CN114805653B - Phenyl polydiacetylenic acid and preparation method, application and recovery thereof - Google Patents

Phenyl polydiacetylenic acid and preparation method, application and recovery thereof Download PDF

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CN114805653B
CN114805653B CN202210526898.0A CN202210526898A CN114805653B CN 114805653 B CN114805653 B CN 114805653B CN 202210526898 A CN202210526898 A CN 202210526898A CN 114805653 B CN114805653 B CN 114805653B
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acid
pbda
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polydialkynoic
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江力
胡丽
马超群
蒋陈晶
黄文艳
蒋其民
蒋必彪
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Changzhou University
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Abstract

The invention belongs to the field of material preparation, and discloses phenyl polydialkynoic acid, and a preparation method, application and recovery thereof. The invention takes 1, 4-di (4' -carboxybenzene) -1, 3-diacetylene (BDA) which can not generate topological polymerization under the conventional condition as a monomer, and is complexed with 1-naphthylmethyl amine (NMA) by adding the monomer to form eutectic. The high-efficiency topological polymerization of the phenyl diacetylene monomer can be realized by ultraviolet irradiation at normal temperature and normal pressure. And (3) pickling and recovering NMA to obtain the phenyl polydialkynoic acid with the side chain containing active carboxyl. The high-polymerization-degree phenyl polydialkynoic acid prepared by the method can catalyze the efficient degradation of organic matters in water under visible light, and can realize the recovery and regeneration of the catalyst through the reversible recombination and dissociation of the polydialkynoic acid and the magnetic nano material.

Description

Phenyl polydiacetylenic acid and preparation method, application and recovery thereof
Technical Field
The invention belongs to the technical field of photocatalytic degradation materials, and particularly relates to phenyl polydiacetylenic acid, and a preparation method, application and recovery thereof.
Background
Polydialkynes are intelligent materials with excellent performance, for example, common polydialkynes can be converted from blue phase to red phase under the action of external stimulus, and are often used in the field of sensing. In recent years, along with the deep research on polydiacetylene materials, the application prospect of the polydiacetylene materials in different fields is also continuously developed. The phenyl polydialkyne with the side group being a benzene ring can effectively catalyze the degradation of organic pollutants in water under the irradiation of visible light. This is because the phenyl polydialkyne backbone contains conjugated eneyne structure, and the benzene ring of the pendant group greatly increases the conjugation effect of the backbone, so that electrons are more easily transferred and transited. And electrons in the main chain of the phenyl polydialkyne which are transited to an excited state can be combined with dissolved oxygen in water to generate superoxide radicals, so that degradation of organic pollutants is realized. Since the phenyl polydialkyne has a smaller band gap, the phenyl polydialkyne has the capability of catalyzing degradation of pollutants in water under visible light.
Although the phenyl polydiacetylenes materials have shown excellent photocatalytic properties, their preparation, especially of high polymer phenyl polydiacetylenes, still faces significant challenges. This is because topological polymerization of diacetylene monomers often requires a regular arrangement of monomers to obtain a crystal structure that meets certain stacking parameters. The existence of side chain benzene rings in the phenyl diacetylene monomer leads to larger steric hindrance between the diacetylene monomers, and the distance between the diacetylene functional groups is relatively larger under the conventional condition, so that the minimum effective distance for topological polymerization of the diacetylene monomers is difficult to be met. Thus, under conventional conditions (irradiation with ultraviolet or gamma rays at normal temperature), the topological polymerization of the phenyldiacetylene monomer is difficult to achieve or only forms an oligomer with a polymerization degree of less than 10, and the low polymerization degree and the low conversion rate greatly limit the preparation efficiency and the application performance (particularly low photocatalytic efficiency). In order to prepare the high-polymerization-degree phenyl polydialkyne material with more excellent performance, a researcher adopts a high-pressure polymerization method, namely, the distance between phenyl polydialkyne monomers is reduced under the strong pressure of 15GPa, and the distance between the diyne functional groups reaches the minimum distance which satisfies the occurrence of topological polymerization, so that the preparation of the high-polymerization-degree phenyl polydialkyne is realized. The unconventional high-pressure polymerization is obviously unfavorable for the commercial production and practical application of the phenyl polydiacetylene material; and unconventional polymerization conditions are not applicable to phenyldiacetylene monomers containing other reactive side groups. Therefore, the preparation of the high-polymerization-degree phenyl polydiacetylene material with high-efficiency photocatalysis characteristic and side chain containing easily-modified active functional groups under the conventional condition has important theoretical and research values.
Disclosure of Invention
The invention aims to provide phenyl polydialkynoic acid, and a preparation method, application and recovery thereof. The material has wide application prospect in the fields of visible light photocatalysis and other catalysis, and has good experimental repeatability.
The phenyl polydialkynoic acid (PBDA) provided by the invention takes 1, 4-di (4' -carboxybenzene) -1, 3-diacetylene (BDA) which cannot undergo topological polymerization under conventional conditions as a monomer, and is complexed with 1-naphthylmethyl amine (NMA) by adding the monomer to form eutectic. The high-efficiency topological polymerization of the phenyl diacetylene monomer can be realized by ultraviolet irradiation at normal temperature and normal pressure. And (3) pickling and recovering NMA to obtain the phenyl polydialkynoic acid with the side chain containing active carboxyl. The structural formula of phenyl diacetylenic acid (BDA) and phenyl polydialkynoic acid (PBDA) is as follows:
Figure BDA0003644899270000021
the method comprises the following specific steps:
(1) Synthesis of phenyl polydialkynoic acid:
a solution of 1, 4-bis (4' -carboxybenzene) -1, 3-diacetylene (BDA) in N, N-Dimethylformamide (DMF) was prepared (the solution was heated to 90 ℃ and held for 10min to promote dissolution of BDA). 1-Naphthylmethylamine (NMA) monomer (typically at room temperature) is then added thereto to give a clear and transparent solution of the co-assembled monomers. After standing in the dark for a period of time, a yellow co-assembly (BDN) is precipitated from the solution. The BDN solution was directly exposed to 365nm ultraviolet light. After the solid changed from yellow to black, the irradiation was stopped to obtain a complex of phenyl polydialkyne and NMA (PBDN). Adding hydrochloric acid into the polymerization solution, fully mixing and stirring, and centrifuging to obtain black solid powder; and washing the black powder to be neutral by deionized water to obtain the phenyl polydiacetylenic acid (PBDA).
(2) Photocatalytic degradation of methyl orange:
and (3) synthesizing PBDA by adopting the method in the step (1), adding the PBDA into methyl orange aqueous solution with a certain concentration, and illuminating through an LED lamp under magnetic stirring.
(3) Recovery of phenyl polydialkynoic acid:
after the photocatalytic reaction in the step (2) is finished, amino-modified ferroferric oxide nano particles (Fe 3 O 4 @NH 2 ) To Fe (t) 3 O 4 @NH 2 Fully compounding with PBDA to obtain PBDA-Fe 3 O 4 A complex. The magnet pair Fe is arranged outside the reaction vessel 3 O 4 @NH 2 Adsorbing, pouring the supernatant after the complex in the solution is totally adsorbed on the wall of the beaker, washing the precipitate with deionized water, and adsorbing the precipitate outside the beaker by using a magnet after each washing to collect PBDA-Fe 3 O 4 A complex.
(4) Regeneration of phenyl polydialkynoic acid:
to recovered PBDA-Fe 3 O 4 Adding excessive hydrochloric acid into the compound, and then placing a magnet pair Fe outside the beaker 3 O 4 And (5) adsorbing. To be Fe 3 O 4 Fully adsorbing the nano particles on the wall of the beaker to obtain PBDA dispersion; and (3) centrifuging for 3 times and washing with deionized water until the PBDA is neutral, thereby realizing the regeneration of the PBDA.
Preferably, the BDA solution in step (1) has a concentration of 1-10mg/mL. When the concentration of the BDA solution is 1-2mg/mL, BDA can be completely dissolved into clear transparent liquid after heating; when the concentration of BDA solution is 2-10mg/mL, BDA is not completely dissolved into white emulsion after water bath heating. BDA is clear transparent liquid or white emulsion, and the material performance is not affected. In this concentration range, the yield of phenyl polydialkyne material increases with increasing concentration, but at BDA concentrations greater than 10mg/mL, it is detrimental to obtain clear and transparent co-assembled monomer solutions.
Preferably, the NMA monomer is added in step (1), wherein the content of amino groups in the NMA monomer is more than 2 times of the content of carboxyl groups in the BDA monomer. Excess NMA was added to ensure that all BDA molecules in the solution acted upon NMA.
Preferably, the standing time in step (1) is more than 1h and the standing temperature is 25 ℃ to ensure precipitation of the co-assembly.
Preferably, the uv irradiation time in step (1) is greater than 30 minutes to ensure complete polymerization of the diacetylene monomer.
Preferably, in step (1) excess hydrochloric acid is added, H in the hydrochloric acid + The amount of (2) times or more the BDA content to ensure that NMA is completely exfoliated from the polymer to obtain PBDA.
Preferably, in the step (2), the concentration of the methyl orange aqueous solution is 15-20mg/L, and the concentration of the PBDA aqueous solution is 20-40mg/mL. To ensure that the degradation rate of methyl orange is within a suitable range.
Preferably, fe in step (3) 3 O 4 @NH 2 The nano particles are aqueous solution of 4mg/mL, fe 3 O 4 @NH 2 The amount of the nanoparticle is 20 mu LFe per 1mg of PBDA 3 O 4 @NH 2 An aqueous solution.
Preferably, in step (4) excess hydrochloric acid is added, H in the hydrochloric acid + Is PBDA-Fe 3 O 4 The content of the compound is more than 2 times to ensure Fe 3 O 4 The nanoparticles can be derived from PBDA-Fe 3 O 4 The complex is completely detached.
Compared with the prior art, the invention has the following technical advantages:
(1) Compared with the phenyl polydialkyne photocatalytic degradation catalyst in the prior art, the phenyl polydialkyne acid disclosed by the invention is easier to prepare and has a better photocatalytic degradation effect. When the phenyl polydialkyne material (5 mmol/L) with the same concentration is used as a catalyst, the degradation efficiency of the phenyl polydialkynoic acid PBDA prepared by the invention on methyl orange is 0.9%/min; the degradation efficiency of the phenyl polydialkyne material on methyl orange reported in the prior art is only 0.3 percent/min (Nature Materials,2015,14,505-511).
(2) The phenyl polydiacetylenic acid PBDA prepared by the invention takes an 80W LED lamp as a light source, so that the high-efficiency degradation of visible light catalytic methyl orange can be realized; the phenyl polydiacetylene reported in the literature needs to have a photocatalysis function under the illumination of a 300W xenon lamp with larger power (ultraviolet light is filtered by an ultraviolet filter, and lambda is more than 450 nm).
(3) The prepared phenyl polydiacetylenic acid PBDA side chain contains active group carboxyl, and the product performance is easy to improve through post-modification. In the invention, the recovery and regeneration of PBDA are realized by utilizing reversible recombination and dissociation of the side chain carboxyl and the magnetic nano material.
Drawings
Fig. 1 is an SEM image of BDN in example 1.
Fig. 2 is an infrared spectrum of BDN in example 1.
Fig. 3 is an SEM image of PBDN in example 1.
Fig. 4 is an infrared spectrum of PBDN in example 1.
FIG. 5 is a Raman spectrum of BDN and PBDN of example 1 showing that PBDN presents new characteristic peaks at 1450cm-1 and 2100cm-1, corresponding to newly generated C=C and C≡C triple bonds in the PBDN backbone, demonstrating the occurrence of topological polymerization.
Fig. 6 is an SEM image of PBDA in example 1.
FIG. 7 is an infrared spectrum of PBDA in example 1.
FIG. 8 is a solid ultraviolet absorbance spectra of BDN and PBDA of example 1 showing that polydiacetylenic acid PBDA has a broader ultraviolet absorbance wavelength range than BDN and that PBDA has a higher absorbance for visible light.
FIG. 9 is a voltammetric cycle of PBDA of example 1, showing that the oxidation potential of PBDA is 0.66eV and the reduction potential is-0.79 eV.
FIG. 10 is a graph showing the ultraviolet absorbance spectra of PBDA in examples 1 and 4, wherein the maximum ultraviolet absorbance of PBDA is shifted to the right and red after the illumination time is prolonged by 10 times, which proves that the polymerization degree of polydiacetylenic acid can be improved by prolonging the illumination time.
FIG. 11 is an ultraviolet absorption spectrum of the methyl orange solution of example 5 before and after 200min of illumination, showing a significant decrease in absorbance of methyl orange with LED illumination, demonstrating degradation of methyl orange by PBDA.
Fig. 12 shows the time-dependent residual amount of methyl orange in example 5, and it can be seen from the graph that the degradation rate of PBDA to methyl orange can reach 75% when the light is irradiated for 200 min.
FIG. 13 is a graph of the catalytic degradation efficiency of the regenerated r-PBDA for methyl orange in 5 cycles of example 6, showing that the degradation capacity of the PBDA for methyl orange is not significantly reduced in the 5-cycle catalytic degradation methyl orange experiment.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1: preparation of PBDA
30mg of BDA monomer powder was weighed into a 10mL glass bottle and 6mL of DMF solvent was added to prepare a 5mg/mL BDA solution. And (3) placing the BDA solution in a water bath kettle at 90 ℃ and heating for 10min, taking out the BDA solution after the solution turns into white emulsion, and cooling to 25 ℃ at room temperature. 151.55. Mu.L of NMA monomer was added to the white emulsion. The mixture is mixed evenly by rapid shaking, and the solution becomes yellow transparent liquid. And standing at 25 ℃ for 24 hours, wherein yellow particles are precipitated in the solution. The solution was irradiated under a 365nm ultraviolet mercury lamp for 1 hour, and after the irradiation was completed, 100. Mu.L of 12mol/L hydrochloric acid was added thereto. Shaking and mixing uniformly, centrifuging, washing with deionized water to neutrality, and obtaining PBDA powder.
Example 2: preparation of PBDA (BDA Low concentration)
10mg of BDA monomer powder was weighed into a 10mL glass bottle and 5mL of DMF solvent was added to prepare 2mg/mL BDA solution. And (3) placing the BDA solution in a water bath kettle at 90 ℃ and heating for 10min, taking out the BDA solution after the BDA solution becomes clear and transparent liquid, and cooling to 25 ℃ at room temperature. To this was added 50.48. Mu.L of NMA monomer rapidly. The mixture is mixed evenly by rapid shaking, and the solution becomes yellow transparent liquid. And standing at 25 ℃ for 24 hours, wherein yellow particles are precipitated in the solution. The solution was irradiated under a 365nm ultraviolet mercury lamp for 1 hour, and after the irradiation was completed, 50. Mu.L of 12mol/L hydrochloric acid was added thereto. Shaking and mixing uniformly, centrifuging, washing with deionized water to neutrality, and obtaining PBDA powder.
Example 3: preparation of PBDA (BDA high concentration)
27mg of BDA monomer powder was weighed into a 10mL glass bottle and 3mL of DMF solvent was added to prepare 9mg/mL BDA solution. And (3) placing the BDA solution in a water bath kettle at 90 ℃ and heating for 10min, taking out the BDA solution after the solution turns into white emulsion, and cooling to 25 ℃ at room temperature. 151.55. Mu.L NMA was added to the white emulsion. The mixture is mixed evenly by rapid shaking, and the solution becomes yellow transparent liquid. And standing at 25 ℃ for 24 hours, wherein yellow particles are precipitated in the solution. The solution was irradiated under a 365nm ultraviolet mercury lamp for 1 hour, and after the irradiation was completed, 100. Mu.L of 12mol/L hydrochloric acid was added thereto. Shaking and mixing uniformly, centrifuging, washing with deionized water to neutrality, and obtaining PBDA powder.
Example 4: preparation of PBDA (high polymerization degree PBDA)
30mg of BDA monomer powder was weighed into a 10mL glass bottle and 6mL of DMF solvent was added to prepare a 5mg/mL BDA solution. And (3) placing the BDA solution in a water bath kettle at 90 ℃ and heating for 10min, taking out the BDA solution after the solution turns into white emulsion, and cooling to 25 ℃ at room temperature. 151.55. Mu.L of NMA monomer was added to the white emulsion. The mixture is mixed evenly by rapid shaking, and the solution becomes yellow transparent liquid. And standing at 25 ℃ for 24 hours, wherein yellow particles are precipitated in the solution. The solution was irradiated under a 365nm ultraviolet mercury lamp for 10 hours, and after the irradiation was completed, 100. Mu.L of 12mol/L hydrochloric acid was added thereto. Shaking and mixing uniformly, centrifuging, washing with deionized water to neutrality, and obtaining PBDA powder. The relative degree of polymerization was judged by the red shift of the ultraviolet absorbance of PBDA.
Example 5: catalytic degradation of methyl orange by PBDA under visible light
20mg of PBDA material was prepared as in example 1. 30mL of methyl orange aqueous solution with the concentration of 20mg/L is prepared, 20mg of polydiacetylene material is fully and uniformly ground, then added into the methyl orange solution, and stirred for 40min in a dark place. 1.2mL of the solution is extracted from the methyl orange solution every 10min and filtered by a 0.22 mu m filter head, and then 1mL of the filtered solution is extracted into a 10mL centrifuge tube, the concentration is diluted by 5 times, and whether the dark adsorption is balanced or not is judged by visible-ultraviolet spectroscopy. When the absorbance of 464nm wavelength is unchanged, the 80W LED lamp panel is adopted to irradiate the methyl orange solution, the irradiation distance is 5cm, and meanwhile, air is introduced into the solution at a constant speed of 0.5L/h. In the irradiation process, sampling is carried out once every 30min, the sampling method is the same as that of the dark adsorption process, and the change of 464nm wavelength absorbance of the sampled sample is detected through visible-ultraviolet spectroscopy.
Example 6: recovery and regeneration of PBDA
To the reaction solution after completion of the photocatalysis in example 2, 400. Mu.L of Fe having a concentration of 4mg/mL was added 3 O 4 @NH 2 Mixing the aqueous solution by shaking, standing for 30min, and waiting for PBDA and Fe 3 O 4 @NH 2 And (5) completely compounding. Placing a magnet pair Fe outside the beaker 3 O 4 @NH 2 And (3) performing adsorption, pouring the supernatant after the complex in the solution is totally adsorbed to the bottom of the beaker, washing the complex with deionized water for 3 times, and adsorbing the complex outside the beaker by using a magnet after each washing.
To recovered PBDA-Fe in a beaker 3 O 4 To the complex was added 2mL of 12mol/L hydrochloric acid. Uniformly dispersing the compound in hydrochloric acid by stirring; then, the magnet is placed outside the beaker for 60min, when no solid particles are adsorbed to the wall of the beaker, the dispersion liquid is taken out, and the dispersion liquid is centrifuged for 3 times and washed with deionized water until the dispersion liquid is neutral, so that the regenerated r-PBDA can be obtained. For recovered regenerated r-PBDA, its degradation rate to methyl orange solution upon illumination for 200min was characterized.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.

Claims (10)

1. A phenyl polydiacetylenic acid, characterized in that: the structural formula is as follows:
Figure FDA0003644899260000011
2. use of a phenyl polydialkynoic acid according to claim 1, characterized in that: used as a catalyst for photocatalytic degradation of organic pollutants.
3. Use of a phenyl polydialkynoic acid according to claim 2, characterized in that: the organic pollutant is methyl orange.
4. A photocatalytic degradation method of organic pollutants is characterized in that: the method comprises the following steps: the phenyl polydiacetylenic acid of claim 1 is added to an aqueous solution containing organic contaminants and illuminated by LED lamps under magnetic stirring at a power of at least 80W.
5. The method for photocatalytic degradation of organic contaminants according to claim 4, characterized in that: the concentration of the organic pollutant water solution is 15-20mg/L, and the concentration of the phenyl polydiacetylene is 20-40mg/mL.
6. A process for recovering phenyl polydialkynoic acid according to claim 1 from a solution, characterized in that: the method comprises the following steps:
(1) After the photocatalysis reaction is finished, adding amino modified ferroferric oxide nano particle Fe into the reaction solution 3 O 4 @NH 2 To Fe (t) 3 O 4 @NH 2 Fully compounding with PBDA to obtain PBDA-Fe 3 O 4 A compound, a magnet pair Fe is arranged outside the reaction vessel 3 O 4 @NH 2 Adsorbing, pouring supernatant and precipitating after the complex in the solution is totally adsorbed on the wall of the beakerWashing the starch with deionized water, and collecting PBDA-Fe by adsorbing the starch with magnet outside the beaker 3 O 4 A complex;
(2) To recovered PBDA-Fe 3 O 4 Adding excessive hydrochloric acid into the compound, and then placing a magnet pair Fe outside the reaction vessel 3 O 4 Adsorbing Fe 3 O 4 After the nano particles are fully adsorbed on the wall, the phenyl polydialkynoic acid PBDA dispersion liquid is obtained; and filtering and washing to neutrality to realize the regeneration of PBDA.
7. The method of recovering the phenyl polydiacetylenic acid of claim 1 from solution according to claim 6, characterized in that: fe in step (1) 3 O 4 @NH 2 The nano particles are aqueous solution of 4mg/mL, fe 3 O 4 @NH 2 The amount of the nanoparticle is 20 mu LFe per 1mg of PBDA 3 O 4 @NH 2 An aqueous solution;
and/or, in step (2), adding excessive hydrochloric acid, wherein H is contained in the hydrochloric acid + The molar content of (B) is PBDA-Fe 3 O 4 The molar content of the compound is more than 2 times.
8. The method for producing phenyl polydialkynoic acid according to claim 1, wherein: the method comprises the following steps: 1, 4-di (4' -carboxybenzene) -1, 3-diacetylene is taken as a monomer, 1-naphthylmethyl amine is added to complex with the monomer to form eutectic, the topology polymerization of phenyl diacetylene monomer can be realized through ultraviolet irradiation at normal temperature and normal pressure, and the phenyl polydialkynoic acid can be obtained after NMA is recovered through acid washing.
9. The method for producing phenyl polydialkynoic acid according to claim 8, wherein: the method also comprises the following steps:
preparing an N, N-dimethylformamide solution of 1, 4-bis (4' -carboxybenzene) -1, 3-diacetylene, adding a 1-naphthylmethyl amine monomer into the solution to obtain a clear and transparent co-assembly monomer solution, standing in a dark place to co-assemble and separate out a yellow co-assembly body, then placing the yellow co-assembly body under 365nm ultraviolet light for irradiation, stopping the irradiation after the solid is changed from yellow to black to obtain a compound of phenyl polydialkyne and NMA, adding hydrochloric acid into the compound, fully mixing and stirring the compound, and centrifuging the compound to obtain black solid powder; and washing the black powder to be neutral by deionized water to obtain the phenyl polydiacetylenic acid.
10. The method for producing phenyl polydialkynoic acid according to claim 9, wherein: 1, 4-bis (4 '-carboxybenzene) -1, 3-diacetylene in the N, N-dimethylformamide solution, wherein the concentration of the 1, 4-bis (4' -carboxybenzene) -1, 3-diacetylene is 1-10mg/mL;
and/or the content of amino in the NMA monomer is more than 2 times of the molar quantity of carboxyl in the 1, 4-di (4' -carboxybenzene) -1, 3-diacetylene monomer;
and/or, standing and assembling for more than 1h in the step (1), wherein the standing temperature is less than or equal to 30 ℃;
and/or the ultraviolet irradiation time is more than 30min;
h in hydrochloric acid + The dosage of the (B) is more than 2 times of the molar content of the 1, 4-di (4' -carboxybenzene) -1, 3-diacetylene monomer.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4895975A (en) * 1987-05-06 1990-01-23 Kozo Iizuka, Director-General Of Agency Of Industrial Science And Technology Diacetylene compound and process for production of polymer containing diacetylene groups from the diacetylene compound
CN102190747A (en) * 2011-04-19 2011-09-21 复旦大学 Magnetochromic polydiyne/ferroferric oxide composite material as well as preparation method and application thereof
CN113817088A (en) * 2021-08-20 2021-12-21 常州大学 Preparation method of strong-polarity organic solvent tolerance macroscopic blue-phase polydiacetylene material based on co-assembly approach

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4895975A (en) * 1987-05-06 1990-01-23 Kozo Iizuka, Director-General Of Agency Of Industrial Science And Technology Diacetylene compound and process for production of polymer containing diacetylene groups from the diacetylene compound
CN102190747A (en) * 2011-04-19 2011-09-21 复旦大学 Magnetochromic polydiyne/ferroferric oxide composite material as well as preparation method and application thereof
CN113817088A (en) * 2021-08-20 2021-12-21 常州大学 Preparation method of strong-polarity organic solvent tolerance macroscopic blue-phase polydiacetylene material based on co-assembly approach

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