CN111218027A - Preparation method and application of super-crosslinked polymer synthesized by using waste foamed polystyrene - Google Patents
Preparation method and application of super-crosslinked polymer synthesized by using waste foamed polystyrene Download PDFInfo
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Abstract
The invention discloses a preparation method for synthesizing a hypercrosslinked polymer by utilizing waste expanded polystyrene, which recycles the waste expanded polystyrene, takes the waste expanded polystyrene as a raw material, and synthesizes an efficient and recyclable hypercrosslinked polymer WPS-M1-Br by utilizing Friedel-crafts reaction and quaternization reaction. The preparation method has wide raw material source and simple preparation method. The invention also uses the super cross-linked polymer WPS-M1-Br as a catalystFor CO2In the cycloaddition reaction with epoxy compounds, the catalyst has the advantages of high catalytic reaction activity, short reaction time, high product yield (90-99 percent) and high selectivity (up to 99 percent).
Description
Technical Field
The invention relates to the field of organic catalytic synthesis, in particular to a preparation method for synthesizing a hypercrosslinked polymer by utilizing waste expanded polystyrene and application of the hypercrosslinked polymer in CO2Use in a cycloaddition reaction with an epoxide.
Background
At present, the yield of expanded polystyrene accounts for the second place of the amount of foamed plastic all over the world, and the expanded polystyrene is widely applied to different fields of industry, agriculture and the like. However, as the amount of expanded polystyrene is increased, a large amount of expanded polystyrene waste is generated. The foamed polystyrene waste is not easy to age and not degraded for a hundred years, so that the foamed polystyrene waste is visible everywhere, white pollution is caused, the development of the plastic industry is hindered, the resource waste is caused, the environment is deteriorated, the natural environment is seriously influenced, and a series of social problems and economic hazards are brought. The super-crosslinked polymer is a novel porous material, and compared with the traditional inorganic porous material, the super-crosslinked polymer has the unique advantages of stable pore channel structure, relatively low skeleton density, large specific surface area, rich pore structure, strong chemical modifiability, excellent catalytic performance and adsorption performance and the like. In recent years, hypercrosslinked polymers have been extensively studied and exhibit excellent properties in terms of energy storage, gas separation, heterogeneous catalysis, and the like. Generally, the preparation of the hypercrosslinked polymer requires that a linear or low crosslinked polymer is prepared in advance and is taken as a precursor, then lewis acid is taken as a catalyst, difunctional group micromolecules are taken as a solvent, and the preparation of the hypercrosslinked polymer by taking waste polystyrene as a raw material is an economical method.
As people are more and more concerned about the influence of greenhouse gases on the climate, the conversion of carbon dioxide into chemicals with high added values is receiving wide attention, and one potential approach is to form five-membered cyclic carbonates by addition ring of epoxides. CO 22Five-membered cyclic carbonates obtained by the addition reaction of the epoxy ring have a wide range of applications, such as polar solvents, electrolytes, industrial chemicals and the synthesis of polycarbonates and polyurethanes. Reported CO2The epoxy cycloaddition reaction is generally carried out using an alkali metal salt, a metal oxide, a transition metal complex, or the like as a catalyst, and has problems of unsustainability, environmental friendliness, and the like.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a hypercrosslinked polymer by utilizing waste expanded polystyrene, which recycles the waste expanded polystyrene, has wide raw material source and simple preparation method.
Objects of the inventionIt consists in providing the above-mentioned hypercrosslinked polymer as a catalyst in CO2The application of the epoxy cycloaddition reaction has the advantages of high catalytic reaction activity, short reaction time, high product yield and high selectivity.
In order to achieve the above purpose, the solution of the invention is:
a preparation method for synthesizing a hypercrosslinked polymer by utilizing waste expanded polystyrene comprises the following steps:
step 1, adding deionized water, styrene oxide, phenylacetylene, sodium azide and cuprous bromide into a reaction vessel, heating to 75-80 ℃ by microwave of 350-400W, stirring for reaction for 20-30 min, after the reaction is finished, washing and filtering a reaction product by using the deionized water, dissolving the obtained solid by using ethyl acetate, filtering to remove residual cuprous bromide, carrying out rotary evaporation and concentration, and separating and purifying by using column chromatography to obtain a hydroxyl functionalized triazole copolymerization monomer, wherein the hydroxyl functionalized triazole copolymerization monomer is marked as M1;
step 2, adding waste foamed polystyrene, Lewis acid catalyst anhydrous ferric chloride, cross-linking agent methylal and the copolymerized monomer M1 prepared in the step 1 into a round-bottom flask containing a solvent 1, 2-dichloroethane, stirring and refluxing for 4-5 hours at 40-45 ℃, heating to 80-85 ℃, continuing stirring and refluxing for 24-28 hours, washing a reaction product with methanol after the reaction is finished, drying, performing Soxhlet extraction with methanol at 110-120 ℃, and drying for 10-12 hours at 75-80 ℃ to obtain a super-crosslinked polymer precursor, which is marked as WPS-M1;
and 3, adding a solvent DMF, a reaction reagent n-bromobutane and the WPS-M1 prepared in the step 2 into a round-bottom flask, stirring and refluxing for 20-24 hours at 75-80 ℃, after the reaction is finished, washing a reaction product by using ethyl acetate, and drying for 10-12 hours at 75-80 ℃ to obtain the super-crosslinked polymer, which is marked as WPS-M1-Br.
In the step 1, the dosage ratio of the styrene oxide to the deionized water is 1.0g: 15-20 mL, and the dosage ratio of the styrene oxide, the phenylacetylene, the sodium azide and the cuprous bromide is 1: 1.02-1.10: 1.08-1.20: 100-110.
In the step 2, the dosage ratio of the waste expanded polystyrene to the 1, 2-dichloroethane is 1.0g: 10-20 mL, and the dosage ratio of the waste expanded polystyrene, the anhydrous ferric trichloride, the methylal and the M1 is 1.0: 4.50-5.00: 2.10-2.40: 2.44-2.60.
In the step 3, the dosage ratio of the WPS-M1 to the DMF is 1.0g: 20-30 mL, and the dosage ratio of the WPS-M1 to the n-bromobutane is 1.0g: 10-12 mL.
The application of the hypercrosslinked polymer is in CO2As a catalyst in cycloaddition reactions with epoxy compounds.
The application of the hypercrosslinked polymer comprises the following steps:
step 1, sequentially adding an epoxy compound and the super cross-linked polymer (WPS-M1-Br) into an autoclave, vacuumizing the autoclave, and introducing CO into the autoclave2Reacting for 1-2 h at 120-140 ℃, and monitoring the reaction completion by TLC in the reaction process;
step 2, after the reaction is finished, adding ethyl acetate into the high-pressure kettle for dilution, and sequentially performing centrifugation, rotary evaporation and column chromatography separation and purification to obtain a product cyclic carbonate;
in the step 1, the dosage ratio of the epoxy compound to the WPS-M1-Br is 1 mmol: 8-10 mg, and in the step 2, the dosage of the ethyl acetate is 20-30 mL.
In step 1, the epoxy compound is styrene oxide, 2- (phenoxymethyl) ethylene oxide, 2- ((o-tolyloxy) methyl) ethylene oxide, 2- ((allyloxy) methyl) ethylene oxide, 2- (butoxymethyl) ethylene oxide, 2- (((2-ethylhexyl) oxy) methyl) ethylene oxide, 1, 2-bis (oxirane-2-methoxy) ethane, 2- (chloromethyl) ethylene oxide, oxirane-2-methanol, or resorcinol diglycidyl ether.
In step 1, CO is introduced2The pressure of (A) is 2.0 to 2.2 MPa.
In the step 2, the rotation speed of the centrifugation is 3500-4000 revolutions per minute.
In step 2, the cyclic carbonate is 4-phenyl-1, 3-dioxolane-2-one, 4- (phenoxymethyl) -1, 3-dioxolane-2-one, 4- ((o-tolyloxy) methyl) -1, 3-dioxolane-2-one, 4- ((allyloxy) methyl) -1, 3-dioxolane-2-one, 4- (butoxymethyl) - -1, 3-dioxolane-2-one, 4- (((2-ethylhexyl) oxy) methyl) -1, 3-dioxolane-2-one, 4- ((2- ((4-oxo-1, 3-dioxolane-2-yl) methoxy) ethoxy) methyl) -1, 3-dioxolan-2-one, 4- (chloromethyl) -1, 3-dioxolan-2-one, 4- (hydroxymethyl) -1, 3-dioxolan-2-one, 4' - ((1, 3-phenylenebis (oxy)) bis (methylene)) bis-1, 3-dioxolan-2-one.
In the invention, the structural formulas of waste expanded polystyrene, prepared M1, WPS-M1 and WPS-M1-Br are shown as formulas I-IV:
in the present invention, the preparation route of the hypercrosslinked polymer is as follows:
after the technical scheme is adopted, the preparation method for synthesizing the super-crosslinked polymer by utilizing the waste expanded polystyrene recycles the waste expanded polystyrene, synthesizes the high-efficiency and recyclable super-crosslinked polymer WPS-M1-Br by taking the waste expanded polystyrene as a raw material and utilizing Friedel-crafts reaction and quaternization reaction, and uses the high-efficiency and recyclable super-crosslinked polymer WPS-M1-Br for catalyzing CO2And the epoxy compound is converted into various cyclic carbonates, so that the method has important potential application value. The preparation method has wide raw material source and simple preparation method.
The invention also applies the super cross-linked polymer WPS-M1-Br as a catalyst to CO2In the cycloaddition reaction with epoxy compounds, the catalyst has the advantages of high catalytic reaction activity, short reaction time, high product yield (90-99 percent) and high selectivity (up to 99 percent).
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
EXAMPLE 1 preparation of hypercrosslinked Polymer
A preparation method for synthesizing a hypercrosslinked polymer by utilizing waste expanded polystyrene comprises the following steps:
step 1, adding 1.0g of styrene oxide into a round-bottom flask containing 15mL of deionized water, then sequentially adding 1.02g of phenylacetylene, 1.08g of sodium azide and 100mg of cuprous bromide, heating to 80 ℃ by 400W of microwave, stirring, reacting for 20min, after the reaction is finished, washing and filtering a reaction product by using 20-30 mL of deionized water, dissolving the obtained solid by using 100mL of ethyl acetate, filtering to remove residual cuprous bromide, performing rotary evaporation and concentration, and performing separation and purification by using column chromatography to obtain a hydroxyl functionalized triazole copolymerization monomer, which is marked as M1, wherein the yield is 85%;
step 2, adding 0.5g of waste foamed polystyrene into a round-bottom flask containing 5mL of 1, 2-dichloroethane, then sequentially adding 2.25g of anhydrous ferric trichloride, 1.05g of methylal and 1.22g of copolymerized monomer M1 prepared in the step 1, stirring and refluxing for 5h at 45 ℃, heating to 80 ℃, continuing stirring and refluxing for 24h, washing a reaction product by using 20-30 mL of methanol after the reaction is finished, drying at 80 ℃, performing Soxhlet extraction by using methanol at 120 ℃, and drying at 80 ℃ for 12h to obtain a super-crosslinked polymer precursor, which is marked as WPS-M1;
and 3, adding 0.5g of WPS-M1 prepared in the step 2 into a round-bottom flask containing 10mL of DMF, then adding 5mL of n-bromobutane, stirring and refluxing for 24h at 80 ℃, after the reaction is finished, washing a reaction product by using 20-30 mL of ethyl acetate, and drying for 12h at 80 ℃ to obtain a super-crosslinked polymer, namely WPS-M1-Br.
Example 2
Preparation of 4-phenyl-1, 3-dioxolan-2-one (structural formula below):
step 1, 5mmol of styrene oxide and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were sequentially added to an autoclave, the autoclave was evacuated, and 2.0MPa of CO was introduced into the autoclave2Reacting for 2 hours at 120 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 20mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 3500 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain the product cyclic carbonate-4-phenyl-1, 3-dioxolane-2-one, wherein the yield is 93%, and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1789(C＝O),1163(C-O),1065(C-O),732,697；1H NMR(500MHz,CDCl3)δ:7.45-7.37(m,Ar-H,5H),5.69(t,J＝8.4Hz,1H),4.81(t,J＝8.2Hz,1H),4.35(t,J＝8.2Hz,1H).
Example 3
Preparation of 4- (phenoxymethyl) -1, 3-dioxolan-2-one (structural formula below):
step 1, 5mmol of 2- (phenoxymethyl) ethylene oxide and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were sequentially added to an autoclave, the autoclave was evacuated, and 2.0MPaCO was introduced into the autoclave2Reacting for 2 hours at 120 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 20mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 3500 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain the product cyclic carbonate-4- (phenoxymethyl) -1, 3-dioxolane-2-one, wherein the yield is 97%, and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1788(C＝O),1597,1492,1242,1167(C-O),1052(C-O),754,692；1H NMR(500MHz,CDCl3)δ:7.33(m,2H),7.04(t,J＝7.6Hz,1H),6.93(d,J＝7.8Hz,2H),5.05(m,1H),4.63(t,J＝8.3Hz,1H),4.56(dd,J＝5.8,8.6Hz,1H),4.26(dd,J＝4.3,10.5Hz,1H),4.17(dd,J＝3.6,10.5Hz,1H).
Example 4
Preparation of 4- ((o-tolyloxy) methyl) -1, 3-dioxolan-2-one (structural formula:
step 1, 5mmol of 2- ((o-tolyloxy) methyl) ethylene oxide and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were added in this order to an autoclave, the autoclave was evacuated, and 2.0MPaCO was introduced into the autoclave2Reacting for 2 hours at 120 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 20mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 3500 rpm, and then performing rotary evaporation and column chromatography separation and purification to obtain the product cyclic carbonate-4- ((o-tolyloxy) methyl) -1, 3-dioxolane-2-one, wherein the yield is 99% and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1789(C＝O),1602,1495,1264,1245,1163(C-O),1049(C-O),732,703；1H NMR(500MHz,CDCl3)δ:7.19(m,2H),6.95(t,J＝7.0Hz,1H),6.80(d,J＝8.6Hz,2H),5.08(m,1H),4.66(t,J＝8.3Hz,1H),4.60(dd,J＝5.3,8.4Hz,1H),4.29(dd,J＝3.6,10.7Hz,1H),4.16(dd,J＝3.0,10.6Hz,1H),2.24(s,3H).
Example 5
Preparation of 4- ((allyloxy) methyl) -1, 3-dioxolan-2-one (structural formula:
step 1, adding 5mmol of 2- ((allyl) into an autoclave in sequenceOxy) methyl) ethylene oxide and 40mg of the hypercrosslinked polymer (WPS-M1-Br) obtained in example 1, the autoclave was evacuated and 2.0MPa of CO was introduced into the autoclave2Reacting for 2 hours at 120 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 20mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 3500 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain the product cyclic carbonate-4- ((allyloxy) methyl) -1, 3-dioxolane-2-one, wherein the yield is 99% and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1794(C＝O),1735(C＝C),1163(C-O),1046(C-O),734,714；1H NMR(500MHz,CDCl3)δ:5.86(m,1H),5.28-5.21(m,2H),4.83(m,1H),4.50-4.39(m,2H),4.05(d,2H),3.69-3.61(m,2H).
Example 6
Preparation of 4- (butoxymethyl) - -1, 3-dioxolan-2-one (formula below):
step 1, 5mmol of 2- (butoxymethyl) ethylene oxide and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were sequentially charged into an autoclave, the autoclave was evacuated, and 2.0MPaCO was introduced into the autoclave2Reacting for 2 hours at 120 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 20mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 3500 rpm, and then performing rotary evaporation and column chromatography separation and purification to obtain the product cyclic carbonate-4- (butoxymethyl) -1, 3-dioxolane-2-one, wherein the yield is 90%, and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1789(C＝O),1166(C-O),1047(C-O),734,714；1H NMR(500MHz,CDCl3)δ:4.81(m,1H),4.50-4.40(m,2H),3.68-3.61(m,2H),3.51(m,2H),1.56(m,2H),1.37(m,2H),0.92(t,J＝7.39,3H).
Example 7
Preparation of 4- (((2-ethylhexyl) oxy) methyl) -1, 3-dioxolan-2-one (formula:
step 1, 5mmol of 2- (((2-ethylhexyl) oxy) methyl) oxirane and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were added in succession to an autoclave, the autoclave was evacuated, and 2.2MPa of CO was introduced into the autoclave2Reacting for 1h at 140 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 30mL of ethyl acetate into the autoclave for dilution, centrifuging at the rotating speed of 4000 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain the product cyclic carbonate-4- (((2-ethylhexyl) oxy) methyl) -1, 3-dioxolane-2-one, wherein the yield is 92% and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1788(C＝O),1166(C-O),1043(C-O),732,714；1H NMR(500MHz,CDCl3)δ:4.81(m,1H),4.49-4.39(m,2H),3.66-3.58(m,2H),3.39(m,2H),1.50(m,1H),1.42-1.19(m,8H),0.92(m,6H).
Example 8
Preparation of 4- ((2- ((4-oxo-1, 3-dioxolan-2-yl) methoxy) ethoxy) methyl) -1, 3-dioxolan-2-one (structural formula:
step 1, 5mmol of 1, 2-bis (oxirane-2-methoxy) ethane and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were sequentially added to an autoclave, the autoclave was evacuated, and the autoclave was evacuatedIntroducing 2.2MPa CO into the autoclave2Reacting for 1h at 140 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 30mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 4000 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain a product, namely the cyclic carbonate-4- ((2- ((4-oxo-1, 3-dioxolane-2-yl) methoxy) ethoxy) methyl) -1, 3-dioxolane-2-one, wherein the yield is 92% and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1784(C＝O),1170(C-O),1048(C-O),733,714；1H NMR(500MHz,CDCl3)δ:4.85(m,2H),4.53-4.44(m,4H),3.76-3.58(m,6H).
Example 9
Preparation of 4- (chloromethyl) -1, 3-dioxolan-2-one (structural formula below):
step 1, 5mmol of 2- (chloromethyl) oxirane and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were added in succession to an autoclave, the autoclave was evacuated, and 2.2MPa of CO was introduced into the autoclave2Reacting for 1h at 140 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 30mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 4000 rpm, and then performing rotary evaporation and column chromatography separation and purification to obtain the product, namely the cyclic carbonate-4- (chloromethyl) -1, 3-dioxolane-2-one, wherein the yield is 92% and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1812(C＝O),1264,1162(C-O),1073(C-O),731,702；1H NMR(500MHz,CDCl3)δ:4.99(m,1H),4.58(t,J＝8.6Hz,1H),4.39(m,1H),3.81-3.72(m,2H).
Example 10
Preparation of 4- (hydroxymethyl) -1, 3-dioxolan-2-one (structural formula below):
step 1, 5mmol of ethylene oxide-2-methanol and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were sequentially added to an autoclave, the autoclave was evacuated, and 2.2MPa of CO was introduced into the autoclave2Reacting for 1h at 140 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 30mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 4000 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain the product, namely the cyclic carbonate-4- (hydroxymethyl) -1, 3-dioxolane-2-one, wherein the yield is 95% and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:3416(OH),1770(C＝O),1170(C-O),1048(C-O),732,715；1H NMR(500MHz,CDCl3)δ:4.83(m,1H),4.54-4.49(m,2H),3.84-3.73(m,2H).
Example 11
Preparation of 4,4' - ((1, 3-phenylenebis (oxy)) bis (methylene)) bis-1, 3-dioxolan-2-one (structural formula:
step 1, 5mmol of resorcinol diglycidyl ether and 40mg of the hypercrosslinked polymer (WPS-M1-Br) prepared in example 1 were sequentially added to an autoclave, the autoclave was evacuated, and 2.2MPaCO was introduced into the autoclave2Reacting for 1h at 140 ℃, monitoring the reaction by TLC in the reaction process, and stopping the reaction when the raw material point completely disappears;
and 2, after the reaction is finished, adding 30mL of ethyl acetate into the high-pressure kettle for dilution, centrifuging at the rotating speed of 4000 revolutions per minute, and then performing rotary evaporation and column chromatography separation and purification to obtain the product, namely the cyclic carbonate-4, 4' - ((1, 3-phenylene bis (oxy)) bis (methylene)) bis-1, 3-dioxolane-2-one, wherein the yield is 97%, and the selectivity is 99%.
The infrared and nuclear magnetic characterization of the cyclic carbonate is as follows: FT-IR (KBr disc) cm-1:1790(C＝O),1158(C-O),1051(C-O),731,702；1H NMR(500MHz,CDCl3)δ:7.22(t,J＝8.2Hz,2H),6.59-6.47(m,3H),5.04(m,2H),4.62-4.52(m,4H),4.24(m,2H),4.12(m,2H).
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (10)
1. A preparation method for synthesizing a hypercrosslinked polymer by utilizing waste expanded polystyrene is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding deionized water, styrene oxide, phenylacetylene, sodium azide and cuprous bromide into a reaction vessel, heating to 75-80 ℃ by microwave of 350-400W, stirring for reaction for 20-30 min, after the reaction is finished, washing and filtering a reaction product by using the deionized water, dissolving the obtained solid by using ethyl acetate, filtering to remove residual cuprous bromide, carrying out rotary evaporation and concentration, and separating and purifying by using column chromatography to obtain a hydroxyl functionalized triazole copolymerization monomer, wherein the hydroxyl functionalized triazole copolymerization monomer is marked as M1;
step 2, adding waste foamed polystyrene, Lewis acid catalyst anhydrous ferric chloride, cross-linking agent methylal and the copolymerized monomer M1 prepared in the step 1 into a round-bottom flask containing a solvent 1, 2-dichloroethane, stirring and refluxing for 4-5 hours at 40-45 ℃, heating to 80-85 ℃, continuing stirring and refluxing for 24-28 hours, washing a reaction product with methanol after the reaction is finished, drying, performing Soxhlet extraction with methanol at 110-120 ℃, and drying for 10-12 hours at 75-80 ℃ to obtain a super-crosslinked polymer precursor, which is marked as WPS-M1;
and 3, adding a solvent DMF, a reaction reagent n-bromobutane and the WPS-M1 prepared in the step 2 into a round-bottom flask, stirring and refluxing for 20-24 hours at 75-80 ℃, after the reaction is finished, washing a reaction product by using ethyl acetate, and drying for 10-12 hours at 75-80 ℃ to obtain the super-crosslinked polymer, which is marked as WPS-M1-Br.
2. The method for preparing the hypercrosslinked polymer synthesized by the waste expanded polystyrene as claimed in claim 1, wherein: in the step 1, the dosage ratio of the styrene oxide to the deionized water is 1.0g: 15-20 mL, and the dosage ratio of the styrene oxide, the phenylacetylene, the sodium azide and the cuprous bromide is 1: 1.02-1.10: 1.08-1.20: 100-110.
3. The method for preparing the hypercrosslinked polymer synthesized by the waste expanded polystyrene as claimed in claim 1, wherein: in the step 2, the dosage ratio of the waste expanded polystyrene to the 1, 2-dichloroethane is 1.0g: 10-20 mL, and the dosage ratio of the waste expanded polystyrene, the anhydrous ferric trichloride, the methylal and the M1 is 1.0: 4.50-5.00: 2.10-2.40: 2.44-2.60.
4. The method for preparing the hypercrosslinked polymer synthesized by the waste expanded polystyrene as claimed in claim 1, wherein: in the step 3, the dosage ratio of the WPS-M1 to the DMF is 1.0g: 20-30 mL, and the dosage ratio of the WPS-M1 to the n-bromobutane is 1.0g: 10-12 mL.
5. Use of a hypercrosslinked polymer prepared by the process according to claim 1, characterized in that: is that the hypercrosslinked polymer is in CO2As a catalyst in cycloaddition reactions with epoxy compounds.
6. Use of a hypercrosslinked polymer according to claim 5, characterised in that: the method comprises the following steps:
step 1, sequentially adding an epoxy compound and the hypercrosslinked polymer into an autoclave, vacuumizing the autoclave, and introducing CO into the autoclave2At 120 to 1Reacting for 1-2 h at 40 ℃, and monitoring the reaction completion by TLC in the reaction process;
step 2, after the reaction is finished, adding ethyl acetate into the high-pressure kettle for dilution, and sequentially performing centrifugation, rotary evaporation and column chromatography separation and purification to obtain a product cyclic carbonate;
in the step 1, the dosage ratio of the epoxy compound to the WPS-M1-Br is 1 mmol: 8-10 mg, and in the step 2, the dosage of the ethyl acetate is 20-30 mL.
7. Use of a hypercrosslinked polymer according to claim 6, characterised in that: in step 1, the epoxy compound is styrene oxide, 2- (phenoxymethyl) ethylene oxide, 2- ((o-tolyloxy) methyl) ethylene oxide, 2- ((allyloxy) methyl) ethylene oxide, 2- (butoxymethyl) ethylene oxide, 2- (((2-ethylhexyl) oxy) methyl) ethylene oxide, 1, 2-bis (oxirane-2-methoxy) ethane, 2- (chloromethyl) ethylene oxide, oxirane-2-methanol, or resorcinol diglycidyl ether.
8. Use of a hypercrosslinked polymer according to claim 6, characterised in that: in step 1, CO is introduced2The pressure of (A) is 2.0 to 2.2 MPa.
9. Use of a hypercrosslinked polymer according to claim 6, characterised in that: in the step 2, the rotation speed of the centrifugation is 3500-4000 revolutions per minute.
10. Use of a hypercrosslinked polymer according to claim 6, characterised in that: in step 2, the cyclic carbonate is 4-phenyl-1, 3-dioxolane-2-one, 4- (phenoxymethyl) -1, 3-dioxolane-2-one, 4- ((o-tolyloxy) methyl) -1, 3-dioxolane-2-one, 4- ((allyloxy) methyl) -1, 3-dioxolane-2-one, 4- (butoxymethyl) - -1, 3-dioxolane-2-one, 4- (((2-ethylhexyl) oxy) methyl) -1, 3-dioxolane-2-one, 4- ((2- ((4-oxo-1, 3-dioxolane-2-yl) methoxy) ethoxy) methyl) -1, 3-dioxolan-2-one, 4- (chloromethyl) -1, 3-dioxolan-2-one, 4- (hydroxymethyl) -1, 3-dioxolan-2-one, 4' - ((1, 3-phenylenebis (oxy)) bis (methylene)) bis-1, 3-dioxolan-2-one.
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