CN115400791B - Quaternary phosphonium salt functionalized fiber and preparation method and application thereof - Google Patents
Quaternary phosphonium salt functionalized fiber and preparation method and application thereof Download PDFInfo
- Publication number
- CN115400791B CN115400791B CN202110578127.1A CN202110578127A CN115400791B CN 115400791 B CN115400791 B CN 115400791B CN 202110578127 A CN202110578127 A CN 202110578127A CN 115400791 B CN115400791 B CN 115400791B
- Authority
- CN
- China
- Prior art keywords
- phosphonium salt
- quaternary phosphonium
- fiber
- organic
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention is suitable for the technical field of materials, and provides a quaternary phosphonium salt functionalized fiber, a preparation method and application thereof, wherein the quaternary phosphonium salt functionalized fiber is obtained by grafting quaternary phosphonium salt organic small molecules subjected to alkalization to the surface of acrylic fiber in a covalent bond manner under the action of an organic solvent and water. The quaternary phosphonium salt functionalized fiber is a bifunctional fiber with adsorption and catalysis functions, and has strong polarizability due to the large atomic radius of phosphine atoms, compared with other adsorbents, the quaternary phosphonium salt functionalized fiber has obvious advantages in adsorption quantity, recyclability and the like when being used for adsorbing anionic organic pollutants with large anion radius.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a quaternary phosphonium salt functionalized fiber, and a preparation method and application thereof.
Background
The problem of water pollution has become one of the most urgent environmental problems worldwide, and anionic pollutants are one of the most widespread sources of pollution. Representative contaminants are nitrophenols, organic pesticides, detergents and polycyclic aromatic hydrocarbons. Adsorption is the most effective method for purifying polluted water sources, and is receiving attention because of its advantages such as low cost, simple operation, low energy consumption and high efficiency.
In recent years, various ionic adsorbents including modified hydrotalcite-like materials, activated carbon, chitosan and the like have been developed, but these adsorbents have problems of complicated preparation process, low adsorption capacity, poor cycle performance and the like in practical application. Therefore, the prepared adsorbent with low cost, easy obtainment and excellent performance has higher research value.
Disclosure of Invention
The embodiment of the invention aims to provide quaternary phosphonium salt functionalized fiber and aims to solve the problems of complex preparation process, low adsorption capacity and poor cycle performance of the existing adsorbent.
The embodiment of the invention is realized in such a way that the quaternary phosphonium salt functionalized fiber is obtained by grafting the quaternary phosphonium salt organic micromolecules subjected to alkalization to the surface of acrylic fiber in a covalent bond way under the action of an organic solvent and water.
Another object of the embodiment of the invention is a method for preparing the quaternary phosphonium salt functionalized fiber, comprising the following steps:
adding acrylic fiber, quaternary phosphonium salt organic micromolecules, an organic solvent and water into a reaction container, reacting for 5-10h at the temperature of 110-140 ℃, and washing and drying after the reaction is finished to obtain the acrylic fiber/quaternary phosphonium salt organic micromolecule composite material.
Another object of an embodiment of the invention is the use of the quaternary phosphonium salt functionalized fiber in adsorbing anionic organic contaminants.
Another object of an embodiment of the present invention is the use of the quaternary phosphonium salt functionalized fiber in catalyzing the cyclization reaction of carbon dioxide and an epoxy compound.
The quaternary phosphonium salt functionalized fiber obtained by grafting the quaternary phosphonium salt organic micromolecules subjected to alkalization treatment onto the surface of acrylic fiber in a covalent bond mode under the action of an organic solvent and water is a dual-functional fiber with adsorption and catalysis purposes, and has strong polarizability due to the large atomic radius of phosphine atoms.
Drawings
FIG. 1 is a scanning electron microscope image of acrylic fiber, quaternary phosphonium salt functionalized fiber and quaternary phosphonium salt functionalized fiber after ten times of adsorption cycle use provided by the embodiment of the invention;
FIG. 2 is an infrared spectrum of acrylic fiber and quaternary phosphonium salt functionalized fiber provided by an embodiment of the invention;
FIG. 3 is a graph of the results of adsorption tests of organic anionic pollutants by quaternary phosphonium salt functionalized fibers provided in an embodiment of the invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The quaternary phosphonium salt functionalized material is currently applied to a plurality of fields, such as conversion reaction which is used as an asymmetric phase transfer catalyst to realize enantioselectivity, and the quaternary phosphonium salt ionic liquid can be used as a high-activity antibacterial material to catalyze a plurality of organic reactions such as Diels-Alder reaction, hydroformylation reaction, carbonylation reaction and the like in a green way. However, there is little research on the multifunctional application of quaternary phosphonium salt modified materials. The invention explores the application of the quaternary phosphonium salt functionalized acrylic fiber in adsorbing anionic pollutants in water and catalyzing the reaction of carbon dioxide and epoxy compounds based on the advantages of strong polarizability, high thermal stability, simple preparation and the like of the quaternary phosphonium salt group.
The embodiment of the invention provides a quaternary phosphonium salt functionalized fiber (PAN) QPS F, fiber), the quaternary phosphonium salt difunctional fiber is obtained by grafting the quaternary phosphonium salt organic micromolecule after alkalization to the surface of acrylic fiber in a covalent bond way under the action of an organic solvent and water.
In the embodiment of the invention, the quaternary phosphonium salt organic small molecule can be obtained by purchasing on the market, and when the quaternary phosphonium salt organic small molecule is (3-aminopropyl) triphenyl phosphonium bromide, the quaternary phosphonium salt organic small molecule can be prepared by the following preparation method, which comprises the following steps:
step S1: dissolving 3-bromoprop-1-amine hydrobromide and triphenylphosphine in acetonitrile for heating reflux reaction, and standing at low temperature and filtering to obtain a solid substance.
In the embodiment of the present invention, step S1 may specifically be:
3-Bromopropan-1-amine hydrobromide (2.19 g,10 mmol) and triphenylphosphine (2.62 g,10 mmol) were dissolved in 25mL acetonitrile, heated under reflux for 18h, allowed to stand at low temperature for 12h after the reaction was completed, and the precipitated solid was filtered and collected.
Step S2: dissolving the solid substance in water, alkalizing with saturated potassium carbonate aqueous solution, extracting, rotary steaming, and drying.
In the embodiment of the present invention, step S2 may specifically be:
the solid matter precipitated above was dissolved in water and treated with a saturated aqueous potassium carbonate solution to a pH of 11, the product was extracted into methylene chloride, and the solvent was removed by rotary evaporation, and the obtained white solid product was dried for 12 hours to obtain the objective product (3-aminopropyl) triphenylphosphonium bromide.
In the embodiment of the invention, whether the alkalization treatment of the quaternary phosphonium salt organic micromolecules determines whether the obtained quaternary phosphonium salt organic micromolecules can be successfully grafted on acrylic fiber or not, specifically, NH is obtained without the alkalization treatment 3+ Is also a quaternary phosphonium salt, but cannot be successfully grafted onto acrylic fibers; and the NH is obtained by alkalizing 2 The quaternary phosphonium salt organic small molecule containing amino can be successfully grafted on the CN group of the acrylic fiber.
The embodiment of the invention also provides a preparation method of the quaternary phosphonium salt functionalized fiber, which comprises the following steps:
adding acrylic fiber, quaternary phosphonium salt organic micromolecules, an organic solvent and water into a reaction container, reacting for 5-10h at the temperature of 110-140 ℃, and washing and drying after the reaction is finished to obtain the acrylic fiber/quaternary phosphonium salt organic micromolecule composite material.
In the embodiment of the invention, the mass ratio of the acrylic fiber to the quaternary phosphonium salt organic micromolecule is (0.3-1.5) to (0.1-10). Experiments show that the mass ratio of the acrylic fiber to the quaternary phosphonium salt organic small molecule has a certain influence on the fiber loading effect, and the mass ratio of the acrylic fiber to the quaternary phosphonium salt organic small molecule is preferably 0.3:2.5.
In the embodiment of the invention, in the process of preparing the quaternary phosphonium salt functionalized fiber through the acrylic fiber and the quaternary phosphonium salt organic micromolecule, water is needed to participate in the formation of an amide bond, and no weight increase is caused by the failure of grafting the fiber due to the fact that water is not introduced, so that a part of water is needed to be introduced as a solvent besides the selection of an organic solvent. The ratio of the organic solvent to the water also has a certain influence on the fiber grafting effect, and experiments prove that the preferable volume ratio is (10-30): 2-10, and more preferably, the volume ratio of the organic solvent to the water is 4:1.
In the embodiment of the invention, the organic solvent is one or more of glycol, ethanol, methanol and 1,4-dioxane in any proportion.
In the embodiment of the invention, acrylic fiber, quaternary phosphonium salt organic micromolecule, organic solvent and water are added into a reaction container to react for 5-10 hours at the temperature of 110-140 ℃, and after the reaction is finished, the steps of washing and drying are carried out, thus obtaining the acrylic fiber/quaternary phosphonium salt composite material specifically comprising:
adding acrylic fiber, quaternary phosphonium salt organic micromolecule, organic solvent and water into a reaction container, reacting for 7-8h at 120-130 ℃, and repeatedly washing and drying by distilled water at 60-70 ℃ after the reaction is finished.
The embodiment of the invention provides an application of the quaternary phosphonium salt functionalized fiber in adsorbing anionic organic pollutants.
Specifically, 10mg of dry PAN QPS F, respectively immersing the fiber into 20mL of different anionic organic pollutants with initial concentration of 200ppm, stirring at room temperature to adsorption equilibrium, respectively measuring the absorbance of each pollutant at the maximum absorption wavelength by an ultraviolet spectrophotometer, and calculating the corresponding concentration according to the corresponding standard curve. PAN calculation from the decrease in concentration of substance before and after adsorption QPS F adsorption properties for different substances. The adsorption amount was calculated as follows:
qe is the equilibrium adsorption of the fiber to anionic organic contaminants (mmol- 1 )，C 0 And C e Corresponding to the adsorption start and end concentrations (ppm), respectively, V is the volume of the contaminant (L), M is the mass of the functionalized fiber (g), M is the molecular weight of the contaminant, and f is the functionalized fiber functionality (mmol g- 1 )。
The embodiment of the invention provides an application of the quaternary phosphonium salt functionalized fiber in catalyzing cyclization reaction of carbon dioxide and epoxy compounds.
The promotion of the industrialization process not only brings water pollution, but also influences the living environment of human beings due to atmospheric pollution. The emission of greenhouse gas carbon dioxide is rising year by year, and how to realize efficient green conversion is one of the hot spots of research. Among the numerous carbon dioxide fixation methods, the reaction of carbon dioxide with an epoxy compound to prepare a cyclic carbonate has been attracting attention because of the advantages of no solvent, 100% atomic efficiency, and the like. In addition, the cyclic carbonate has the characteristics of strong polarity, high boiling point, low toxicity, biodegradability and the like, can be used for polymer synthesis, is an important fine chemical intermediate, and has higher industrial value. The invention initially explores the green conversion of the quaternary phosphonium salt functionalized acrylic fiber, and aims to develop the versatility of the material and improve the practical application value.
Specifically, 2-chloromethyloxirane (5 mmol), 0.5mol% equivalent of fiber catalyst, were added sequentially to a 10mL dry Schlenk tube. Introducing the system into a balloon filled with carbon dioxide, replacing the system gas with a vacuum pump for 3-4 times, and continuously introducing CO of 0.1Mpa into the reaction system 2 Stirring for a certain time at a certain water bath temperature. After the experiment is finished, the reaction device is cooled and residual CO is discharged 2 The reaction system was purged with 2mL of acetone to thereby clean the fibers, and the reaction filtrate was analyzed by gas chromatography.
It is worth noting that the current research mainly tends to realize the realization and optimization of one application of the functionalized material, and the quaternary phosphonium salt functionalized fiber prepared by the invention realizes double functions (adsorption and catalysis), so that the quaternary phosphonium salt functionalized fiber has higher practical application value.
Examples of certain embodiments of the invention are given below and are not intended to limit the scope of the invention.
In addition, it should be noted that the numerical values set forth in the following examples are as precise as possible, but those skilled in the art will understand that each numerical value should be construed as a divisor rather than an absolute precise numerical value due to measurement errors and experimental operation problems that cannot be avoided. For example, due to errors in the weighing apparatus, it should be understood that the weight value of each raw material for preparing the quaternary phosphonium salt functionalized fiber with respect to each example may have an error of ±2% or ±1%.
Example 1
3-Bromopropan-1-amine hydrobromide (2.19 g,10 mmol) and triphenylphosphine (2.62 g,10 mmol) were dissolved in 25mL acetonitrile, heated under reflux for 18h, left standing at low temperature for 12h after the reaction was completed, the precipitated solid was filtered and collected, then dissolved in water and treated with saturated aqueous potassium carbonate to pH 11, the product was extracted into dichloromethane, and the solvent was removed by rotary evaporation, and the resulting white solid product was dried for 12h to give the desired product (3-aminopropyl) triphenylphosphonium bromide (yield 76%).
Into a dry 100mL round bottom flask equipped with a reflux condenser was charged 0.5g of dry acrylic fiber (PANF), 0.1g of (3-aminopropyl) triphenylphosphonium bromide, 10mL of distilled water and 2mL of ethylene glycol, and the system was heated to 110℃for reaction for 5h. After the reaction is finished, taking out the fiber, repeatedly washing the fiber with distilled water at 65 ℃, and drying the fiber in a baking oven at 60 ℃ for 12 hours to obtain the quaternary phosphonium salt functionalized fiber PAN QPS F，PAN QPS The F weight gain was 11% and the functionality was 0.25mmol/g.
Example 2
Into a dry 100mL round bottom flask equipped with a reflux condenser was charged 0.7g of dry acrylic fiber (PANF), 2g of the one prepared in example 1(3-aminopropyl) triphenyl phosphonium bromide, 12mL distilled water and 4mL ethylene glycol, and the system was heated to 115℃for reaction for 6 hours. After the reaction is finished, taking out the fiber, repeatedly washing the fiber with distilled water at 65 ℃, and drying the fiber in a baking oven at 60 ℃ for 12 hours to obtain the quaternary phosphonium salt functionalized fiber PAN QPS F，PAN QPS The F weight gain was 17% and the functionality was 0.36mmol/g.
Example 3
Into a dry 100mL round bottom flask equipped with a reflux condenser was charged 0.9g of dry acrylic fiber (PANF), 4g of (3-aminopropyl) triphenylphosphonium bromide prepared in example 1, 15mL of distilled water and 6mL of ethylene glycol, and the system was heated to 120℃for 7h of reaction. After the reaction is finished, taking out the fiber, repeatedly washing the fiber with distilled water at 65 ℃, and drying the fiber in a baking oven at 60 ℃ for 12 hours to obtain the quaternary phosphonium salt functionalized fiber PAN QPS F，PAN QPS The F weight gain was 25% and the functionality was 0.5mmol/g.
Example 4
Into a dry 100mL round bottom flask equipped with a reflux condenser was charged 1.3g of dry acrylic fiber (PANF), 6g of (3-aminopropyl) triphenylphosphonium bromide prepared in example 1, 25mL of distilled water and 8mL of ethylene glycol, and the system was heated to 130℃to react for 8h. After the reaction is finished, taking out the fiber, repeatedly washing the fiber with distilled water at 65 ℃, and drying the fiber in a baking oven at 60 ℃ for 12 hours to obtain the quaternary phosphonium salt functionalized fiber PAN QPS F，PAN QPS The F weight gain was 32% and the functionality was 0.6mmol/g.
Example 5
Into a dry 100mL round bottom flask equipped with a reflux condenser was charged 1.5g of dry acrylic fiber (PANF), 10g of (3-aminopropyl) triphenylphosphonium bromide prepared in example 1, 30mL of distilled water and 10mL of ethylene glycol, and the system was heated to 140℃to react for 8h. After the reaction is finished, taking out the fiber, repeatedly washing the fiber with distilled water at 65 ℃, and drying the fiber in a baking oven at 60 ℃ for 12 hours to obtain the quaternary phosphonium salt functionalized fiber PAN QPS F，PAN QPS The F weight gain was 39% and the functionality was 0.7mmol/g.
Example 6
Into a dry 100mL round bottom flask equipped with a reflux condenser was charged 1.00g of dry acrylic fiber (PANF), 8.5g of the one described in example 1The prepared (3-aminopropyl) triphenyl phosphonium bromide, 24mL distilled water and 6mL ethylene glycol was heated to 126℃and reacted for 8h. After the reaction is finished, taking out the fiber, repeatedly washing the fiber with distilled water at 65 ℃, and drying the fiber in a baking oven at 60 ℃ for 12 hours to obtain the quaternary phosphonium salt functionalized fiber PAN QPS F，PAN QPS The F weight gain was 31.57% and the functionality was 0.6mmol/g.
The morphology of the quaternary phosphonium salt functionalized fiber prepared in the embodiment 6 of the invention is observed, as shown in a Scanning Electron Microscope (SEM) of the quaternary phosphonium salt functionalized fiber shown in figure 1, wherein figure 1 (a) is acrylic fiber PANF, and figure 1 (b) is quaternary phosphonium salt functionalized fiber PAN QPS F, FIG. 1 (c) shows a quaternary phosphonium salt functionalized fiber PAN after ten times of adsorption cycle use QPS-10 And F, the surface of the acrylic fiber after loading the quaternary phosphonium salt organic micromolecules becomes rough, but the overall morphology is not changed greatly, and the surface structure of the fiber is not damaged.
Infrared test is carried out on the quaternary phosphonium salt functionalized fiber prepared in the embodiment 6 of the invention to obtain acrylic fiber PANF and quaternary phosphonium salt functionalized fiber PAN QPS F is shown in figure 2, wherein figure 2 (a) is acrylic fiber and figure 2 (b) is quaternary phosphonium salt functionalized fiber PAN QPS F. Acrylic fiber contains a large amount of cyano-CN and a small amount of ester-COCH 3 At 2243cm -1 And 1733cm -1 There is a strong absorption peak caused by stretching vibration of c≡n bond and c=o bond, respectively. After fiber is loaded with quaternary phosphonium salt micromolecules, 2243cm -1 The relative intensity of the absorption peak at the position is reduced, and the absorption peak of the C=O bond is red-shifted to 1660cm -1 This suggests that part of the cyano groups of the fiber PANF participate in the grafting reaction, and that the ester groups react more easily with the amino groups. After grafting the quaternary phosphonium salt small molecule, the grafting of the quaternary phosphonium salt small molecule is carried out at 3438cm due to the formation of an amide bond -1 A corresponding telescopic vibration absorption peak appears nearby, 1248cm -1 Stretching vibration corresponding to C-P bond, furthermore, 740cm -1 And 689cm -1 The absorption peak at this point is due to out-of-plane bending vibrations of the C-H bond of the benzene ring.
Further, the quaternary phosphonium salt functionalized fiber prepared in example 6 of the present invention was directed against anionic organic pollutant-dodecylbenzeneThe removal capacity of sodium sulfonate was tested by first adjusting the pH with a 0.1mol/L NaOH solution and a 0.1mol/L HCl solution, and distilled water used to prepare the different pH solutions was adjusted to the corresponding pH values in advance. Specifically, 10mg of PANQPSF fibers were immersed in 20.00mL of sodium dodecylbenzenesulfonate solution having an initial concentration of 500ppm and different pH values (ph=3, 4, 5, 6, 7, 8, 9, 10, 11), respectively, and stirred at room temperature for 12 hours to adsorption equilibrium. After the adsorption is finished, the residual concentration of the solution under different pH values is respectively measured by an ultraviolet spectrophotometer, the adsorption quantity is calculated, the test result is shown in figure 3, wherein the abscissa is the pH value of the solution, the ordinate is the adsorption quantity of PANQPSF to sodium dodecyl benzene sulfonate, and the functional fiber PAN is known QPS F has excellent adsorption performance on the adsorption quantity of the anionic organic pollutant sodium dodecyl benzene sulfonate which is maintained between 4.3 and 5 mol/mol. Further, the quaternary phosphonium salt functionalized fiber prepared in example 6 of the present invention was used for cycloaddition reaction of carbon dioxide and epichlorohydrin, specifically, 2-chloromethyloxirane (5 mmol), 1mol% equivalent PAN were sequentially added to 10mL of dried Schlemk tube QPS F, a fiber catalyst; introducing the system into a balloon filled with carbon dioxide, replacing the system gas with a vacuum pump for 3-4 times, and continuously introducing CO of 0.1Mpa into the reaction system 2 Stirring for a certain time at a certain water bath temperature; after the experiment is finished, the reaction device is cooled and residual CO is discharged 2 The reaction system was purged with 2mL of acetone, and the reaction filtrate was analyzed by gas chromatography to give cyclic carbonate having a time-dependent yield as shown in table 1.
TABLE 1
In summary, the embodiment of the invention synthesizes an organic micromolecule with an amino functional group and a quaternary phosphonium salt functional group, screens conditions such as reaction solvent, reaction temperature, reaction time and the like, can graft the quaternary phosphonium salt functional micromolecule with a large steric hindrance group on the surface of acrylic fiber, and discovers that the quaternary phosphonium salt functional fiber prepared by the invention is a bifunctional fiber with adsorption and catalysis purposes through experiments on adsorption and catalysis, and has strong polarizability due to large atomic radius of phosphine atoms.
In addition, the technical key of the invention is the immobilization of quaternary phosphonium salt organic small molecules on acrylic fiber. Because the quaternary phosphonium salt group has larger steric hindrance and is difficult to graft in the micro-environment of the acrylic fiber with dense active sites, the invention screens the reaction solvent in the early research and development process and explores the grafting time and the reaction temperature to improve the functionality of the functionalized fiber, and the corresponding exploration result is shown in table 2.
TABLE 2
As can be seen from Table 2, a single solvent such as water, 1,4-Dioxane, (CH) 2 OH) 2 The grafting ratio of the fibers is lower when the solvent is changed to a higher boiling point (CH 2 OH) 2 When the ratio of the fiber to water is controlled, the fiber can achieve a higher grafting rate, and the immobilization is successful.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The quaternary phosphonium salt functionalized fiber is characterized in that the quaternary phosphonium salt functionalized fiber is obtained by grafting quaternary phosphonium salt small organic molecules subjected to alkalization to the surface of acrylic fiber in a covalent bond way under the action of an organic solvent and water;
the preparation method of the quaternary phosphonium salt organic micromolecule comprises the following steps:
dissolving 3-bromopropan-1-amine hydrobromide and triphenylphosphine in acetonitrile for heating reflux reaction, and standing at low temperature and filtering to obtain a solid substance;
dissolving the solid substance in water, alkalizing with saturated potassium carbonate aqueous solution, extracting, rotary steaming, and drying to obtain the final product;
the preparation method of the quaternary phosphonium salt functionalized fiber comprises the following steps:
adding acrylic fiber, quaternary phosphonium salt organic micromolecules, an organic solvent and water into a reaction container, reacting for 5-10 hours at the temperature of 110-140 ℃, and washing and drying after the reaction is finished to obtain the acrylic fiber/quaternary phosphonium salt composite material;
the mass ratio of the acrylic fiber to the quaternary phosphonium salt organic micromolecule is (0.3-1.5) (0.1-10);
the volume ratio of the organic solvent to the water is (10-30) to (2-10); the organic solvent is one or more of glycol, ethanol, methanol and 1,4-dioxane in any proportion;
the quaternary phosphonium salt organic small molecule is (3-aminopropyl) triphenyl phosphonium bromide.
2. A method of making the quaternary phosphonium salt functionalized fiber according to claim 1, comprising:
adding acrylic fiber, quaternary phosphonium salt organic micromolecules, an organic solvent and water into a reaction container, reacting for 5-10 hours at the temperature of 110-140 ℃, and washing and drying after the reaction is finished to obtain the acrylic fiber/quaternary phosphonium salt composite material;
the mass ratio of the acrylic fiber to the quaternary phosphonium salt organic micromolecule is (0.3-1.5) (0.1-10);
the volume ratio of the organic solvent to the water is (10-30) to (2-10); the organic solvent is one or more of glycol, ethanol, methanol and 1,4-dioxane in any proportion;
the quaternary phosphonium salt organic small molecule is (3-aminopropyl) triphenyl phosphonium bromide.
3. The method for producing a quaternary phosphonium salt-functionalized fiber according to claim 2, comprising:
adding acrylic fiber, quaternary phosphonium salt organic micromolecules, an organic solvent and water into a reaction container, reacting for 7-8 hours at the temperature of 120-130 ℃, and repeatedly washing and drying by distilled water at 60-70 ℃ after the reaction is finished;
the mass ratio of the acrylic fiber to the quaternary phosphonium salt organic micromolecule is (0.3-1.5) (0.1-10);
the volume ratio of the organic solvent to the water is (10-30) to (2-10); the organic solvent is one or more of glycol, ethanol, methanol and 1,4-dioxane in any proportion;
the quaternary phosphonium salt organic small molecule is (3-aminopropyl) triphenyl phosphonium bromide.
4. Use of the quaternary phosphonium salt functionalized fiber according to claim 1 for adsorbing anionic organic pollutants.
5. Use of a quaternary phosphonium salt functionalized fiber according to claim 1 for catalyzing the cyclization reaction of carbon dioxide and an epoxy compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110578127.1A CN115400791B (en) | 2021-05-26 | 2021-05-26 | Quaternary phosphonium salt functionalized fiber and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110578127.1A CN115400791B (en) | 2021-05-26 | 2021-05-26 | Quaternary phosphonium salt functionalized fiber and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115400791A CN115400791A (en) | 2022-11-29 |
| CN115400791B true CN115400791B (en) | 2023-08-11 |
Family
ID=84154930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110578127.1A Active CN115400791B (en) | 2021-05-26 | 2021-05-26 | Quaternary phosphonium salt functionalized fiber and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115400791B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266473A (en) * | 2013-06-24 | 2013-08-28 | 河南省科学院化学研究所有限公司 | Phosphonium salt modified acrylic fibre antibacterial material and preparation method thereof |
| WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
| WO2019239149A1 (en) * | 2018-06-15 | 2019-12-19 | Seren Technologies Limited | Ionic liquid preparation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7687646B2 (en) * | 2006-03-28 | 2010-03-30 | Azad Pharmaceutical Ingredients, Ag | Polymorphic forms of olopatadine hydrochloride and methods for producing olopatadine and salts thereof |
-
2021
- 2021-05-26 CN CN202110578127.1A patent/CN115400791B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103266473A (en) * | 2013-06-24 | 2013-08-28 | 河南省科学院化学研究所有限公司 | Phosphonium salt modified acrylic fibre antibacterial material and preparation method thereof |
| WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
| WO2019239149A1 (en) * | 2018-06-15 | 2019-12-19 | Seren Technologies Limited | Ionic liquid preparation |
Non-Patent Citations (1)
| Title |
|---|
| "Removal of anionic azo dyes from aqueous solutions by quaternary ammonium salt-functionalized fibers with adjustable surface microenvironments";Jingyan Zhao et al.;《Reactive and Functional Polymers》;第154卷;第104684（1-10）页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115400791A (en) | 2022-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20230256377A1 (en) | Amino sorbents for capturing of co2 from gas streams | |
| Chaikittisilp et al. | Poly (L‐lysine) Brush–Mesoporous Silica Hybrid Material as a Biomolecule‐Based Adsorbent for CO2 Capture from Simulated Flue Gas and Air | |
| CN109232781B (en) | Preparation method of nitrogen-containing porous organic polymer | |
| Xiao et al. | A nanoporous graphene analog for superfast heavy metal removal and continuous-flow visible-light photoredox catalysis | |
| Zhang et al. | Microporous polybenzoxazoles with tunable porosity and heteroatom concentration for dynamic adsorption/separation of CO2 mixed gases | |
| Du et al. | Dehydrative Formation of Isosorbide from Sorbitol over Poly (ionic liquid)–Covalent Organic Framework Hybrids | |
| WO2023104656A1 (en) | Method for separating gaseous carbon dioxide from a gas mixture | |
| CN111171212B (en) | Metal organic framework surface molecularly imprinted polymer and preparation method and application thereof | |
| Manna et al. | Dithia-crown-ether integrated self-exfoliated polymeric covalent organic nanosheets for selective sensing and removal of mercury | |
| CN115400791B (en) | Quaternary phosphonium salt functionalized fiber and preparation method and application thereof | |
| Alahmed et al. | Covalent and electrostatic incorporation of amines into hypercrosslinked polymers for increased CO2 selectivity | |
| CN116535593A (en) | Ethylenediimine covalent organic framework and preparation method and application thereof | |
| CN106866900A (en) | A kind of photoresponse molecularly imprinted material on surface and its preparation method and application | |
| CN114456337B (en) | Preparation method of ionic porous organic cage material applied to radioactive iodine adsorption under high-temperature and low-concentration conditions | |
| CN113318707B (en) | Organic supermolecule gel system of binuclear rhodium-porphyrin derivative and preparation method thereof | |
| CN106984279A (en) | The preparation method and obtained material of a kind of modified metal organic framework material | |
| CN107915788B (en) | Cyclodextrin-based micromolecular pollutant adsorption material and preparation method thereof | |
| Oxelbark et al. | Investigation of a tartaric acid‐based linear polyamide and dimer as chiral selectors in liquid chromatography | |
| CN115894912B (en) | Perrhenate adsorption method based on three-dimensional covalent organic framework | |
| CN114805762A (en) | Porous organic polymer containing azobenzene, and preparation method and application thereof | |
| Wulff | Imprinting techniques in synthetic polymers—new options for chemosensors | |
| CN111318270B (en) | Monomer, polymer, filter, adsorbent preparation method and application | |
| CN116947860A (en) | Cationic cyclopean material, preparation method thereof and application thereof in iodine adsorption | |
| CN1298919C (en) | Method for preparing functional fiber in type of even hole on large net | |
| Srividhya et al. | Stilbene-Cross-Linked Pillar [5] arene-Based Polymer for Efficient Iodine Vapor Capture and Adsorption from Water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |