CN113582934B - Preparation method and application of Pentane metal-free homogeneous catalyst - Google Patents
Preparation method and application of Pentane metal-free homogeneous catalyst Download PDFInfo
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002815 homogeneous catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004593 Epoxy Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 34
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 34
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 4
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 4
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 6
- 239000003054 catalyst Substances 0.000 abstract description 22
- 238000006352 cycloaddition reaction Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 6
- -1 amine salt Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- RIPZIAOLXVVULW-UHFFFAOYSA-N pentane-2,4-dione Chemical compound CC(=O)CC(C)=O.CC(=O)CC(C)=O RIPZIAOLXVVULW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 19
- 230000035484 reaction time Effects 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000643 oven drying Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
- C07D243/08—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
- C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D243/00—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms
- C07D243/06—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4
- C07D243/10—Heterocyclic compounds containing seven-membered rings having two nitrogen atoms as the only ring hetero atoms having the nitrogen atoms in positions 1 and 4 condensed with carbocyclic rings or ring systems
- C07D243/12—1,5-Benzodiazepines; Hydrogenated 1,5-benzodiazepines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D259/00—Heterocyclic compounds containing rings having more than four nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/26—Polythioesters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a preparation method of a Pentane metal-free homogeneous catalyst, which takes acetylacetone (2, 4-pentanedione) and organic amine salt as raw materials, and obtains the Pentane metal-free homogeneous catalyst by a one-step method; the prepared catalyst can be used for catalyzing the cycloaddition reaction of the epoxy compound and carbon dioxide to prepare cyclic carbonate and catalyzing the copolymerization reaction of the epoxy compound and sulfur dioxide to prepare the polysulfite; the raw materials required by the preparation of the catalyst are simple and easy to obtain, and the preparation method is simple, economical and environment-friendly. The catalyst has the advantages of small dosage, high activity, mild reaction conditions in catalytic reaction, convenience for large-scale production and important industrial application prospect.
Description
Technical Field
The invention relates to a preparation technology and application of a Pentane metal-free homogeneous catalyst, in particular to a preparation method of the Pentane metal-free homogeneous catalyst, a method for catalyzing copolymerization of sulfur dioxide and an epoxy compound, and a cycloaddition reaction method of the carbon dioxide and the epoxy compound.
Background
Sulfur dioxide (SO) 2 ) As a product of fossil combustion, is a toxic, odorous gaseous pollutant; along with SO 2 Acid rain and photochemical smog can be generated, and the human health and the ecological environment are seriously endangered. In recent years, researchers have found the use of epoxy compounds with SO 2 Copolymerization reaction is carried out, and sulfonyl (-SO) can be introduced into the product 2 (-), which gives the polymer excellent mechanical properties, chemical resistance, good permeability and biocompatibility, etc. Can be applied to the fields of electrode composite materials, thermosetting adhesives, drug transportation, sewage purification and the like. However, in the copolymerization reaction, monomers are difficult to react with SO 2 Low selectivity of polymerization or product polysulfides, and the like, leading toSO-causing 2 The copolymerization is difficult to realize industrialization. Over the past few decades, researchers have developed a variety of catalysts to catalyze SO 2 The catalyst is copolymerized with epoxy compound, including organic metal catalyst, peroxide catalyst, lewis acid/base catalyst, inorganic salt catalyst, etc. However, these catalysts still have problems of metal ion content, difficulty in separation, complex preparation method, poor catalytic effect and the like. Therefore, it is urgent to find an environment-friendly and efficient metal-free catalyst.
Carbon dioxide (CO) 2 ) Is a main greenhouse gas, and is a non-toxic, low-cost and rich renewable carbon source. Development of CO 2 The green utilization technology improves the added value of the product and has important economic and environmental significance. CO 2 The cyclic carbonate can be obtained through cycloaddition reaction with epoxy compound, and has wide application prospect in the fields of plastic raw materials, pharmacy, fine chemicals and the like. However, due to CO 2 Therefore, there is a need to develop a high performance catalyst to promote CO 2 Is a ring-opening addition reaction of (a). Researchers have developed catalysts such as metal complexes, organic bases, alkali halides, etc. to catalyze CO 2 Cycloaddition reaction with epoxy compounds. However, there are problems of metal ion pollution, high metal cost, complicated operation, and the like, so that development of a green, efficient and low-cost catalyst is required.
In recent years, nonmetallic catalysts are widely researched by researchers by virtue of the characteristics of low price, high activity, mild reaction conditions and the like. The catalyst contains-OH, -NH 2 Hydrogen bond donors such as-COOH and the like can form hydrogen bonds with oxygen atoms of epoxy groups, so that C-O bonds in the epoxy groups are polarized, the electron cloud density of the epoxy groups is weakened, metal ions and halides can be effectively replaced, and the problems of catalyst poisoning, corrosion of the halides on a stainless steel reaction kettle and the like caused by falling of the metal ions are avoided.
Disclosure of Invention
Aiming at the problems of harsh copolymerization of sulfur dioxide and an epoxy compound, low catalytic activity of a traditional catalyst, environmental protection and the like of a cycloaddition reaction condition of the carbon dioxide and the epoxy compound, the invention provides a preparation method of a Pentane type metal-free homogeneous catalyst.
The organic ammonium salt can be one of tetraethylenepentamine, ethylenediamine, o-phenylenediamine, 1, 8-diaminonaphthalene and 2, 3-diaminotoluene; the molar ratio of the acetylacetone to the organic amine salt is 2:1-5:1.
The invention also aims to apply the Pentane type metal-free homogeneous catalyst prepared by the method to the preparation of the poly-sulfite by catalyzing the copolymerization of sulfur dioxide and an epoxy compound, and specifically, sequentially adding the epoxy compound and the Pentane type metal-free homogeneous catalyst into a high-pressure reaction kettle; and then introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, then introducing sulfur dioxide with the purity of 99%, setting the pressure of the sulfur dioxide to be 0.2MPa, setting the reaction temperature to be 50-90 ℃, cooling after reacting for 4-24 hours, dissolving a reaction product by using methylene dichloride, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 3-4 times, and vacuum drying the washed precipitate at 40 ℃ for 24 hours to obtain the copolymer of the sulfur dioxide and the epoxy compound, namely the polysulfite.
In the copolymerization reaction of sulfur dioxide and an epoxy compound, the mole ratio of the Pentane-type metal-free homogeneous catalyst to the epoxy compound is 1:100-1:1000.
The invention also aims to apply the Pentane type metal-free homogeneous catalyst prepared by the method to the cycloaddition reaction of carbon dioxide and an epoxy compound, and specifically, sequentially adding the epoxy compound and the Pentane type metal-free homogeneous catalyst into a high-pressure reaction kettle; and then introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, then introducing carbon dioxide with the purity of 99%, setting the reaction temperature to be 70-110 ℃ under the pressure of 0.5-4 MPa, cooling after the reaction is carried out for 3-7 hours, and obtaining the product after the reaction is the cyclic carbonate.
In the cycloaddition reaction of carbon dioxide and an epoxy compound, the molar ratio of the Pentane type metal-free homogeneous catalyst to the epoxy compound is 1:100-1:1000.
The epoxy compound is one of epoxycyclohexane, epoxypropane, 1, 2-epoxybutane, styrene oxide and epoxychloropropane.
Compared with the prior art, the invention has the following advantages:
(1) The invention prepares the Pentane metal-free homogeneous catalyst by using acetylacetone and organic amine salt through a one-step method for the first time, and the catalyst can be used for catalyzing the cycloaddition reaction of an epoxy compound and carbon dioxide to prepare cyclic carbonate and catalyzing the copolymerization reaction of the epoxy compound and sulfur dioxide to prepare polysulfite;
(2) The preparation method of the catalyst is simple, the operation is easy, the catalyst dosage is small, the cost is low, the yield is high, and the green industrial production is easy to realize.
Drawings
FIG. 1 is a Fourier transform infrared spectroscopy (FTIR) plot of a Pentane-type metal-free homogeneous catalyst prepared in example 1;
FIG. 2 is a Fourier transform infrared spectroscopy (FTIR) plot of the polysulfides prepared in example 2;
FIG. 3 is a cyclic carbonate prepared in example 3 1 H NMR spectrum;
FIG. 4 is a diagram of the polysulfides prepared in example 4 1 H NMR spectrum.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the scope of the present invention is not limited to the above.
Example 1:
(1) 8.23mL of acetylacetone and 70mL of absolute ethyl alcohol are sequentially added into a 50mL three-neck flask, 7.57mL of tetraethylenepentamine is added dropwise, and the three-neck flask is placed into an oil bath kettle for heating reflux reaction for 24h at 75 ℃;
(2) After the reaction is finished, transferring the reacted solution into a single-neck flask, rotationally steaming out ethanol solution at 60 ℃, drying for 12 hours at 50 ℃ in a vacuum drying oven, and adopting Fourier transform infraredThe resulting product was characterized spectroscopically (FTIR), as shown in fig. 1; as can be seen from FIG. 1, at 3352cm -1 And 1708cm -1 Where no reactant-NH-was found 2 Characteristic peak at 1623cm instead of c=o -1 The stretching vibration of the c=n bond occurring at the site, preliminarily demonstrates successful synthesis of the catalyst.
(3) Sequentially adding 5mL of epoxy cyclohexane and 0.034g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1; then introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 80 ℃, and the reaction time is 6 hours; dissolving the reaction product by using methylene dichloride, adding methanol for precipitation, filtering to obtain precipitation, washing the precipitation by using methanol for 3 times, placing the washed precipitation in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and the epoxy compound. Wherein, the conversion rate of the epoxycyclohexane is 93 percent, and the selectivity of the polysulfite is 88 percent.
(4) Sequentially adding 5mL of epichlorohydrin and 0.089g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the proportion of 250:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is set to 280r/min, the temperature is 100 ℃, the carbon dioxide pressure is 1MPa, and the reaction time is 6 hours; the cycloaddition product of the carbon dioxide and the epoxy compound is obtained after cooling, the product yield is 98%, and the selectivity can reach 99%.
Example 2:
(1) 8.23mL of acetylacetone and 60mL of absolute ethyl alcohol are sequentially added into a 50mL three-neck flask, 2.67mL of ethylenediamine is added dropwise, and the three-neck flask is placed in an oil bath kettle for heating reflux reaction for 12h at 60 ℃ after the dropwise addition is finished;
(2) After the reaction, the solution after the reaction is transferred into a single-neck flask, ethanol solution is distilled off at 60 ℃ in a rotary way, and then the solution is dried for 12 hours at 50 ℃ in a vacuum drying oven.
(3) Sequentially adding 5mL of cyclohexene oxide and 0.110g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 100:1; then introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 50 ℃, and the reaction time is 4 hours; dissolving a reaction product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 3 times, placing the washed precipitate in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound. Characterization of the resulting product by Fourier transform Infrared Spectroscopy (FTIR), as can be seen in FIG. 2 at 1202cm -1 And 725cm -1 Vibration peaks associated with s=o and S-O appear, respectively, confirming that sulfur dioxide is present on the main chain; wherein, the conversion rate of the epoxycyclohexane is 96 percent, and the selectivity of the polysulfite is 73 percent;
(4) Sequentially adding 5mL of epichlorohydrin and 0.143g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 100:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is set to 280r/min, the temperature is 70 ℃, the carbon dioxide pressure is 0.5MPa, and the reaction time is 3 hours; after cooling, the cycloaddition product cyclic carbonate of carbon dioxide and epoxy compound is obtained, the product yield is 89%, and the selectivity can reach 94%.
Example 3:
(1) Sequentially adding 20.57mL of acetylacetone and 80mL of absolute ethyl alcohol into a 50mL three-neck flask, dropwise adding 7.57mL of tetraethylenepentamine, and placing the three-neck flask into an oil bath kettle for heating reflux reaction at 90 ℃ for 24h after the dropwise adding is finished;
(2) After the reaction, the solution after the reaction is transferred into a single-neck flask, ethanol solution is distilled off at 60 ℃ in a rotary way, and then the solution is dried for 12 hours at 50 ℃ in a vacuum drying oven.
(3) Sequentially adding 5mL of epoxy cyclohexane and 0.017g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the mol ratio of 1000:1; then introducing nitrogen with the purity of 99.99% into a high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 90 ℃, and the reaction time is 24 hours; dissolving a reaction product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 4 times, placing the washed precipitate in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain a copolymer of sulfur dioxide and an epoxy compound; the conversion of epoxycyclohexane was 97% and the selectivity to polysulfate was 74%.
(4) Sequentially adding 5mL of epichlorohydrin and 0.023g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the proportion of 1000:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is set to 280r/min, the temperature is 110 ℃, the carbon dioxide pressure is 4MPa, and the reaction time is 7 hours; and cooling to obtain the cycloaddition product of the carbon dioxide and the epoxy compound, namely the cyclic carbonate. By using 1 The H NMR spectrum characterizes the resulting product, as in fig. 3; the yield of the product is 82%, and the selectivity can reach 98%.
Example 4:
(1) 8.23mL of acetylacetone and 80mL of absolute ethyl alcohol are sequentially added into a 50mL three-neck flask, 4.2mL of o-phenylenediamine is added dropwise, and the three-neck flask is placed into an oil bath kettle for heating reflux reaction for 12 hours at 90 ℃ after the dropwise addition is finished;
(2) After the reaction is finished, transferring the solution after the reaction into a single-neck flask, steaming out ethanol solution at 60 ℃ in a rotary way, and drying for 12 hours at 50 ℃ in a vacuum drying oven;
(3) 5mL of propylene oxide and 0.039g of Pentane type metal-free homogeneous catalyst are sequentially added into a 50mL high-pressure reaction kettle according to the mol ratio of 500:1; then the nitrogen with the purity of 99.99 percent is addedIntroducing gas into a high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the pressure of the sulfur dioxide is 0.2MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 110 ℃, and the reaction time is 4 hours; dissolving a reaction product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 4 times, placing the washed precipitate in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and an epoxy compound. By using 1 The H NMR spectrum characterizes the resulting product, as in fig. 4; the conversion of epoxycyclohexane was 99% and the selectivity to polysulfate was 65%.
(4) Sequentially adding 5mL of propylene oxide and 0.078g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 250:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is set to 280r/min, the temperature is 110 ℃, the carbon dioxide pressure is 1MPa, and the reaction time is 5 hours; cooling to obtain cycloaddition product cyclic carbonate of carbon dioxide and epoxy compound; the yield of the product is 80%, and the selectivity can reach 95%.
Example 5:
(1) 8.23mL of acetylacetone and 75mL of absolute ethyl alcohol are sequentially added into a 50mL three-neck flask, 5.61mL of 1, 8-diaminonaphthalene is added dropwise, and the three-neck flask is placed into an oil bath kettle for heating reflux reaction for 18h at 75 ℃ after the dropwise addition is finished;
(2) After the reaction is finished, transferring the solution after the reaction into a single-neck flask, steaming out ethanol solution at 60 ℃ in a rotary way, and drying for 12 hours at 50 ℃ in a vacuum drying oven;
(3) Sequentially adding 5mL of epichlorohydrin and 0.0451g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the sulfur dioxide pressure is 0.2MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 90 ℃, and the reaction time is 9h; dissolving the obtained product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 3 times, placing the washed precipitate in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and epoxy compound, wherein the conversion rate of epichlorohydrin is 90%, and the selectivity of the polysulfite is 60%.
(4) Sequentially adding 5mL of epichlorohydrin and 0.0451g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 80 ℃, the carbon dioxide pressure is 2MPa, and the reaction time is 20 hours; the cycloaddition product cyclic carbonate of carbon dioxide and epoxy compound is obtained after cooling, the product yield is 83%, and the selectivity can reach 99%.
Example 6:
(1) 8.34mL of acetylacetone and 75mL of absolute ethyl alcohol are sequentially added into a 50mL three-neck flask, 4.89g of 2, 3-diaminotoluene is added, and the three-neck flask is placed in an oil bath kettle for heating reflux reaction for 20h at 65 ℃;
(2) After the reaction is finished, transferring the solution after the reaction into a single-neck flask, steaming out ethanol solution at 60 ℃ in a rotary way, and drying for 12 hours at 50 ℃ in a vacuum drying oven;
(3) Sequentially adding 5mL of 1, 2-epoxybutane and 0.033g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the molar ratio of 500:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 3 times, and then introducing sulfur dioxide with the purity of 99% into the high-pressure reaction kettle, wherein the sulfur dioxide pressure is 0.5MPa; after the air is introduced, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 90 ℃, and the reaction time is 9h; dissolving the obtained product by using dichloromethane, adding methanol for precipitation, filtering to obtain a precipitate, washing the precipitate with methanol for 3 times, placing the washed precipitate in a vacuum drying oven, and vacuum drying at 40 ℃ for 24 hours to obtain the copolymer of sulfur dioxide and epoxy compound, wherein the conversion rate of epichlorohydrin is 87%, and the selectivity of the polysulfite is 60%.
(4) Sequentially adding 5mL of styrene oxide and 0.051g of Pentane type metal-free homogeneous catalyst into a 50mL high-pressure reaction kettle according to the proportion of 250:1, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, repeatedly introducing nitrogen for 2 times, and then introducing carbon dioxide with the purity of 99% into the high-pressure reaction kettle; after the introduction, the inlet valve and the outlet valve are closed, the rotating speed is set to be 280r/min, the temperature is 80 ℃, the carbon dioxide pressure is 2MPa, and the reaction time is 20 hours; the cycloaddition product cyclic carbonate of carbon dioxide and epoxy compound is obtained after cooling, the product yield is 64%, and the selectivity can reach 97%.
Claims (3)
1. The application of a Pentane-type metal-free homogeneous catalyst in catalyzing copolymerization of sulfur dioxide and an epoxy compound is characterized in that: sequentially adding an epoxy compound and a Pentane type metal-free homogeneous catalyst into a high-pressure reaction kettle, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing sulfur dioxide gas with the purity of 99%, reacting for 4-24 hours at 50-90 ℃ under the sulfur dioxide pressure of 0.2MPa, cooling, dissolving a reaction product by adopting methylene dichloride, adding methanol for precipitation, filtering, collecting the precipitate, washing the precipitate with methanol for 3-4 times, and drying to obtain a copolymer of sulfur dioxide and the epoxy compound, namely the poly sulfite;
the Pentane metal-free homogeneous catalyst is prepared by dissolving acetylacetone and organic amine in 60-80 mL of absolute ethyl alcohol, reacting for 12-24 hours at 60-90 ℃, then steaming the reaction product to remove the ethyl alcohol, and drying;
the organic amine is one of tetraethylenepentamine, ethylenediamine, o-phenylenediamine, 1, 8-diaminonaphthalene and 2, 3-diaminotoluene; the molar ratio of the acetylacetone to the organic amine is 2:1-5:1;
the epoxy compound is one of epoxycyclohexane, epoxypropane, 1, 2-epoxybutane and epoxychloropropane.
2. The application of a Pentane-type metal-free homogeneous catalyst in catalyzing an addition reaction of carbon dioxide and an epoxy compound is characterized in that: sequentially adding an epoxy compound and a Pentane metal-free homogeneous catalyst into a high-pressure reaction kettle, then introducing nitrogen with the purity of 99.99% into the high-pressure reaction kettle, replacing the nitrogen with air in the kettle for 2-3 times, introducing carbon dioxide with the purity of 99%, reacting at 70-110 ℃ for 3-7 h under the pressure of 0.5-4 MPa, and cooling to obtain a product after the reaction is finished, namely the cyclic carbonate;
the Pentane metal-free homogeneous catalyst is prepared by dissolving acetylacetone and organic amine in 60-80 mL of absolute ethyl alcohol, reacting for 12-24 hours at 60-90 ℃, then steaming the reaction product to remove the ethyl alcohol, and drying;
the organic amine is one of tetraethylenepentamine, ethylenediamine, o-phenylenediamine, 1, 8-diaminonaphthalene and 2, 3-diaminotoluene; the molar ratio of the acetylacetone to the organic amine is 2:1-5:1; the epoxy compound is one of propylene oxide, styrene oxide and epichlorohydrin.
3. Use according to claim 1 or 2, characterized in that: the molar ratio of the Pentane type metal-free homogeneous catalyst to the epoxy compound is 1:100-1:1000.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356086A (en) * | 2009-03-18 | 2012-02-15 | 泰恩河畔纽卡斯尔大学 | Aluminum complexes and their use in the synthesis of cyclic carbonates |
| CN102580775A (en) * | 2011-12-30 | 2012-07-18 | 河北工业大学 | Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol |
| CN103030557A (en) * | 2013-01-09 | 2013-04-10 | 四川大学 | Method for generating phenylacetate by acetophenone in one step |
| CN107827764A (en) * | 2017-11-27 | 2018-03-23 | 上海应用技术大学 | A kind of preparation method of double β amino ketones or double β amino esters |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102356086A (en) * | 2009-03-18 | 2012-02-15 | 泰恩河畔纽卡斯尔大学 | Aluminum complexes and their use in the synthesis of cyclic carbonates |
| CN102580775A (en) * | 2011-12-30 | 2012-07-18 | 河北工业大学 | Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol |
| CN103030557A (en) * | 2013-01-09 | 2013-04-10 | 四川大学 | Method for generating phenylacetate by acetophenone in one step |
| CN107827764A (en) * | 2017-11-27 | 2018-03-23 | 上海应用技术大学 | A kind of preparation method of double β amino ketones or double β amino esters |
Non-Patent Citations (1)
| Title |
|---|
| "催化剂催化二氧化硫共聚的研究进展";李珍 等;《高分子材料科学与工程》;第36卷(第6期);第184-190页 * |
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