylamine, and stirring at room temperature for 24h to enable full reaction.
S31, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (5mmol) and 0.56g N-hydroxysuccinimide (5mmol) were added to the succinic anhydride modified polyvinyl alcohol solution of step S2, and the reaction was stirred at room temperature for 0.5 h.
S32, after the reaction in step S31, 30mL of 100g/L amino-terminated hyperbranched polymer aqueous solution is added into step S31, and the reaction is continued for 24 hours under stirring at room temperature.
S33, dropwise adding 10mL of silver nitrate aqueous solution with the concentration of 0.1mol/L into the mixed solution obtained in the step S32 while stirring, and after the dropwise adding is finished, adding 5mL of sodium borohydride aqueous solution with the concentration of 0.4mol/L, and stirring and reducing for 0.5 h.
And S4, pouring the mixed solution obtained in the step S33 into a polytetrafluoroethylene mold, and drying and molding to obtain the modified polyvinyl alcohol/nano silver composite flexible tensile strain film sensing material.
Example 6
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.5g succinic anhydride (5mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step S1, then adding 0.10g triethylamine, and stirring at room temperature for 24h to enable full reaction.
S31, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (5mmol) and 0.56g N-hydroxysuccinimide (5mmol) were added to the succinic anhydride modified polyvinyl alcohol solution of step S2, and the reaction was stirred at room temperature for 60 min.
S32, after the reaction in step S31, 30mL of the amino-terminated hyperbranched polymer aqueous solution with the concentration of 50g/L is added into step S31, and the reaction is continued to be stirred at room temperature for 12 h.
S33, dropwise adding 10mL of silver nitrate aqueous solution with the concentration of 0.1mol/L into the mixed solution obtained in the step S32 while stirring, and after the dropwise adding is finished, adding 5mL of sodium borohydride aqueous solution with the concentration of 0.4mol/L, and stirring and reducing for 0.5 h.
And S4, pouring the mixed solution obtained in the step S33 into a polytetrafluoroethylene mold, and drying and molding to obtain the modified polyvinyl alcohol/nano silver composite flexible tensile strain film sensing material.
Example 7
The invention relates to a preparation method of a flexible tensile strain sensing material compounded by modified polyvinyl alcohol and nano metal, which comprises the following steps:
s1, 4.4g of polyvinyl alcohol (0.1mol-OH) was added to 200mL of dimethyl sulfoxide, and the mixture was heated in a water bath at 60 ℃ with stirring to be sufficiently dissolved.
S2, slowly adding 0.5g succinic anhydride (5mmol) into the polyvinyl alcohol dimethyl sulfoxide solution obtained in the step S1, then adding 0.10g triethylamine, and stirring at room temperature for 24h to enable full reaction.
S31, 0.96g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (5mmol) and 0.56g N-hydroxysuccinimide (5mmol) were added to the succinic anhydride modified polyvinyl alcohol solution of step S2, and the reaction was stirred at room temperature for 10 min.
S32, after the reaction in step S31, 30mL of 200g/L amino-terminated hyperbranched polymer aqueous solution is added into step S31, and the reaction is continued for 48 hours under stirring at room temperature.
S33, dropwise adding 10mL of silver nitrate aqueous solution with the concentration of 0.1mol/L into the mixed solution obtained in the step S32 while stirring, and after the dropwise adding is finished, adding 5mL of sodium borohydride aqueous solution with the concentration of 0.4mol/L, and stirring and reducing for 0.5 h.
And S4, pouring the mixed solution obtained in the step S33 into a polytetrafluoroethylene mold, and drying and molding to obtain the modified polyvinyl alcohol/nano silver composite flexible tensile strain film sensing material.
The above embodiments are described below with reference to the drawings. Referring to fig. 1 to 3, it can be seen from fig. 1 that the common polyvinyl alcohol shows a stronger crystalline diffraction peak, and the modified amino-terminated hyperbranched polymer has a significantly reduced diffraction peak and an increased peak width, indicating that the modified polyvinyl alcohol has a significantly reduced crystalline region. Compared with pure polyvinyl alcohol, the modified polyvinyl alcohol in fig. 2 has significantly enhanced stretchability and an elongation at break of 341%.
The invention takes succinic anhydride as an intermediate, one end of the succinic anhydride reacts with hydroxyl on polyvinyl alcohol, and the other end of the succinic anhydride reacts with amino on amino-terminated hyperbranched polymer, so that hyperbranched polymer is grafted on a polyvinyl alcohol main chain, and meanwhile, due to rich terminal functional groups of the hyperbranched polymer, polyvinyl alcohol molecular chains are cross-linked together through the amino-terminated hyperbranched polymer. On one hand, the modification increases the steric hindrance among polyvinyl alcohol molecular chains, so that the polyvinyl alcohol molecular chains cannot be regularly arranged, the crystallinity is obviously reduced (see figure 1), and it can be seen from figure 1 that common polyvinyl alcohol shows a strong crystallization diffraction peak, and the diffraction peak is obviously reduced and the peak width is increased after the amino-terminated hyperbranched polymer is modified, which indicates that the modified polyvinyl alcohol has greatly reduced crystalline regions and increased amorphous regions, and greatly improves the flexibility of the material. As shown in fig. 2, compared with pure polyvinyl alcohol, the modified polyvinyl alcohol has significantly enhanced stretchability, the elongation at break can reach 341%, and the amino-terminated hyperbranched polymer crosslinked between polyvinyl alcohol molecules can generate deformation of a spatial structure during stretching due to the difference between the three-dimensional structure of the hyperbranched polymer and the linear polymer, and the deformation is reversible, so that the polyvinyl alcohol can have good elasticity and elastic recovery performance through the modification. On the other hand, the uniformity and the stability of the distribution of the amino-terminated hyperbranched polymer on the polyvinyl alcohol molecular chain are effectively ensured through grafting modification. Because the amino-terminated hyperbranched polymer contains rich amino groups, nanometer metal precursor ions (such as silver ions and chloroauric acid radical ions) can be gathered in the hyperbranched polymer through the complexing or adsorbing action, and metal nanometer materials (such as nanometer silver and nanometer gold) can be generated in the hyperbranched polymer through the reducing action, so that the nanometer metal materials with the conductive performance are positioned and assembled on the modified polyvinyl alcohol molecular chain. Based on the uniform and stable grafting of the amino-terminated hyperbranched polymer on a polyvinyl alcohol molecular chain, the continuity and uniformity of the distribution of the nano metal material are ensured, and the stability of the induction performance of the modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material is ensured.
Due to the regulation and protection effects of the amino-terminated hyperbranched polymer on the generation of the nano metal material, the modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material can be implemented by two different schemes. The preparation method comprises the following steps of firstly preparing a dispersion liquid of a nano metal material by using an amino-terminated hyperbranched polymer, then modifying polyvinyl alcohol by using the amino-terminated hyperbranched polymer wrapped with metal nano particles, and loading the metal nano particles onto a polyvinyl alcohol molecular chain by using a grafting reaction to prepare the composite tensile strain sensing material. And the scheme b is that the amino-terminated hyperbranched polymer is firstly used for grafting the modified polyvinyl alcohol, then the amino-terminated hyperbranched polymer in the modified polyvinyl alcohol is used for removing the precursor of the complexing adsorption nano metal material, and then the metal nano material is generated in situ in the modified polymer to prepare the composite tensile strain sensing material. The composite tensile strain sensing material prepared by the two schemes has good performance. As shown in fig. 3, in the stretching process by applying an external force, the resistance value of the film increases as the stretching deformation increases; after the external stretching force is reduced, the film retracts, and the resistance value gradually becomes smaller. When the external force is completely removed, the device can quickly recover to an approximately original state, and shows better deformation detectability. And in the stretching and retracting processes, under the same deformation degree, the resistance value difference is small, and the inspection stability is high
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example" or "some examples" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples described in this specification can be combined and combined by one skilled in the art.
While embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications and variations may be made therein by those of ordinary skill in the art within the scope of the present invention.
Claims (3)
1. A preparation method of a modified polyvinyl alcohol/nano metal composite flexible tensile strain sensing material is characterized by comprising the following steps:
s1, adding polyvinyl alcohol into dimethyl sulfoxide, and heating to 40-80 ℃ to fully dissolve the polyvinyl alcohol to obtain a polyvinyl alcohol solution with the solution concentration of 5-30 g/L;
s2, adding succinic anhydride and a catalyst into the polyvinyl alcohol solution, and stirring for 12-48 hours at room temperature to fully react to obtain a modified mixed solution; the molar ratio of succinic anhydride to hydroxyl on a polyvinyl alcohol molecular chain in a polyvinyl alcohol solution is 1: 20-1: 60, the catalyst is triethylamine, and the molar ratio of triethylamine to succinic anhydride is 1: 1-1: 20;
s3, reacting 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, a nano metal precursor aqueous solution, an amino-terminated hyperbranched polymer aqueous solution and the mixed solution obtained in the step S2 as raw materials to obtain a composite material solution;
s4, carrying out post-treatment on the composite material solution obtained in the step S3 to obtain a modified polyvinyl alcohol/nano metal composite flexible tensile strain film sensing material;
wherein, step S3 specifically includes: s31, dropwise adding 0.01-0.5 mol/L of nano metal precursor water solution into 50-200 g/L of amino-terminated hyperbranched polymer water solution, and performing reduction reaction by heating high temperature reduction or adding a reducing agent after dropwise adding to obtain amino-terminated hyperbranched polymer/nano metal dispersion, wherein the volume ratio of the nano metal precursor water solution to the amino-terminated hyperbranched polymer water solution is 1: 1-1: 5, and the nano metal precursor is silver nitrate or chloroauric acid;
s32, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the modified mixed solution obtained in the step S2, and stirring and reacting at room temperature for 10-60 min, wherein the molar ratio of the total amount of the 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and the N-hydroxysuccinimide to the succinic anhydride is 1: 10-1: 1;
s33, adding the amino-terminated hyperbranched polymer/nano-metal dispersion liquid obtained in the step S31 into the solution obtained in the step S32, and stirring and reacting at room temperature for 12-48 hours to obtain a composite material solution, wherein the volume ratio of the amino-terminated hyperbranched polymer/nano-metal dispersion liquid obtained in the step S31 to the modified mixed solution obtained in the step S2 is 1: 2-1: 10; or
Step S3 specifically includes: s301, adding 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the mixed solution obtained in the step S2, and stirring and reacting at room temperature for 10-60 min;
s302, adding an amino-terminated hyperbranched polymer aqueous solution with the concentration of 50-200 g/L into the mixed solution obtained in the step S301, wherein the volume ratio of the added amino-terminated hyperbranched polymer aqueous solution to the mixed solution obtained in the step S301 is 1: 2-1: 10, and continuously stirring and reacting for 12-48 h at room temperature;
and S303, dropwise adding a nano metal precursor aqueous solution with the concentration of 0.01-0.5 mol/L into the mixed solution obtained in the step 302, wherein the volume ratio of the dropwise added nano metal precursor aqueous solution to the mixed solution obtained in the step S302 is 1: 10-1: 30, stirring while dropwise adding, and reducing by heating at high temperature or adding a reducing agent after dropwise adding is finished, wherein the nano metal precursor is silver nitrate or chloroauric acid.
2. The method according to claim 1, wherein in step S31, the reduction reaction is a reduction at a high temperature by heating or a reduction by adding a reducing agent,
the heating high-temperature reduction is to heat the mixed solution obtained in the step S31 to 90-100 ℃, and the reaction time is 1-3 hours;
and the reducing agent is added into the mixed solution in the step S31, and the reducing agent is one or more of sodium borohydride, hydrazine hydrate, vitamin C, sodium citrate and ascorbic acid.
3. The method according to claim 1, wherein in step S4, the post-processing includes: the composite material solution obtained in step S3 is placed in a polytetrafluoroethylene mold and dried, or,
and spinning the composite material solution obtained in the step S3.
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