CN114085195A - Biodegradable film material with light conversion function, preparation method thereof and film doping material thereof - Google Patents
Biodegradable film material with light conversion function, preparation method thereof and film doping material thereof Download PDFInfo
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Abstract
The invention discloses a film doping material with a light conversion function, which can emit red fluorescence with the wavelength absorbed by corresponding plants by absorbing the wavelength of a specific part in sunlight, achieves the effect of supplementing light to the plants by using natural light, and can be used for cultivation and production of various agricultural products. The invention also discloses a biodegradable film material with the light conversion function, which is prepared by mixing the film doping material with the light conversion function and polylactic acid. The invention also discloses a preparation method of the biodegradable film material with the light conversion effect.
Description
Technical Field
The invention relates to the field of biodegradable film materials, in particular to a biodegradable film material with a light conversion effect, a preparation method thereof and a film doping material thereof.
Background
The plastic greenhouse film has very wide application in agricultural production, plays an extremely important role in adjusting the environmental temperature, humidity, carbon dioxide concentration and the like in the growth process of crops, is an essential part for realizing the production of high-quality and high-yield crops, and is an important guarantee for coping with national food safety and food crisis.
At present, the more big-arch shelter membrane of using in the market mainly has two main types: the first type is a film prepared by taking transparent polymers such as polyvinyl chloride (PVC), Polyethylene (PE) and the like as raw materials, has good heat preservation, light transmission and weather resistance, is soft and easy to shape, and is the most widely used plastic greenhouse film in China at present. The second kind of light regulating agricultural film is one with light regulating film of RE and other functional assistant added into PE and other polymer, and is one new kind of covering material capable of utilizing sunlight energy selectively.
However, after the united ecological environment department of the national development and improvement issues the opinion on further enhanced plastic pollution control in 16/1/2020, each province and the city actively respond to the relevant policy of 'forbidden plastic', which will cause that the non-degradable plastics mainly comprising PVC, PE and the like will be quickly replaced by the novel environment-friendly plastics represented by polylactic acid and the like, and the development and production of the novel greenhouse film material mainly comprising the environment-friendly plastics become the problems to be solved urgently, especially the light-regulating agricultural film with stronger applicability and pertinence.
Disclosure of Invention
The first purpose of the invention is to provide a thin film doping material with light conversion function, which has the advantages of light conversion function and good compatibility.
The technical purpose of the invention is realized by the following technical scheme:
a thin film doped material with light conversion function has a structure shown as a formula (I):
by adopting the technical scheme, the method has the advantages that,
the second purpose of the invention is to provide a biodegradable film material with light conversion function, which has the advantages of light conversion function and biodegradability.
The technical purpose of the invention is realized by the following technical scheme:
a biodegradable film material having a light-converting effect, which is obtained by mixing the film-doped material having a light-converting effect according to claim 1 with polylactic acid.
By adopting the technical scheme, the method has the advantages that,
the third purpose of the present invention is to provide a method for preparing the biodegradable film material with light conversion function, which has the advantages of complete reaction and high yield.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene:
the synthetic route is as follows:
weighing 1, 9-dibromonaphthalene, p-cyanomethyl phenylboronic acid and tetrakis (triphenylphosphine) palladium, dissolving in a toluene/tetrahydrofuran mixed solution, and adding K2CO3A solution; heating and refluxing for reaction under the condition of nitrogen; cooling the reaction liquid, extracting, combining organic phases, adding anhydrous magnesium sulfate and drying; filtering, concentrating under reduced pressure to obtain residue, separating with silica gel column chromatography, and rotary steaming under reduced pressure to obtain intermediate 1, 9-dibenzyl cyanide naphthalene, wherein the structure of 1, 9-dibenzyl cyanide naphthalene is formula (II);
step 2, synthesizing a film doping material with a light conversion effect:
the synthetic route is as follows:
weighing 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzylcyanonaphthalene, dissolving in an absolute ethanol solution, adding sodium methoxide after uniformly stirring, heating and stirring for reaction, filtering and washing filter residue by using the absolute ethanol solution after the reaction is finished, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding anhydrous magnesium sulfate for drying, filtering, concentrating under reduced pressure to obtain a residue, carrying out silica gel column chromatography separation on the residue, and carrying out reduced pressure rotary evaporation on a solvent to obtain a product DNPCBTM, wherein the structure of the DNPCBTM is shown as a formula (I).
Step 3, preparing the biodegradable film material with the light conversion function:
and (3) adding the DNPCBTM obtained in the step (2) into a solvent for dissolving, adding polylactic acid, heating and stirring until the DNPCBTM is completely dissolved, continuing heating and stirring until the solution becomes viscous, stopping heating, completely volatilizing the viscous liquid solvent, and drying to obtain the DNPCBTM-doped polylactic acid film.
Further setting: 1, 9-dibromonaphthalene in step 1: p-cyanomethyl phenylboronic acid: tetrakis (triphenylphosphine) palladium: k2CO32mmol, 4-6mmol, 0.1-0.3:3-5 mmol; toluene: the volume ratio of the tetrahydrofuran is 30-60ml to 30-60 ml.
Further setting: the time of heating reflux reaction in the step 1 is 8-16 h; the temperature of the heating reflux is 80-140 ℃.
Further setting: the eluent used for column chromatography in step 1 was dichloromethane: petroleum ether is compounded according to the proportion of 2: 1.
Further setting: 1, 9-dibenzyl cyanide naphthalene in step 2: 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-carbaldehyde anhydrous ethanol sodium methoxide 1mmol:2-4mmol:30-60mL:10-20 mmol.
Further setting: the heating temperature in the step 2 is 40-60 ℃; the reaction time is 8-16 h.
Further setting: eluent used for column chromatography separation in step 2 is dichloromethane: petroleum ether is compounded according to the proportion of 2: 1.
Further setting: the mass-volume ratio of the DNPCBTM solid powder to the solvent is 1-50mg:10mL, and the mass ratio of the DNPCBTM solid powder to the polylactic acid particles is 1 g: 100-100000 g.
Further setting: the preparation method of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde is as follows:
heating a (4- (2'- (4' -methoxyphenyl) amino) phenyl) boric acid solution, a 7-bromo-4-aldehyde benzothiadiazole, tetrakis (triphenylphosphine) palladium and a K2CO3 solution in a toluene/tetrahydrofuran mixed solution under the condition of inert gas to 80-140 ℃ for reflux reaction; after the reaction is finished, the benzothiadiazole derivative is obtained by silica gel column chromatography separation.
The invention has the following beneficial effects:
the DNPCBTM can emit red fluorescence required by photosynthesis by absorbing ultraviolet and green light parts which are not utilized by plants in natural light through organic micromolecules, so that the DNPCBTM can be protected from being damaged by ultraviolet rays and can regulate the growth of crops through natural 'light supplement'; DNPCBTM also has very good compatibility with environment-friendly plastics such as polylactic acid and the like, and can be dispersed and doped in a monomolecular mode on the basis of not changing the original physical properties of the plastic film, so that the DNPCBTM is applied to the production of the light-adjusting agricultural film.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a fluorescence spectrum of a 0.005% wt doped film of DNPCBTM in PLA in accordance with the present invention;
FIG. 2 is an absorption spectrum of DNPCBTM in toluene in the present invention;
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
a preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene: 2mmol (0.5719g) of 1, 9-dibromonaphthalene, 2mmol (0.3219g) of p-cyanomethylbenzeneboronic acid and 0.1mmol (0.116g) of tetrakis (triphenylphosphine) palladium were weighed, and 3mmol (0.415g) of K2CO3 was further dissolved in a mixed solution of 30ml of toluene and 30ml of tetrahydrofuran. Heating to 90 ℃ under the condition of nitrogen, and carrying out reflux reaction for 10 h. And cooling the reaction liquid, extracting, combining organic phases, and adding anhydrous magnesium sulfate for drying. The residue obtained after filtration and concentration under reduced pressure was subjected to silica gel column chromatography with eluent (dichloromethane/petroleum ether ═ 1: 1), and the solvent was rotary-distilled under reduced pressure to obtain 0.5122g of dibenzylcyanonaphthalene as a white powdery intermediate with an overall yield of 71.4%.
Step 2, synthesizing the biodegradable film material with the light conversion effect:
weighing 2mmol (0.936g) of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanonaphthalene (II) (0.3584g), dissolving in 30ml of absolute ethanol solution, stirring uniformly, adding 10mmol (0.54g) of sodium methoxide, heating to 40 ℃, stirring and reacting for 8h, filtering, washing the filter residue with absolute ethanol solution, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding anhydrous magnesium sulfate, drying, filtering, concentrating the obtained residue under reduced pressure, and carrying out silica gel column chromatography separation, wherein the eluent is (dichloromethane/petroleum ether: 2:1), the solvent is reduced pressure and rotary evaporated to obtain 0.9411g of a deep red powdery product PCBDNTMM, and the total yield is 74.9%.
Step 3, preparing the biodegradable film material with the light conversion function:
taking 0.01g of DNPCBTM obtained in the step 2, putting into a small clean beaker, adding 10ml of dichloromethane to dissolve the DNPCBTM, adding 0.99g of polylactic acid, heating and stirring at 40 ℃ for about 5min until PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid onto a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining a DNPCBTM1 wt% doped PLA film;
taking 0.1g of the DNPCBTM1 wt% doped PLA film into a clean small beaker, adding 0.90g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining the DNPCBTM0.1 wt% doped PLA film;
and then taking 0.1g of the DNPCBTM0.1 wt% doped PLA film into a clean small beaker, adding 9.9g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring the viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form the film, thus obtaining the DNPCBTM0.001 wt% doped PLA film.
Example 2
A preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene: 2mmol (0.5719g) of 1, 9-dibromonaphthalene, 3mmol (0.4828g) of p-cyanomethylbenzeneboronic acid and 0.1mmol (0.116g) of tetrakis (triphenylphosphine) palladium were weighed, and 3mmol (0.415g) of K2CO3 was further dissolved in a mixed solution of 30ml of toluene and 30ml of tetrahydrofuran. Heating to 90 ℃ under the condition of nitrogen, and carrying out reflux reaction for 10 h. And cooling the reaction liquid, extracting, combining organic phases, and adding anhydrous magnesium sulfate for drying. The residue obtained after filtration and concentration under reduced pressure was subjected to silica gel column chromatography with an eluent (dichloromethane/petroleum ether ═ 1: 1), and the solvent was rotary-distilled under reduced pressure to obtain 0.5521g of dibenzylcyanonaphthalene as a white powder intermediate, in a total yield of 77%.
Step 2, synthesizing the biodegradable film material with the light conversion effect:
weighing 2.5mmol (1.172g) of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanonaphthalene (II) (0.3584g), dissolving in 30ml of absolute ethanol solution, stirring uniformly, adding 10mmol (0.54g) of sodium methoxide, heating to 40 ℃, stirring and reacting for 8h, filtering, washing the filter residue with the absolute ethanol solution, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding anhydrous magnesium sulfate, drying, filtering, concentrating the obtained residue under reduced pressure, and carrying out silica gel column chromatography separation, wherein an eluent is (dichloromethane/petroleum ether 2:1), and the solvent is reduced pressure and rotary evaporated to obtain a dark red powdery product DNPCBTM1.021g, and the total yield is 81.3%.
Step 3, preparing the biodegradable film material with the light conversion function:
taking 0.01g of DNPCBTM obtained in the step 2, putting into a small clean beaker, adding 10ml of dichloromethane to dissolve the DNPCBTM, adding 0.99g of polylactic acid, heating and stirring at 40 ℃ for about 5min until PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid onto a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining a DNPCBTM1 wt% doped PLA film;
taking 0.1g of the DNPCBTM1 wt% doped PLA film into a clean small beaker, adding 0.90g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining the DNPCBTM0.1 wt% doped PLA film;
and then taking 0.1g of the DNPCBTM0.1 wt% doped PLA film into a clean small beaker, adding 9.9g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring the viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form the film, thus obtaining the DNPCBTM0.001 wt% doped PLA film.
Example 3
A preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene: 2mmol (0.5719g) of 1, 9-dibromonaphthalene, 3mmol (0.4828g) of p-cyanomethylbenzeneboronic acid and 0.3mmol (0.347g) of tetrakis (triphenylphosphine) palladium were weighed, and 3mmol (0.415g) of K2CO3 was further dissolved in a mixed solution of 30ml of toluene and 30ml of tetrahydrofuran. Heating to 90 ℃ under the condition of nitrogen, and carrying out reflux reaction for 10 h. And cooling the reaction liquid, extracting, combining organic phases, and adding anhydrous magnesium sulfate for drying. The residue obtained after filtration and concentration under reduced pressure was subjected to silica gel column chromatography with an eluent (dichloromethane/petroleum ether ═ 1: 1), and the solvent was rotary-distilled under reduced pressure to obtain 0.5201g of dibenzylcyanonaphthalene as a white powder intermediate, in an overall yield of 72.5%.
Step 2, synthesizing the biodegradable film material with the light conversion effect:
weighing 3mmol (1.404g) of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanonaphthalene (II) (0.3584g), dissolving in 50ml of absolute ethanol solution, stirring uniformly, adding 10mmol (0.54g) of sodium methoxide, heating to 40 ℃, stirring and reacting for 8h, filtering, washing the filter residue with the absolute ethanol solution, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding anhydrous magnesium sulfate, drying, filtering, concentrating the obtained residue under reduced pressure, and carrying out silica gel column chromatography separation, wherein the eluent is (dichloromethane/petroleum ether: 2:1), the solvent is reduced pressure and rotary evaporated to obtain DNPCBTM1.102g of a dark red powdery product, and the total yield is 87.7%.
Step 3, preparing the biodegradable film material with the light conversion function:
taking 0.01g of DNPCBTM obtained in the step 2, putting into a small clean beaker, adding 10ml of dichloromethane to dissolve the DNPCBTM, adding 0.99g of polylactic acid, heating and stirring at 40 ℃ for about 5min until PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid onto a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining a DNPCBTM1 wt% doped PLA film;
taking 0.1g of the DNPCBTM1 wt% doped PLA film into a clean small beaker, adding 0.90g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining the DNPCBTM0.1 wt% doped PLA film;
and then taking 0.1g of the DNPCBTM0.1 wt% doped PLA film into a clean small beaker, adding 9.9g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring the viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form the film, thus obtaining the DNPCBTM0.001 wt% doped PLA film.
Example 4
A preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene: 2mmol (0.5719g) of 1, 9-dibromonaphthalene, 3mmol (0.4828g) of p-cyanomethylbenzeneboronic acid and 0.3mmol (0.347g) of tetrakis (triphenylphosphine) palladium were weighed, and 5mmol (0.691g) of K2CO3 was further dissolved in a mixed solution of 30ml of toluene and 50ml of tetrahydrofuran. Heating to 90 ℃ under the condition of nitrogen, and carrying out reflux reaction for 10 h. And cooling the reaction liquid, extracting, combining organic phases, and adding anhydrous magnesium sulfate for drying. The residue obtained after filtration and concentration under reduced pressure was subjected to silica gel column chromatography with an eluent (dichloromethane/petroleum ether ═ 1: 1), and the solvent was rotary-distilled under reduced pressure to obtain 0.4955g of dibenzylcyanonaphthalene as a white powder intermediate, with an overall yield of 69.1%.
Step 2, synthesizing the biodegradable film material with the light conversion effect:
weighing 3mmol (1.404g) of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanonaphthalene (II) (0.3584g), dissolving in 30ml of absolute ethanol solution, stirring uniformly, adding 20mmol (1.08g) of sodium methoxide, heating to 40 ℃, stirring and reacting for 8h, after the reaction is finished, filtering, washing the filter residue with the absolute ethanol solution, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding magnesium sulfate for drying, filtering, concentrating the obtained residue under reduced pressure, and performing silica gel column chromatography separation, wherein the eluent is (dichloromethane/petroleum ether: 2:1), the solvent is evaporated under reduced pressure to obtain 0.995g of a dark red powdery product PCBDNTML, and the total yield is 79.2%.
Step 3, preparing the biodegradable film material with the light conversion function:
taking 0.01g of DNPCBTM obtained in the step 2, putting into a small clean beaker, adding 10ml of dichloromethane to dissolve the DNPCBTM, adding 0.99g of polylactic acid, heating and stirring at 40 ℃ for about 5min until PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid onto a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining a DNPCBTM1 wt% doped PLA film;
taking 0.1g of the DNPCBTM1 wt% doped PLA film into a clean small beaker, adding 0.90g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining the DNPCBTM0.1 wt% doped PLA film;
and then taking 0.1g of the DNPCBTM0.1 wt% doped PLA film into a clean small beaker, adding 9.9g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring the viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form the film, thus obtaining the DNPCBTM0.001 wt% doped PLA film.
Example 5
A preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene: 2mmol (0.5719g) of 1, 9-dibromonaphthalene, 3mmol (0.4828g) of p-cyanomethylbenzeneboronic acid and 0.1mmol (0.116g) of tetrakis (triphenylphosphine) palladium were weighed, and 3mmol (0.415g) of K2CO3 was further dissolved in a mixed solution of 30ml of toluene and 50ml of tetrahydrofuran. Heating to 110 ℃ under the condition of nitrogen, and carrying out reflux reaction for 10 h. And cooling the reaction liquid, extracting, combining organic phases, and adding anhydrous magnesium sulfate for drying. The residue obtained after filtration and concentration under reduced pressure was subjected to silica gel column chromatography, eluent was (dichloromethane/petroleum ether ═ 1: 1), and solvent was rotary-distilled under reduced pressure to obtain 0.5021g of dibenzylcyanonaphthalene as a white powdery intermediate, with a total yield of 70%.
Step 2, synthesizing the biodegradable film material with the light conversion effect:
weighing 3mmol (1.404g) of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanonaphthalene (II) (0.3584g), dissolving in 30ml of absolute ethanol solution, stirring uniformly, adding 20mmol (1.08g) of sodium methoxide, heating to 60 ℃, stirring and reacting for 8h, after the reaction is finished, filtering, washing the filter residue with the absolute ethanol solution, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding magnesium sulfate to dry, filtering, concentrating under reduced pressure to obtain a residue, carrying out silica gel column chromatography separation, wherein the eluent is (dichloromethane/petroleum ether: 2:1), the solvent is reduced pressure and is rotary evaporated to obtain PCBDNTM1.085g of a dark red powdery product, and the total yield is 86.3%.
Step 3, preparing the biodegradable film material with the light conversion function:
taking 0.01g of DNPCBTM obtained in the step 2, putting into a small clean beaker, adding 10ml of dichloromethane to dissolve the DNPCBTM, adding 0.99g of polylactic acid, heating and stirring at 40 ℃ for about 5min until PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid onto a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining a DNPCBTM1 wt% doped PLA film;
taking 0.1g of the DNPCBTM1 wt% doped PLA film into a clean small beaker, adding 0.90g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining the DNPCBTM0.1 wt% doped PLA film;
and then taking 0.1g of the DNPCBTM0.1 wt% doped PLA film into a clean small beaker, adding 9.9g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring the viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form the film, thus obtaining the DNPCBTM0.001 wt% doped PLA film.
Example 6
A preparation method of a biodegradable film material with a light conversion effect comprises the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene: 2mmol (0.5719g) of 1, 9-dibromonaphthalene, 3mmol (0.4828g) of p-cyanobenzylboronic acid and 0.3mmol (0.348g) of tetrakis (triphenylphosphine) palladium were weighed out, and 5mmol (0.691g) of K2CO3 was further dissolved in a mixed solution of 30ml of toluene and 40ml of tetrahydrofuran. Heating to 110 ℃ under the condition of nitrogen, and carrying out reflux reaction for 16 h. And cooling the reaction liquid, extracting, combining organic phases, and adding anhydrous magnesium sulfate for drying. The residue obtained after filtration and concentration under reduced pressure was subjected to silica gel column chromatography with an eluent (dichloromethane/petroleum ether ═ 1: 1), and the solvent was rotary-distilled under reduced pressure to obtain 0.5301g of dibenzylcyanonaphthalene as a white powder intermediate, in an overall yield of 73.9%.
Step 2, synthesizing the biodegradable film material with the light conversion effect:
weighing 3mmol (1.404g) of 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanonaphthalene (II) (0.3584g), dissolving in 30ml of absolute ethanol solution, stirring uniformly, adding 20mmol (1.08g) of sodium methoxide, heating to 60 ℃, stirring and reacting for 12h, after the reaction is finished, filtering, washing the filter residue with the absolute ethanol solution, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding magnesium sulfate to dry, filtering, concentrating the obtained residue under reduced pressure to separate the residue by silica gel column chromatography, wherein the eluent is (dichloromethane/petroleum ether: 2:1), the solvent is evaporated under reduced pressure to obtain PCBDNTM1.102g of a dark red powdery product, and the total yield is 87.6%.
Step 3, preparing the biodegradable film material with the light conversion function:
taking 0.01g of DNPCBTM obtained in the step 2, putting into a small clean beaker, adding 10ml of dichloromethane to dissolve the DNPCBTM, adding 0.99g of polylactic acid, heating and stirring at 40 ℃ for about 5min until PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid onto a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining a DNPCBTM1 wt% doped PLA film;
taking 0.1g of the DNPCBTM1 wt% doped PLA film into a clean small beaker, adding 0.90g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form a film, thus obtaining the DNPCBTM0.1 wt% doped PLA film;
and then taking 0.1g of the DNPCBTM0.1 wt% doped PLA film into a clean small beaker, adding 9.9g of polylactic acid, adding 10ml of dichloromethane, heating and stirring at 40 ℃ for about 5min until the PLA is completely dissolved, continuing heating and stirring for 5min until the solution becomes viscous, stopping heating, pouring the viscous liquid on a clean glass plate prepared in advance, and taking down the solution after the solvent is completely volatilized and dried to form the film, thus obtaining the DNPCBTM0.001 wt% doped PLA film.
Comparative example 1: undoped PLA film.
The hydrogen nuclear magnetic resonance spectrum of dibenzylcyanonaphthalene is as follows:
1H NMR(400MHz,Chloroform-d)δ7.98(dd,1H),7.57(t,1H),7.39(dd,1H),6.96(d,2H),6.92(d,2H),3.65(s,2H)。
the results of nuclear magnetic resonance and mass spectrometry detection of DNPCBTM are as follows:
1H NMR(400MHz,Chloroform-d)δ8.26(s,1H),8.16(dd,J＝7.7,0.7Hz,1H),8.04(dd,J＝8.2,1.4Hz,1H),7.63(dd,J＝8.1,7.1Hz,1H),7.59–7.55(m,2H),7.53(dd,J＝7.0,1.4Hz,1H),7.50–7.46(m,2H),7.22(d,J＝7.7Hz,1H),7.12–7.08(m,2H),7.08–7.03(m,4H),6.96–6.87(m,2H),6.87–6.79(m,5H),3.81(s,6H)；
13C NMR(101MHz,CDCl3)δ156.31,154.49,152.26,149.24,144.42,140.14,138.98,135.42,135.19,134.60,132.35,130.87,130.83,130.01,129.47,129.19,127.59,127.23,126.55,125.48,125.36,125.02,123.60,119.13,118.37,114.83,111.27,77.35,77.24,77.03,76.72,55.48,29.71；
HRMS(ESI):m/z:Calcd for C80H56N8O4S2:1257.39442[M+H]+；Found:1257.38876。
and (3) performance detection:
a sample film was cut out from each red light conversion film, and the fluorescence properties of the light conversion films were measured by a Fluoromax-4 type fluorescence spectrometer manufactured by HORIBA.
The dumbbell-shaped sample films were cut transversely and longitudinally from the light-transmitting films in examples and comparative examples by using a GT-7016 cutting test piece machine in accordance with GB/T1040-92, and the tensile strength and elongation at break of the light-transmitting films were tested by using an electronic universal tester (RG 2000-10) manufactured by Shenzhen Rungel instruments GmbH.
TABLE 1 film Property test results Table
The above-described embodiments do not limit the scope of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the above-described embodiments should be included in the protection scope of the technical solution.
Claims (10)
1. A thin film doped material with light conversion function is characterized in that the material has a structure shown as a formula (I):
2. a biodegradable film material having a light-converting effect, which is obtained by mixing the film dope material having a light-converting effect according to claim 1 with polylactic acid.
3. A preparation method of a biodegradable film material with a light conversion effect is characterized by comprising the following steps:
step 1, synthesizing an intermediate compound dibenzyl cyano naphthalene:
the synthetic route is as follows:
weighing 1, 9-dibromonaphthalene, p-cyanomethyl phenylboronic acid and tetrakis (triphenylphosphine) palladium, dissolving in a toluene/tetrahydrofuran mixed solution, and adding K2CO3A solution; heating and refluxing for reaction under the condition of nitrogen; cooling the reaction liquid, extracting, combining organic phases, adding anhydrous magnesium sulfate and drying; filtering, concentrating under reduced pressure to obtain residue, separating with silica gel column chromatography, and rotary steaming under reduced pressure to obtain intermediate 1, 9-dibenzyl cyanide naphthalene, wherein the structure of 1, 9-dibenzyl cyanide naphthalene is formula (II);
step 2, synthesizing a film doping material with a light conversion effect:
the synthetic route is as follows:
weighing 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-formaldehyde and 1, 9-dibenzyl cyanide naphthalene, dissolving in an absolute ethanol solution, adding sodium methoxide after uniformly stirring, heating and stirring for reaction, filtering and washing filter residue by using the absolute ethanol solution after the reaction is finished, dissolving the filter residue in dichloromethane, extracting and combining organic phases, adding anhydrous magnesium sulfate for drying, filtering, concentrating under reduced pressure to obtain a residue, carrying out silica gel column chromatography separation on the residue, and carrying out reduced pressure rotary evaporation on a solvent to obtain a product DNPCBTM, wherein the structure of the DNPCBTM is shown as a formula (I).
Step 3, preparing the biodegradable film material with the light conversion function:
and (3) adding the DNPCBTM obtained in the step (2) into a solvent for dissolving, adding polylactic acid, heating and stirring until the DNPCBTM is completely dissolved, continuing heating and stirring until the solution becomes viscous, stopping heating, completely volatilizing the viscous liquid solvent, and drying to obtain the DNPCBTM-doped polylactic acid film.
4. The method for preparing biodegradable film material with light conversion effect as claimed in claim 3, wherein 1, 9-dibromonaphthalene, p-cyanomethyl phenylboronic acid, tetrakis (triphenylphosphine) palladium and K are used in step 12CO3Is 2mmol:4-6mmol:0.1-0.3:3-5 mmol; toluene: the volume ratio of the tetrahydrofuran is 30-60ml:30-60 ml.
5. The method for preparing biodegradable film material with light conversion function as claimed in claim 3, wherein the time of the temperature-raising reflux reaction in step 1 is 8-16 h; the temperature of the heating reflux is 80-140 ℃.
6. The method for preparing biodegradable film material with light conversion effect as claimed in claim 3, wherein the eluent used in column chromatography separation in step 1 is dichloromethane and petroleum ether mixed at a ratio of 2: 1.
7. The method of claim 3, wherein the ratio of 1, 9-dibenzylcyanonaphthalene to 7- (4- (bis (4- (4-methoxyphenyl) amino) phenyl) benzo [ c ] [1,2,5] thiadiazole-4-carbaldehyde to absolute ethanol to sodium methoxide in step 2 is 1mmol:2-4mmol:30-60mL:10-20 mmol.
8. The method for preparing biodegradable film material with light conversion effect according to claim 3, wherein the heating temperature in step 2 is 40-60 ℃; the reaction time is 8-16 h.
9. The method for preparing biodegradable film material with light conversion effect as claimed in claim 3, wherein the eluent used in column chromatography in step 2 is dichloromethane and petroleum ether mixed at a ratio of 2: 1.
10. The method of claim 3, wherein in step 3, the mass-to-volume ratio (mg/mL) of the DNPCBTM solid powder to the solvent is 1: 10 to 50: 10, and the mass ratio (g/g) of the DNPCBTM solid powder to the polylactic acid particles is 1: 100000 to 1: 100.
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