CN115449052B - Stress-induced color-changing high polymer material based on folding-unfolding effect and preparation method thereof - Google Patents
Stress-induced color-changing high polymer material based on folding-unfolding effect and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a mechanochromism polymer material based on folding-unfolding effect and a preparation method thereof. When the polymer film is uniaxially stretched under UV irradiation (λ=365 nm), the excimer unfolds, the fluorescence changes from yellow to green, the film returns from green to yellow with relaxation of the stress, and this process can be repeated multiple times. The strategy provided by the invention is easy to realize, enriches the molecular tweezer type electrochromic material, and further promotes the development of the electrochromic material.
Description
Technical Field
The invention relates to the field of mechanochromism intelligent materials, in particular to a mechanochromism high polymer material based on folding-unfolding effect and a preparation method thereof.
Background
Excessive stress applied to the polymer can lead to molecular chain scission, leading to macroscopic breaking behaviour of the material, and it is therefore important to understand how and where such damage occurs. In recent years, the development of force-responsive, optically-responsive, electrochromic polymers has been of increasing interest, and such polymers have found wide-ranging applications, including pressure sensing materials, and detection of damage in structural materials, among others. The most commonly used force-responsive fluorophores typically have characteristic weak bonds, which are typically covalently linked to the polymer chains, rendering the polymeric material force-responsive. When the stress of the molecular chain exceeds a certain threshold, homolytic or heterolytic reactions occur to these weak bonds. Such structural changes, while resulting in changes in molecular absorption or fluorescence properties, are used to detect stress distribution of materials. However, cleavage of weak bonds in such force-sensitive groups is a typical irreversible process, which directly undermines the utility of the material itself.
It is desirable that the force sensitive fluorophore be pre-warned in a non-sacrificial or even reversible manner, and in recent years, rotaxane has been developed as a highly efficient mechanochromic fluorescent force sensor, which is a mechanically interlocking fluorophore consisting of a macrocyclic ring carrying the fluorophore and dumbbell-like molecules containing a matching quencher, integrated into the polymer backbone, whereby stretching of the molecular chain results in spatial separation of the fluorophore and quencher, thus turning on the fluorescence. By selecting different fluorophores, the optical properties of the rotaxane can be directly adjusted. At the same time, such fluorophores can be used to observe the ultra-small mechanical forces generated upon cell division. But the lengthy synthetic route and the low synthetic yield create a great obstacle to its use. Furthermore, weder et al report a cyclic mechanochromic fluorophore containing two fluorophores capable of forming an intramolecular excimer, the fluorescent emission of polyurethane containing the cyclic fluorophores being predominantly monodispersed by the excimer upon forced deformation, due to the relative dislocation of the dye molecules within the molecule.
Disclosure of Invention
Based on the above, the invention develops a new generation of tweezer type force-sensitive fluorophor which has the advantages similar to the above and is easy to prepare, and thereby synthesizes the force-sensitive color polymer material with folding-unfolding effect. The designed tweezer-type force-sensitive fluorescent molecule is formed by chemically bonding two fluorescent groups through a short connecting unit. Initially, two fluorophores in a force-sensitive fluorophore are stacked together by non-covalent interactions to form a dimer excimer, and when external forces are transferred to the tweezers, the dimer is pulled apart to form monodisperse dominant fluorescence. Thus, by folding-unfolding of pi conjugated dye molecules, reversible force-sensitive photoresponsive properties can be obtained.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the mechanochromism high polymer material based on folding-unfolding effect is obtained by polymerizing dihydric alcohol, diisocyanate and cyano-substituted phenylene ethylene dimer DCOP, wherein the structure of the cyano-substituted phenylene ethylene dimer DCOP is as follows:
the dihydric alcohol is at least one of polyethylene glycol, ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
The diisocyanate is at least one of Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate (MDI), isophorone diisocyanate and toluene diisocyanate.
The preparation method of the mechanochromic polymer material based on the folding-unfolding effect comprises the following steps: a certain amount of cyano-substituted phenylene ethylene dimer DCOP, dihydric alcohol and diisocyanate are dissolved in tetrahydrofuran, dibutyl tin dilaurate is added dropwise into the mixture, and the mixture is stirred for 3 hours at room temperature; then adding a THF solution dissolved with butanediol, and stirring the mixture at room temperature for reaction for 24 hours; subsequently, ethanol is added into the reaction mixture, and after stirring is carried out for 30 minutes, the reaction mixture is poured into the ethanol; collecting yellow precipitate by filtration; and separating out the solid from THF twice to obtain yellow solid DPU-m, namely the mechanochromic polymer material.
Further, the molar ratio of diisocyanate to diol is 1:0.9-1:1.1.
Further, the mass fraction of DCOP in the polymer DPU is 0.1% -0.5%.
Further, the preparation of the DCOP comprises the following steps:
1) Adding 2, 5-dihydroxy-1, 4-terephthalaldehyde, 1-bromohexane, anhydrous potassium carbonate and DMF into a reaction vessel to obtain a mixture; the mixture was heated at 80℃for 24h, after the reaction was completed, poured into water and treated with CH 2 Cl 2 Extracting for several times, anhydrous Na 2 SO 4 After drying, the organic layer was evaporated in vacuo to give the crude product; obtaining a compound A by recrystallization in methanol;
2) Dissolving triethylene glycol in dried CH 2 Cl 2 Cooling the solution to 0 ℃ with an ice bath under nitrogen atmosphere, and adding triethylamine; subsequently, p-toluenesulfonyl chloride was added to the cooled reaction mixture; after complete addition, the solution was warmed to room temperature and stirred for 24 hours; the mixture was washed with water and Na 2 SO 4 Drying the organic layer, filtering, and vacuum concentrating to obtain a crude product; purifying by column chromatography to obtain a compound B;
3) Parahydroxyphenylacetonitrile, compounds B and K 2 CO 3 Adding the mixture into acetonitrile; the mixture was refluxed for 12h, cooled to room temperature, filtered, washed several times with acetonitrile and the organic layer was washed with anhydrous Na 2 SO 4 Drying and vacuum concentrating; purifying by column chromatography to obtain a compound C;
4) On CH 2 Cl 2 Adding p-hydroxyphenylacetonitrile and anhydrous p-toluenesulfonic acid; cooling the solution to 0 ℃, and then dropwise adding 3, 4-2H-dihydropyran; after complete addition, the mixture was warmed to room temperature and stirred for 6 hours; with Na 2 CO 3 Washing the solution with an aqueous solution; the organic phase was dried over anhydrous sodium sulfate, and then distilled under reduced pressure; purifying by column chromatography to obtain a compound D;
5) Dissolving compound a, compound C and compound D in a mixture of t-BuOH and THF at 70 ℃; fast addition of t-BuOK and n-Bu 4 NOH, the solution immediately turned purple; stirring the mixture at 70deg.C for 15 min, cooling to room temperature, and pouring into water; by CH 2 Cl 2 Extracting the solution twice; the organic layer was treated with anhydrous Na 2 SO 4 Drying and then distilling under reduced pressure; purifying by column chromatography to obtain compound E and MCOP;
6) Adding a compound E and p-toluenesulfonic acid into methanol; the mixture was stirred at room temperature overnight; during this time a red solid precipitate formed; this solid was filtered and washed with methanol; vacuum drying the solid to obtain a red solid compound F;
7) Dissolving tetraethylene glycol and triethylamine in CH 2 Cl 2 Cooling the solution to 0 ℃, and dropwise adding a p-toluenesulfonyl chloride solution; the resulting mixture was stirred at room temperature for 16 hours; the solution was sequentially treated with 5% HCl (aq), saturated NaHCO 3 、H 2 O washing; the organic layer was treated with anhydrous Na 2 SO 4 Drying, and then distilling under reduced pressure; purifying by column chromatography to obtain a compound G;
8) Compound F, compound G, K 2 CO 3 And acetonitrile was added to the flask; reflux the mixture 24h, after cooling to room temperature, filtering, washing with acetonitrile for several times, and vacuum drying to obtain the red solid DCOP.
Further, the reaction mole ratio of the 2, 5-dihydroxyl-1, 4-terephthalaldehyde, 1-bromohexane and anhydrous potassium carbonate in the step 1) is as follows: 1/2.5/2.5; p-hydroxyphenylacetonitrile, compounds B and K in step 3) 2 CO 3 The molar ratio of the reaction is as follows: 1/1.2/1.5.
Further, the molar ratio of the compound A, the compound C and the compound D in the step 5) is as follows: 1/1.1/1.2; the molar ratio of compound E to p-toluenesulfonic acid in step 6) is: 100/0.5.
Further, compound F, compound G, K in step 8) 2 CO 3 The molar ratio of the reaction is as follows: 2/1/2.5.
The invention also protects the application of the mechanochromatic polymer material based on the folding-unfolding effect in reversible mechanochromatic materials.
Compared with the prior art, the invention has the beneficial effects that:
the DCOP tweezer molecule-based mechanochromism high molecular material designed by the invention has good reversible mechanochromism performance. The force response characteristic of DCOP tweezer molecules in the high molecular material is mainly derived from the intramolecular folding-unfolding effect of COP groups under the stimulation of external force. In the ground state, there is a degree of intramolecular interaction between COP groups, forming excimer. When the polymer film is uniaxially stretched under UV irradiation (λ=365 nm), the excimer unfolds, the fluorescence changes from yellow to green, the film returns from green to yellow with relaxation of the stress, and this process can be repeated multiple times. The strategy provided by the invention is easy to realize, enriches the molecular tweezer type electrochromic material, and further promotes the development of the electrochromic material.
Drawings
Fig. 1. Uv-vis absorption spectrum and fluorescence emission spectrum of dcop and MCOP in THF solution (c=5 um/L, λex=365 nm).
FIG. 2. (a) images of DPU-0.2 and MPU-0.2 under UV light and visible light; fluorescence decay spectra of DPU-0.2 (b) and MPU-0.2 (c) films.
FIG. 3 normalized fluorescence spectrum of DPU-0.2 film (strain gradually increasing).
Detailed Description
The above-described matters of the present invention will be further described in detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
The prepared electrochromic polymer material is tested according to the following method:
the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum are measured by a Bruker AVANCE II nuclear magnetic resonance apparatus, tetramethyl silicon is used as an internal standard, and the solvent is deuterated chloroform or deuterated dimethyl sulfoxide. The fluorescence spectrum was measured by using a Shimadzu RF-5301PC fluorescence spectrophotometer.
The preparation of DCOP comprises the following steps:
1) Adding 2, 5-dihydroxy-1, 4-terephthalaldehyde, 1-bromohexane, anhydrous potassium carbonate and DMF into a reaction vessel to obtain a mixture; the mixture was heated at 80℃for 24h, after the reaction was completed, poured into water and treated with CH 2 Cl 2 Extracting for several times, anhydrous Na 2 SO 4 After drying, the organic layer was evaporated in vacuo to give the crude product; obtaining a compound A by recrystallization in methanol;
2) Dissolving triethylene glycol in dried CH 2 Cl 2 Cooling the solution to 0 ℃ with an ice bath under nitrogen atmosphere, and adding triethylamine; subsequently, p-toluenesulfonyl chloride was added to the cooled reaction mixture; after complete addition, the solution was warmed to room temperature and stirred for 24 hours; the mixture was washed with water and Na 2 SO 4 Drying the organic layer, filtering, and vacuum concentrating to obtain a crude product; purifying by column chromatography to obtain a compound B;
3) Parahydroxyphenylacetonitrile, compounds B and K 2 CO 3 Added into acetonitrileThe method comprises the steps of carrying out a first treatment on the surface of the The mixture was refluxed for 12h, cooled to room temperature, filtered, washed several times with acetonitrile and the organic layer was washed with anhydrous Na 2 SO 4 Drying and vacuum concentrating; purifying by column chromatography to obtain a compound C;
4) On CH 2 Cl 2 Adding p-hydroxyphenylacetonitrile and anhydrous p-toluenesulfonic acid; cooling the solution to 0 ℃, and then dropwise adding 3, 4-2H-dihydropyran; after complete addition, the mixture was warmed to room temperature and stirred for 6 hours; with Na 2 CO 3 Washing the solution with an aqueous solution; the organic phase was dried over anhydrous sodium sulfate, and then distilled under reduced pressure; purifying by column chromatography to obtain a compound D;
5) Dissolving compound a, compound C and compound D in a mixture of t-BuOH and THF at 70 ℃; fast addition of t-BuOK and n-Bu 4 NOH, the solution immediately turned purple; stirring the mixture at 70deg.C for 15 min, cooling to room temperature, and pouring into water; by CH 2 Cl 2 Extracting the solution twice; the organic layer was treated with anhydrous Na 2 SO 4 Drying and then distilling under reduced pressure; purifying by column chromatography to obtain compound E and MCOP;
6) Adding a compound E and p-toluenesulfonic acid into methanol; the mixture was stirred at room temperature overnight; during this time a red solid precipitate formed; this solid was filtered and washed with methanol; vacuum drying the solid to obtain a red solid compound F;
7) Dissolving tetraethylene glycol and triethylamine in CH 2 Cl 2 Cooling the solution to 0 ℃, and dropwise adding a p-toluenesulfonyl chloride solution; the resulting mixture was stirred at room temperature for 16 hours; the solution was sequentially treated with 5% HCl (aq), saturated NaHCO 3 、H 2 O washing; the organic layer was treated with anhydrous Na 2 SO 4 Drying, and then distilling under reduced pressure; purifying by column chromatography to obtain a compound G;
8) Compound F, compound G, K 2 CO 3 And acetonitrile was added to the flask; the mixture was refluxed for 24h, cooled to room temperature, filtered, washed several times with acetonitrile and dried in vacuo to give DCOP as a red solid.
Reaction molar ratio of 2, 5-dihydroxy-1, 4-terephthalaldehyde, 1-bromohexane and anhydrous potassium carbonate in step 1)The method comprises the following steps: 1/2.5/2.5; p-hydroxyphenylacetonitrile, compounds B and K in step 3) 2 CO 3 The molar ratio of the reaction is as follows: 1/1.2/1.5.
The molar ratio of compound A, compound C and compound D in step 5) is: 1/1.1/1.2; the molar ratio of compound E to p-toluenesulfonic acid in step 6) is: 100/0.5.
Compound F, compound G, K in step 8) 2 CO 3 The molar ratio of the reaction is as follows: 2/1/2.5.
Example 1: preparation of mechanochromatic high molecular material DPU-0.1
The preparation route is as follows:
5mg of DCOP, hydroxyl-terminated polytetrahydrofuran (Mn=2000 g/mol,3.20g,1.60 mmol) and MDI (1.23 g,4.90 mmol) were dissolved in 30mL of tetrahydrofuran, dibutyltin dilaurate (2 drops) was added dropwise to the mixture, and stirred at room temperature for 3 hours. Then, 10mL of a THF solution in which butanediol (288 mg,3.20 mmol) was dissolved was added, and the mixture was stirred at room temperature for reaction for 24 hours. Then, 5mL of ethanol was added to the reaction mixture, and after stirring for 30 minutes, the reaction mixture was poured into ethanol (200 mL). The yellow precipitate was collected by filtration. The solid was precipitated from THF twice more to give DPU-0.1 as a yellow solid.
Example 2: preparation of mechanochromatic high molecular material DPU-0.2
The preparation method comprises the following specific steps: the same parts as those of example 1 are not repeated, but the difference from example 1 is that the addition amount of DCOP is 10mg.
Example 3: preparation of mechanochromatic high molecular material DPU-0.4
The preparation method comprises the following specific steps: the same parts as those of example 1 are not repeated, but the difference from example 1 is that the addition amount of DCOP is 20mg.
Comparative example 1: preparation of control Polymer Material MPU-0.2
The preparation route is as follows:
10mg of MCOP, hydroxyl-terminated polytetrahydrofuran (Mn=2000 g/mol,3.20g,1.60 mmol) and MDI (1.23 g,4.90 mmol) were dissolved in 30mL of tetrahydrofuran, dibutyltin dilaurate (2 drops) was added dropwise to the mixture, and stirred at room temperature for 3 hours. Then, 10mL of a THF solution in which butanediol (288 mg,3.20 mmol) was dissolved was added, and the mixture was stirred at room temperature for reaction for 24 hours. Then, 5mL of ethanol was added to the reaction mixture, and after stirring for 30 minutes, the reaction mixture was poured into ethanol (200 mL). The yellow precipitate was collected by filtration. The solid was precipitated from THF twice more to give MPU-0.2 as a yellow solid.
Comparative example 2: preparation of control Polymer Material MPU-0.4
The preparation method comprises the following specific steps: the same parts as those of comparative example 1 are not described in detail, and the difference from comparative example 1 is that the addition amount of MCOP is 20mg.
Hereinafter, the mechanochromatic polymer material based on the folding-unfolding effect and the preparation method thereof according to the present invention will be further described with reference to examples.
First, the optical properties of MCOP and DCOP (c=5um/L) in THF solution were studied by uv-vis absorption spectroscopy and fluorescence spectroscopy (fig. 1). In the absorption spectrum, MCOP exhibits S 0 -S 1 Transition vibration band, two absorption peaks at 365 and 431nm, respectively belonging to A 0-1 And A 0-0 Vibrating band (fig. 1 (a)); there is a distinct emission band at 505nm in the emission spectrum and distinct bright green fluorescence is emitted ((b) in fig. 1). The maximum vibration band of DCOP (-366, 431 nm) is similar to the wavelength of MCOP, but A 0-1 Is stronger than MCOP. This suggests that the COP moiety in DCOP has some degree of interaction in the ground state, favoring excimer formation. Furthermore, the DCOP was stronger in the emission band at 550nm, further verifying the formation of excimer (FIG. 1 (b)). A is that 0-1 And A 0-0 Intensity ratio of vibration band (A 0-1 /A 0-0 ) Can be used for estimating CO in MCOP or DCOPIntensity of intermolecular or intramolecular interactions of P groups, A 0-1 /A 0-0 The higher the value, the stronger the non-covalent interactions between COP groups or within the molecule. A of MCOP and DCOP calculated from absorption spectra 0-1 /A 0-0 The values were 0.66 and 0.75, respectively.
DPU-m and MPU-n, namely polyurethane electrochromic high molecular materials containing DCOP and MCOP groups, are prepared by polyaddition reaction among polytetrahydrofuran, methylene diphenyl diisocyanate (MDI), MCOP or DCOP, wherein m and n respectively represent the mass percentage of the DCOP and the MCOP in polyurethane. All polyurethanes synthesized had a number average molecular weight between 31000 and 58100g/mol and a degree of polymerization between 1.6 and 2, which is consistent with the expected results for the polymers obtained by polymerization (Table 1). The films DPU-0.4, DPU-0.2, DPU-0.1, MPU-0.4 and MPU-0.2 were obtained by directly coating the THF solutions of the polymers of the respective concentrations on the polytetrafluoroethylene film after evaporation of the solvents. The results show that the optical properties of DPU and MPU films are independent of dye content (at lower concentrations), so we take DPU-0.2 and MPU-0.2 as examples, further confirming the decisive role of DCOP tweezer molecules for the material force electrochromic properties. (fig. 2 (a)) shows that the DPU-0.2 and MPU-0.2 films respectively exhibited yellow and yellow-green colors under visible light, and green and yellow fluorescence under 365nm UV. The fluorescence lifetime measurement of the film showed that (fig. 2 (b), fig. 2 (c)), the decay curve of the MPU-0.2 film exhibited a single exponential function, verifying that only one species with a lifetime of 3.2ns was present, which may belong to the monodisperse state of COP groups. In contrast, the decay curve of the DPU-0.2 film exhibits a double exponential function, indicating the presence of two different species with lifetimes of 2.8ns and 14.2ns, respectively, which are believed to be associated with monodisperse COP (2.8 ns) and weakly coupled excimer (14.2 ns). This conclusion illustrates the formation of dimer excimer between COP groups in DPU-0.2 films.
After a certain knowledge of the photophysical properties of MCOP, DCOP and their polymer films, we further studied the mechanochromatic properties of MPU-0.2 and DPU-0.2 films. The initial DPU-0.2 film exhibits typical stress-strain behavior of rubber polymers. Under UV irradiationWhen uniaxially stretching is performed at lower (λ=365 nm), a change in fluorescence from yellow to green is detected due to the expansion of COP tweezers, and when the external force is relaxed, the green fluorescence can be restored to the original state, and this process can be repeated a plurality of times. However, MPU-0.2 film did not appear to be similarly during stretching, and when the strain reached 300%, the fluorescence of the film remained green. And transmitting a fluorescence signal to a detector by using an optical fiber, and analyzing the fluorescence response of the film in the in-situ uniaxial stretching process. With increasing strain, the fluorescence spectrum of DPU-0.2 shows a significant blue shift, with the emission band intensity at 550nm gradually decreasing and the emission band intensity at 510nm gradually increasing (FIG. 3). It was found that in this process, I 550 /I 510 The values are approximately linear with strain, indicating that the stress is effectively transferred to the COP dimer mechanics. After stress relaxation, the fluorescence spectrum returns to the original state, indicating that the folding and unfolding of COD is mechanically reversible. These results indicate that the linking units in the DCOP fluorophores favor the formation of excimer, ultimately achieving fold-unfolding behavior.
The following tables are the number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (PDI) of the polymers DPU-m and MPU-n.
TABLE 1
Therefore, the polyurethane polymer material based on the folding-unfolding effect provided by the invention has good reversible force electrochromic performance. The technical route is easy to realize, enriches molecular tweezer type electrochromic materials, and further promotes the development of the electrochromic materials.
The present invention is not limited to the preferred embodiments, and any simple modification, equivalent replacement, and improvement made to the above embodiments by those skilled in the art without departing from the technical scope of the present invention, will fall within the scope of the present invention.
Claims (10)
1. The stress-induced color-changing high polymer material based on folding-unfolding effect is characterized in that the stress-induced color-changing high polymer material is obtained by polymerizing dihydric alcohol, diisocyanate and cyano-substituted phenylene ethylene dimer DCOP, and the structure of the cyano-substituted phenylene ethylene dimer DCOP is as follows:
2. the stress-induced color change polymer material based on folding-unfolding effect according to claim 1, wherein the dihydric alcohol is at least one of polyethylene glycol, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, and 1, 6-hexanediol.
3. The stress-induced color change polymer material based on folding-unfolding effect according to claim 1, wherein the diisocyanate is at least one of hexamethylene diisocyanate HDI, dicyclohexylmethane diisocyanate, diphenylmethane diisocyanate MDI, isophorone diisocyanate, toluene diisocyanate.
4. A method for preparing a mechanochromatic polymeric material based on the folding-unfolding effect as claimed in any one of claims 1 to 3, characterized by comprising the following steps: a certain amount of cyano-substituted phenylene ethylene dimer DCOP, dihydric alcohol and diisocyanate are dissolved in tetrahydrofuran, dibutyl tin dilaurate is added dropwise into the mixture, and the mixture is stirred for 3 hours at room temperature; then adding a THF solution dissolved with butanediol, and stirring the mixture at room temperature for reaction for 24 hours; subsequently, ethanol is added into the reaction mixture, and after stirring is carried out for 30 minutes, the reaction mixture is poured into the ethanol; collecting yellow precipitate by filtration; and separating out the solid from THF twice to obtain yellow solid DPU, namely the mechanochromic polymer material.
5. The method for preparing a mechanochromatic polymer material based on a folding-unfolding effect according to claim 4, wherein the molar ratio of diisocyanate to dihydric alcohol is 1:0.9-1:1.1.
6. The method for preparing a stress-induced color change polymer material based on a folding-unfolding effect according to claim 4, wherein the mass fraction of DCOP in the polymer DPU is 0.1% -0.5%.
7. The method for preparing the stress-induced color change polymer material based on the folding-unfolding effect according to claim 4, wherein the preparation of the DCOP comprises the following steps:
1) Adding 2, 5-dihydroxy-1, 4-terephthalaldehyde, 1-bromohexane, anhydrous potassium carbonate and DMF into a reaction vessel to obtain a mixture; the mixture was heated at 80℃for 24h, after the reaction was completed, poured into water and treated with CH 2 Cl 2 Extracting for several times, anhydrous Na 2 SO 4 After drying, the organic layer was evaporated in vacuo to give the crude product; obtaining a compound A by recrystallization in methanol;
2) Dissolving triethylene glycol in dried CH 2 Cl 2 Cooling the solution to 0 ℃ with an ice bath under nitrogen atmosphere, and adding triethylamine; subsequently, p-toluenesulfonyl chloride was added to the cooled reaction mixture; after complete addition, the solution was warmed to room temperature and stirred for 24 hours; the mixture was washed with water and Na 2 SO 4 Drying the organic layer, filtering, and vacuum concentrating to obtain a crude product;
purifying by column chromatography to obtain a compound B;
3) Parahydroxyphenylacetonitrile, compounds B and K 2 CO 3 Adding the mixture into acetonitrile; the mixture was refluxed for 12h, cooled to room temperature, filtered, washed several times with acetonitrile, and the organic phase was taken upAnhydrous Na for layer 2 SO 4 Drying and vacuum concentrating; purifying by column chromatography to obtain a compound C;
4) On CH 2 Cl 2 Adding p-hydroxyphenylacetonitrile and anhydrous p-toluenesulfonic acid; cooling the solution to 0 ℃, and then dropwise adding 3, 4-2H-dihydropyran; after complete addition, the mixture was warmed to room temperature and stirred for 6 hours; with Na 2 CO 3 Washing the solution with an aqueous solution;
the organic phase was dried over anhydrous sodium sulfate, and then distilled under reduced pressure; purifying by column chromatography to obtain a compound D;
5) Dissolving compound a, compound C and compound D in a mixture of t-BuOH and THF at 70 ℃; fast addition of t-BuOK and n-Bu 4 NOH, the solution immediately turned purple; stirring the mixture at 70deg.C for 15 min, cooling to room temperature, and pouring into water; by CH 2 Cl 2 Extracting the solution twice; the organic layer was treated with anhydrous Na 2 SO 4 Drying and then distilling under reduced pressure;
purifying by column chromatography to obtain compound E and MCOP;
6) Adding a compound E and p-toluenesulfonic acid into methanol; the mixture was stirred at room temperature overnight; during this time a red solid precipitate formed; this solid was filtered and washed with methanol; vacuum drying the solid to obtain a red solid compound F;
7) Dissolving tetraethylene glycol and triethylamine in CH 2 Cl 2 Cooling the solution to 0 ℃, and dropwise adding a p-toluenesulfonyl chloride solution; the resulting mixture was stirred at room temperature for 16 hours; the solution was sequentially treated with 5% aqueous HCl, saturated NaHCO 3 、H 2 O washing; the organic layer was treated with anhydrous Na 2 SO 4 Drying, and then distilling under reduced pressure; purifying by column chromatography to obtain a compound G;
8) Compound F, compound G, K 2 CO 3 And acetonitrile was added to the flask; the mixture was refluxed for 24h, cooled to room temperature, filtered, washed several times with acetonitrile and dried in vacuo to give DCOP as a red solid.
8. The high stress-induced color change based on fold-unfold effect according to claim 7The preparation method of the molecular material is characterized in that the reaction mole ratio of the 2, 5-dihydroxyl-1, 4-terephthalaldehyde, 1-bromohexane and anhydrous potassium carbonate in the step 1) is as follows: 1/2.5/2.5; p-hydroxyphenylacetonitrile, compounds B and K in step 3) 2 CO 3 The molar ratio of the reaction is as follows: 1/1.2/1.5.
9. The method for preparing a mechanochromatic polymer material based on the folding-unfolding effect according to claim 7, wherein the molar ratio of the reaction of the compound A, the compound C and the compound D in the step 5) is as follows: 1/1.1/1.2; the molar ratio of compound E to p-toluenesulfonic acid in step 6) is: 100/0.5; compound F, compound G, K in step 8) 2 CO 3 The molar ratio of the reaction is as follows: 2/1/2.5.
10. Use of a mechanochromatic polymeric material according to any one of claims 1 to 3, based on the fold-unfold effect, in reversible mechanochromatic materials.
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