CN109054308B

CN109054308B - Acetone-responsive biomimetic material and preparation and application thereof

Info

Publication number: CN109054308B
Application number: CN201810650424.0A
Authority: CN
Inventors: 张利东; 王福顺
Original assignee: East China Normal University
Current assignee: East China Normal University
Priority date: 2018-06-22
Filing date: 2018-06-22
Publication date: 2020-08-04
Anticipated expiration: 2038-06-22
Also published as: CN109054308A

Abstract

The invention discloses an acetone response bionic material and preparation and application thereof, which is characterized in that a fluorine-containing aromatic ring with stronger rigidity is adopted as a functional response unit, an alkyl chain for adjusting flexibility and stretchability is adopted, an interpenetrating network structure of epoxy curing and double bond crosslinking is adopted to prepare a bionic response type film material which has high elasticity and can deform when being sensitive to acetone. Compared with the prior art, the invention has very good flexibility and operability, has extremely high response performance to acetone, can be further designed into acetone sensitive devices suitable for the requirements of various fields, and particularly has huge development potential and wide application prospect in the field of forward bionics.

Description

Acetone-responsive biomimetic material and preparation and application thereof

Technical Field

The invention relates to the technical field of preparation and application of bionic materials, in particular to a high-elasticity acetone stimulus response artificial muscle bionic material and preparation and application thereof.

Background

With the increasingly deep understanding and understanding of the natural biological structure of human beings and the high-precision sharpening of the living and production requirements of human society, the technology for simulating the biological structure by utilizing physical and chemical synthesis and preparation skills also tends to be hot and mature, and the development of the bionic material is greatly promoted. The device developed by the bionic material is well applied to the fields of industry, electronics, military and the like. Especially bionic soft materials, have been applied to wearable sensors, and the future application value of the bionic soft materials is more huge, especially in the aspect of flexible electronic industry. The novel intelligent flexible bionic material is prepared by simulating a biological structure derivation rule, so that the bionic performance is structurally realized, and the control on the bionic behavior of the material can be realized through external stimulation, so that the application field of the material is greatly expanded, and the material which has stress response to acetone gas is always a research hotspot.

At present, most of acetone-sensitive film materials are prepared from inorganic materials, and are less related to novel synthetic polymers and mechanical properties meeting application requirements. In order to realize the efficient controllable bionic deformation performance of the film driven by acetone, the film needs to have good tensile wear resistance in addition to the precise design of the bionic structure of the film, and can still maintain ideal mechanical performance after long-time stimulation of acetone steam, namely, the film needs to have reversible stimulation response behavior, has certain resistance to adverse environmental conditions such as acid-base high temperature and low temperature, and the like, and is a basic element for realizing the bionic performance of a bionic material and a basic condition for expanding the application of the bionic material. Therefore, only by designing a reasonable bionic structure, deeply understanding the bionic mechanism and optimizing the mechanical property of the material, the dynamic bionic process can be controlled and the application pace of the material can be promoted.

Disclosure of Invention

The invention aims to provide an acetone response bionic material and preparation and application thereof aiming at the defects of the prior art, wherein a fluorine-containing aromatic ring with stronger rigidity is adopted as a functional response unit, an alkyl chain for adjusting flexibility and stretchability is used as an auxiliary material, an interpenetrating network structure of epoxy curing and double bond crosslinking is used for preparing a bionic response type film material which has high elasticity and is sensitive to acetone and can generate deformation, the mechanical property of the material is further improved by adjusting the stretchability and the viscosity of the material through silane, the material is endowed with acid, alkali, solvent and high temperature tolerance, the compatibility of raw material molecules is promoted, the film material is cut into film devices with different shapes, the controllable deformation of a flexible device is realized by absorbing reversible curling, bending, twisting, winding, circling and rolling caused by acetone steam, and the film and bone slices are combined to be used as artificial muscles, the film material has excellent flexibility and operability, has extremely high response performance to acetone, can be further designed into acetone sensitive devices suitable for requirements of various fields, and particularly has huge development potential and wide application prospect in the field of forward bionics.

The specific technical scheme for realizing the purpose of the invention is as follows: an acetone-responsive biomimetic material is characterized in that the biomimetic material is a yellow transparent elastomer compounded by a C polymer and a D polymer which are acetone-responsive, and the content of the D polymer in the composite material is 0.1-20 wt%; the structure of the C polymer is shown as the following formula (I):

wherein: n is a positive integer.

The structure of the D polymer is shown as the following formula (II):

wherein: n is a positive integer.

The preparation of bionic material responding to acetone features that 2,3,5, 6-tetrafluoro-1, 4-bis- (10, 11-epoxy undecanoic acid) dimethyl benzene (compound B), 4-methyl hexahydrophthalic anhydride and 3- (methacryloxy) propyl trimethoxy silane are mixed in the ratio of 1: 0.5-4: 0.01-0.2 weight ratio, and carrying out a crosslinking reaction of the following structural reaction formula (III) at a temperature of 90-110 ℃:

and then curing for 1-4 hours to obtain a product which is a yellow transparent elastomer compounded by the polymer C and the polymer D, namely the target product is an acetone response composite material.

The preparation of the 2,3,5, 6-tetrafluoro-1, 4-bis- (10, 11-epoxy undecanoic acid) dimethyl benzene ester comprises the following steps:

step a, mixing 2,3,5, 6-tetrafluoro-p-xylene glycol and tetrahydrofuran according to the mass volume ratio of 1g to 10-40 m L to obtain solution A for standby, mixing 10-undecenoyl chloride and tetrahydrofuran according to the mass volume ratio of 1g to 15-40 m L to obtain solution B for standby, then mixing the solution A and the solution B according to the volume ratio of 1: 0.5-8, dropwise adding a Triethylamine (TEA) acid-binding agent, and carrying out the synthesis reaction of the following structural reaction formula (IV) at normal temperature:

reacting for 16-25 hours, purifying the obtained product to obtain 2,3,5, 6-tetrafluoro-1, 4-di- (10-undecylenic acid) dimethyl benzene (A compound), and dripping amount of TEA is 5-10 wt% of the A liquid.

And b, mixing the prepared 2,3,5, 6-tetrafluoro-1, 4-di- (10-undecylenic acid) benzene dimethyl ester (A compound) and DCM according to the mass-volume ratio of 1 g: 10-40 m L to obtain a solution C for standby, mixing 3-chloroperoxybenzoic acid and DCM according to the mass-volume ratio of 1 g: 20-40 m L to obtain a solution D for standby, mixing the solution C and the solution D according to the volume ratio of 1: 1-16, and then carrying out the synthetic reaction of the following structural reaction formula (V) at normal temperature.

Reacting for 12-20 hours to obtain a

product

2,3,5, 6-tetrafluoro-1, 4-di- (10, 11-epoxy undecanoic acid) dimethyl benzene (product B), wherein the structure of the product is as follows (VI):

the application of the bionic material responding to acetone is characterized in that the composite material is cut into film devices with different shapes, the controllable deformation of a flexible device is realized by absorbing reversible curling, bending, twisting, winding, circling and rolling caused by acetone steam, the film devices are combined with bone fragments to be used as artificial muscles, and the bone fragments are driven to move under the stimulation of the acetone to realize bionic movement.

Compared with the prior art, the invention has very excellent flexibility and operability, greatly improves the tolerance of physical treatment and chemical modification of the film by using general polymers, such as acid, alkali, solvent, high temperature and the like, prepares the bionic environment-sensitive material by taking fluorine-containing aromatic rings with stronger rigidity as functional response units and simultaneously assisting alkyl chains for adjusting the flexibility and the stretchability, prepares the bionic response type material by an interpenetrating network structure of epoxy curing and double bond crosslinking, further improves the mechanical property of the material by adjusting the stretchability and the viscosity of the material through silane, endows the material with the acid, alkali, solvent and high temperature tolerance, promotes the compatibility of raw material molecules, has very excellent flexibility and operability, has extremely high response performance to acetone, and can be further designed and prepared into acetone sensitive devices.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound B prepared in example 1;

FIG. 2 is a nuclear magnetic carbon spectrum of the compound B prepared in example 1;

FIG. 3 is an infrared spectrum of the compound B prepared in example 1;

FIG. 4 is a mass spectrum of the compound B prepared in example 1;

FIG. 5 is a photograph of the acetone responsive composite prepared in example 1 in a state where it is not exposed to acetone;

FIG. 6 is a photograph of an acetone responsive composite prepared in example 1 after exposure to acetone;

FIG. 7 is an infrared spectrum of an acetone responsive composite prepared in example 2;

FIG. 8 is an AFM photograph of an acetone responsive composite prepared in example 2 without an acid-base treatment;

FIG. 9 is an AFM photograph of an acid treated acetone responsive composite prepared in example 2;

FIG. 10 is an AFM photograph of an acetone responsive composite prepared in example 2 without alkali treatment;

FIG. 11 is a TG-DSC analysis of acetone responsive composites prepared in examples 2-5;

fig. 12 is a photograph of a bionic artificial palm made of the acetone responsive composite material prepared in example 2.

Detailed Description

The present invention is further described in detail below with reference to specific examples to assist those skilled in the art in more fully, accurately and deeply understanding the inventive concept and technical solutions of the present invention.

Example 1

Preparation of compound A

Step a, adding 2.10g of 2,3,5, 6-tetrafluoroterephthalyl alcohol into a 100m L round-bottom flask, dissolving the mixture by redistilled Tetrahydrofuran (THF) with 25m L, diluting 6.08g of 10-undecenoyl chloride by Tetrahydrofuran (THF) with 25m L, adding the diluted mixture into a constant-pressure dropping funnel, adding a magnetic stirrer, dropwise adding the acyl chloride in an ice-water bath, taking 3.03g of TEA as an acid-binding agent, finishing dropping for about 15min, and reacting for 20h at normal temperature to obtain a crude product of the compound A, namely 2,3,5, 6-tetrafluoro-1, 4-di- (10-undecenoic acid) dimethyl benzoate (compound A).

b, step (b): and (2) performing suction filtration on the crude product of the compound A by using a Buchner funnel to remove triethylamine salt to obtain a light yellow or colorless solution, performing rotary drying on the solution by using a rotary evaporator to remove the solvent, preparing a developing agent of PE (polyethylene) EA (20: 1), performing column chromatography separation to obtain a solution of the compound A with high purity, preparing a developing agent of PE (polyethylene) EA (10: 1), monitoring the reaction process by using thin-layer chromatography, performing rotary drying on the solution containing the pure compound A, and drying overnight by using a vacuum drying oven to obtain white flocculent crystals, namely the high-

purity

2,3,5, 6-tetrafluoro-1, 4-di- (10-undecylenic acid) benzene dimethyl ester (compound A).

(II) Synthesis of Compound B

Taking 1.08g of the compound A purified in the previous step, adding the compound A into a 100m L round-bottom flask, dissolving the compound A in redistilled 15m L of DCM, adding 1.01g of 3-chloroperoxybenzoic acid in redistilled 20m L of DCM into a constant-pressure dropping funnel, adding a magnetic stirrer, dropwise adding the 3-chloroperoxybenzoic acid in an ice-water bath, finishing dropping for about 15min, and reacting for 16 hours at normal temperature to obtain a crude product of the compound B, namely 2,3,5, 6-tetrafluoro-1, 4-di- (10, 11-epoxy undecanoic acid) dimethyl benzene.

And washing the crude product of the compound B with a 30m L sodium sulfite saturated solution and a 30m L potassium carbonate saturated solution in sequence, stirring for 20min, washing the product with deionized water to be neutral, drying the organic phase with anhydrous sodium sulfate to obtain a pure compound B solution, spin-drying the solution, and drying the solution in a vacuum drying oven overnight to obtain a pure compound B.

Referring to the attached figure 1, the prepared B compound is characterized by nuclear magnetic hydrogen spectrum, and the position and the number of hydrogen atoms of a synthetic product are proved to accord with the molecular structure of the B compound from the peak position and the integral area.

Referring to the attached figure 2, the B compound prepared above is characterized by nuclear magnetic carbon spectrum, and the peak position proves that the carbon atom skeleton of the synthesized product conforms to the molecular structure of the B compound.

Referring to fig. 3, the molecular structure of the compound B is characterized by the aid of infrared spectroscopy.

Referring to FIG. 4, the compound B prepared above was characterized by mass spectrometry, and the resulting product was confirmed to be the same as the compound B by relative molecular mass, and was judged to be the compound B by other means of characterization.

(III) preparation of acetone response composite material

Step a, weighing 0.25g of the prepared B compound and 0.073g of 4-methylhexahydrophthalic anhydride, uniformly mixing at room temperature, adding 2-methylimidazole with the total weight of the B compound and the 4-methylhexahydrophthalic anhydride being 3 percent as a curing accelerator, uniformly mixing and dissolving with DMF, heating and concentrating the solution to 2m L, step B, paving the prepared mixture on a glass slide with the thickness of 25mm x 76mm, volatilizing the solvent and curing at the temperature of 90 ℃ for 1h, curing at the temperature of 110 ℃ for 4h, curing at the temperature of 130 ℃ for 4h, finally curing at the temperature of 150 ℃ for 4h to obtain a yellow transparent elastomer, and slowly stripping the elastomer from the glass slide by using a tool to obtain a yellow elastomer product which is an acetone response composite material.

Referring to fig. 5, the acetone responsive composite prepared above is a flat yellow transparent elastomer.

Referring to the attached figure 6, the prepared acetone response composite material deforms under the condition of acetone steam, and shows that the target product is a bionic environment sensitive material with extremely high acetone response performance, the material is cut into film devices in different shapes, the controllable deformation of a flexible device is realized by reversible curling, bending, twisting, winding, circling and rolling caused by absorbing the acetone steam, the film device is combined with bone fragments to be used as artificial muscles, and the bone fragments are driven to move under the stimulation of the acetone to realize bionic movement.

Example 2

Step a, weighing 0.25g of the compound B prepared in example 1 and 0.073g of 4-methylhexahydrophthalic anhydride, uniformly mixing at room temperature, adding 3 wt% of 2-methylimidazole serving as a curing accelerator, 5 wt% of MPS serving as a modifier and 1 wt% (calculated by double bond content) of AIBN serving as a double bond thermal initiator, uniformly mixing and dissolving with DMF, and heating the concentrated solution to 2m L.

b, step (b): spreading the mixture on a template, volatilizing the solvent at the temperature of 90 ℃ and curing for 1h, curing at the temperature of 110 ℃ for 4h, curing at the temperature of 130 ℃ for 4h, and finally curing at the temperature of 150 ℃ for 4h to obtain a yellow transparent elastomer, and slowly stripping the elastomer from the template by using a tool to obtain a yellow elastomer product, namely an acetone-responsive composite material, mainly comprising a polymer C and a polymer D, wherein the polymer D is formed by self-polymerization of 3- (methacryloyloxy) propyltrimethoxysilane (MPS) and has the following structure (V):

wherein: n is a positive integer.

The structure of the C polymer is shown as the following formula (IV):

wherein: n is a positive integer.

Referring to FIG. 7, the molecular structure of the acetone responsive composite material can be determined by infrared spectroscopic characterization of the acetone responsive composite material prepared in example 2.

The acetone responsive composite material prepared in example 2 above was cut into three samples of specified shapes for acid and alkali resistance control experiments.

Referring to fig. 8, the acetone responsive composite prepared in example 2 was not acid-base treated.

Referring to fig. 9, when the acetone responsive composite material prepared in example 2 is placed in an environment with a pH of about 1 and heated in a water bath for 6 hours at a temperature of 40 ℃, the surface morphology of the sample after acid treatment is not changed significantly, as shown by an Atomic Force Microscope (AFM), indicating that the film has good corrosion resistance under the acid condition.

Referring to fig. 9, when the acetone responsive composite material prepared in example 2 is placed in an environment with a pH of about 1 and heated in a water bath for 6 hours at a temperature of 40 ℃, the surface morphology of the sample after acid treatment is not changed significantly by an Atomic Force Microscope (AFM) characterization, which indicates that the film has good corrosion resistance under the acid condition.

Referring to fig. 10, when the acetone responsive composite material prepared in example 2 is placed in an environment with a pH of about 13 and heated in a water bath for 6 hours at a temperature of 40 ℃, the surface morphology of the sample after alkali treatment is not changed significantly, as shown by an Atomic Force Microscope (AFM), indicating that the film has good corrosion resistance under alkali conditions.

Example 3

Weighing 0.25g of the compound B prepared in the example 1 and 0.073g of 4-methylhexahydrophthalic anhydride, uniformly mixing at room temperature, adding 3 wt% of 2-methylimidazole serving as a curing accelerator, 10 wt% of MPS serving as a modifier and 1 wt% of AIBN (calculated by double bond content) serving as a double bond thermal initiator, uniformly mixing and dissolving the mixture by using DMF (dimethyl formamide), and heating the concentrated solution to 2m L.

b, step (b): spreading the mixture on a template, volatilizing the solvent at the temperature of 90 ℃ and curing for 1h, curing at the temperature of 110 ℃ for 4h, curing at the temperature of 130 ℃ for 4h, and finally curing at the temperature of 150 ℃ for 4h to obtain a yellow transparent elastomer, and slowly stripping the elastomer from the template by using a tool to obtain a yellow elastomer product, namely an acetone-responsive composite material, mainly comprising a polymer C and a polymer D, wherein the polymer D is formed by self-polymerization of 3- (methacryloyloxy) propyltrimethoxysilane (MPS).

Example 4

Weighing 0.25g of the compound B prepared in the example 1 and 0.073g of 4-methylhexahydrophthalic anhydride, uniformly mixing at room temperature, adding 3 wt% of 2-methylimidazole serving as a curing accelerator, 15 wt% of MPS serving as a modifier and 1 wt% of AIBN (calculated by double bond content) serving as a double bond thermal initiator, mixing and dissolving uniformly by using DMSO, and heating and concentrating the solution to 2m L.

Example 5

Weighing 0.25g of the compound B prepared in the example 1 and 0.073g of 4-methylhexahydrophthalic anhydride, uniformly mixing at room temperature, adding 2 wt% of 2-methylimidazole serving as a curing accelerator, 20 wt% of MPS serving as a modifier and 1 wt% (calculated by double bond content) of AIBN serving as a double bond thermal initiator, uniformly mixing and dissolving by using DMSO, and heating and concentrating the solution to 2m L.

Referring to fig. 11, thermogravimetric analysis (TG-DSC) was performed on the acetone-responsive composite materials prepared in examples 2 to 5, respectively, and the results of the experiments showed that the decomposition temperature of the film was about 350 ℃, which indicates that the film had good heat resistance.

Example 6

Referring to the attached drawing 12, 10 pieces of joints of 3mm × 2mm and a trapezoidal palm (upper bottom 8 mm; lower bottom 11 mm; height 4mm) of the yellow elastomer prepared in example 2 are cut out for standby, a certain number of fingers (3mm × 2mm) and connecting wood pieces (8mm × 2mm) are cut out from small wood pieces, the small wood pieces are bonded into the artificial palm shown in the attached drawing 12 by using adhesives such as double-sided adhesive and quick-drying adhesive, the artificial palm is bonded and fixed with a long wood strip, the long wood strip of the bionic hand is fixed, an acetone steam source with the concentration of 300ppm or more is close to the back of the hand, the artificial hand bends to the front under the stimulation response to perform the bionic action of grasping and grasping, when the acetone gas source is removed, the palm gradually opens and recovers to the original shape along with the continuous volatilization of the acetone gas, and the process can be repeated for multiple times. The prepared double-layer film can also be cut into other film devices with different shapes, and the controllable deformation of the flexible device is realized by absorbing reversible curling, bending, twisting, winding, circling and rolling caused by acetone vapor. The film is combined with the bone fragments to be used as artificial muscles, and the bone fragments are driven to move under the stimulation of acetone to realize bionic movement.

The above embodiments are only for further illustration of the present invention and are not intended to limit the present invention, and all equivalent implementations of the present invention should be included in the scope of the claims of the present invention.

Claims

1. An acetone-responsive biomimetic material is characterized in that the biomimetic material is a yellow transparent elastomer compounded by a C polymer and a D polymer which are acetone-responsive, and the content of the D polymer in the composite material is 0.1-20 wt%; the structure of the C polymer is shown as the following formula (I):

wherein: n is a positive integer;

the structure of the D polymer is shown as the following formula (II):

wherein: n is a positive integer.

2. A method of preparing an acetone responsive biomimetic material as described in claim 1, wherein 2,3,5, 6-tetrafluoro-1, 4-bis- (10, 11-epoxyundecanoic acid) benzenedimethylester is reacted with 4-methylhexahydrophthalic anhydride and 3- (methacryloyloxy) propyltrimethoxysilane in a ratio of 1: 0.5-4: 0.01-0.2 weight ratio, and carrying out a crosslinking reaction of the following structural reaction formula (III) at a temperature of 90-110 ℃:

and then curing for 1-4 hours to obtain a yellow transparent elastomer compounded by the polymer C and the polymer D, namely the target product is a bionic material responding to acetone.

3. The method for preparing an acetone-responsive biomimetic material as in claim 2, wherein the preparation of 2,3,5, 6-tetrafluoro-1, 4-bis- (10, 11-epoxyundecanoic acid) benzenedimethylester comprises the following steps:

step a, mixing 2,3,5, 6-tetrafluoro-p-xylene glycol and tetrahydrofuran according to the mass-volume ratio of 1g to 10-40 m L to obtain solution A for standby, mixing 10-undecenoyl chloride and tetrahydrofuran according to the mass-volume ratio of 1g to 15-40 m L to obtain solution B for standby, then mixing the solution A and the solution B according to the volume ratio of 1: 0.5-8, dropwise adding a triethylamine acid agent, and carrying out the synthesis reaction of the following structural binding reaction formula (IV) at normal temperature:

reacting for 16-25 hours, purifying the obtained product to obtain 2,3,5, 6-tetrafluoro-1, 4-di- (10-undecylenic acid) dimethyl benzene, and adding triethylamine acid-binding agent in an amount of 5-10 wt% of the solution A;

b, mixing the prepared 2,3,5, 6-tetrafluoro-1, 4-di- (10-undecylenic acid) benzyl ester and DCM according to the mass-volume ratio of 1g to 10-40 m L to obtain a solution C for standby, mixing 3-chloroperoxybenzoic acid and DCM according to the mass-volume ratio of 1g to 20-40 m L to obtain a solution D for standby, mixing the solution C and the solution D according to the volume ratio of 1: 1-16, and then carrying out the synthesis reaction of the following structural reaction formula (V) at normal temperature:

reacting for 12-20 hours to obtain a product, namely 2,3,5, 6-tetrafluoro-1, 4-di- (10, 11-epoxy undecanoic acid) dimethyl benzene, wherein the structure of the product is as follows (VI):

4. use of the acetone responsive biomimetic material according to claim 1, wherein the biomimetic material is cut into thin film devices of different shapes, and the controllable deformation of the flexible device is achieved by absorbing reversible curling, bending, twisting, winding, circling and rolling induced by acetone vapor, and the thin film device is used in combination with bone fragments as an artificial muscle to drive the bone fragments to move under the stimulation of acetone to achieve biomimetic movement.