CN107233921B - Method for preparing catalyst by using modified cellulose loaded SalenMX and application - Google Patents
Method for preparing catalyst by using modified cellulose loaded SalenMX and application Download PDFInfo
- Publication number
- CN107233921B CN107233921B CN201710425339.XA CN201710425339A CN107233921B CN 107233921 B CN107233921 B CN 107233921B CN 201710425339 A CN201710425339 A CN 201710425339A CN 107233921 B CN107233921 B CN 107233921B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- modified cellulose
- catalyst
- salenmx
- 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
Images
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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a catalyst by using modified cellulose loaded SalenMX; substituting-OH on the 6 th site of cellulose into-Cl, and substituting-OH on the 2 rd and 3 rd sites with low activity, adding an ethylenediamine or polyene polyamine compound, reacting at 80-100 ℃, adding water to obtain orange precipitate, filtering, washing and drying at room temperature to obtain modified cellulose; adding SalenMX and modified cellulose into dimethyl sulfoxide at the same time, stirring for reaction, filtering to obtain brown precipitate, repeatedly washing with ethanol and water, and drying at room temperature to obtain a supported SalenMX catalyst; the invention relates to a modified cellulose loaded SalenMX, which has good application prospect in the fields of olefin epoxidation, epoxy compound copolymerization and the like, has simple preparation method, mild reaction temperature, higher activity for more than 5 times of repeated utilization rate, renewable carrier, high yield and good selectivity, and is beneficial to the catalytic olefin epoxidation industrial production.
Description
Technical Field
The invention relates to a technology of a thermoplastic and degradable polymer high molecular material supported catalyst, in particular to a method for preparing a catalyst by adopting modified cellulose supported SalenMX and application thereof.
Background
The SalenMX catalyst has high catalytic efficiency,the advantages of narrow molecular weight distribution, easy modification and the like have become the most studied catalysts in recent years. SalenMX can be used for epoxidation of olefins, copolymerization of epoxy compounds and the like, but the SalenMX catalyst is often dissolved in a solvent in the reaction process, is difficult to recycle, and easily generates oxygen bridged dimer mu-oxo-Mn (VI) and the like, so that the catalyst is deactivated. Therefore, researchers have focused on loading salemx on various carriers to achieve heterogenization. The microwave method is adopted to prepare the supported SalenMnCl catalyst by Malaya and the like, low-concentration peroxyacetic acid is used as an oxygen source, and CH3Cl3The yield of the catalyst is 91.6 percent as a solvent [ Maai Hao, Hu Shu Wei, Shaanshao Yun, and the like ] NaY molecular sieve supported metal Salen catalyst is used for catalyzing α -pinene epoxidation [ J]Forest chemical and industry 2014, 34(5):115.]. In addition, there is polyaniline-Salen [ patent No.: CN201410137775.3]polypyrrole-Salen and the like, wherein the loading mechanism of the polypyrrole-Salen and the like is mainly that a carrier provides an electron pair and forms a coordination bond with a central metal of a Salen catalyst; however, the carriers are not reproducible or degradable, and have the problems of certain toxicity, higher cost, low repeated utilization rate and the like, so that the carriers are difficult to industrialize. Therefore, the search for a new green, environment-friendly and renewable vector becomes a research hotspot.
The energy synthesized by global plants through photosynthesis is 40 times of the total energy consumption of human beings. As a big agricultural country, the annual yield of crop straws is higher than 7 hundred million tons in China, but the real utilization rate is only 3 percent. In recent years, the development and utilization of crop straws arouse extensive attention of people, but because the treatment cost of the straws is too high and the technological conversion is not enough, more than 70 percent of the straws are still used as fuel or directly incinerated in the field every year, thus not only destroying the ecological balance, but also causing environmental pollution. The natural plant fiber is the most abundant renewable resource on the earth, is widely existed in plant straws in various forms, and the main component of the natural plant fiber is cellulose. Cellulose can be grafted with a Salen catalyst through a coupling agent to achieve a loading effect, but the problems of high cost, low catalytic effect of the catalyst, less repeated utilization times and the like [ Mohammadinezhad. A, Nasseri MA, Salimi M. Cellulose as an effective support for Mn (Salen) Cl: application for catalytic oxidation of Cellulose to substrates [ J ]. Rsc Advances, 2014, 4 (75): 39870]. Each ring of cellulose macromolecule has three alcoholic hydroxyl groups, wherein the positions of C2 and C3 are secondary alcoholic hydroxyl groups, and the position of C6 is primary alcoholic hydroxyl group, and the existence of the hydroxyl groups can cause cellulose to have reactions such as oxidation, etherification, swelling, graft copolymerization and the like. When these hydroxyl groups are substituted, cellulose compounds having various structures, properties and effects, i.e., modified celluloses, are obtained.
Renewable forest resources in China are rich, and a natural product, namely turpentine, can be used for synthesis of spices, paint solvents, insecticides and the like. In addition to extracting turpentine from turpentine, some methods of extracting pine root and angelica keiskei with organic solvent and dry distilling coniferous wood can also obtain turpentine. Rich in turpentineαEpoxy pinane generated by epoxidation reaction of-pinene is an important intermediate for medicines and spices, and has high application value and economic value.
At present, no technical scheme related to the invention is reported.
Disclosure of Invention
The invention aims to provide a method for preparing a catalyst by using modified cellulose loaded SalenMX, and the performance of the loaded SalenMX catalyst is tested by using α -pinene as a raw material to perform epoxidation.
The invention discloses a method for preparing a catalyst by using modified cellulose loaded SalenMX, which comprises the following steps:
(1) sequentially adding cellulose and DMF into a three-neck flask and uniformly mixing; adding SOCl with the purity of 99.5 percent2Dropwise adding the mixture into a three-neck flask, continuously stirring at 70-100 ℃ for reacting for 2-5 hours, naturally cooling, pouring the product into ice water, stirring to generate a withered yellow precipitate, filtering, washing the precipitate for 3-5 times by using water and ammonia water alternately, and finally washing the precipitate to be neutral by using water; placing the washed precipitate at room temperature, and drying in vacuum for 8-24 h to obtain chlorinated cellulose;
(2) adding the chlorinated cellulose and the DMSO into a three-neck flask simultaneously and uniformly mixing; dropwise adding an ethylenediamine or polyene polyamine compound with the purity of 99% into a three-neck flask, stirring and reacting at 80-100 ℃ for 12-24 h, adding water into the three-neck flask, cooling overnight to obtain an orange precipitate, filtering, washing the precipitate with water and acetone for 4-6 times alternately, and finally washing off the acetone with water; placing the washed precipitate at room temperature, and drying in vacuum for 12-24 h to obtain modified cellulose;
(3) adding modified cellulose and SalenMX into DMSO, stirring at 40-70 ℃ for reaction for 24-36 h, filtering to obtain brown precipitate, washing with water and ethanol for 3-5 times in sequence, and vacuum drying the washed precipitate at room temperature for 12-24 h to obtain the supported SalenMX catalyst.
The cellulose is microcrystalline cellulose and/or nano microcrystalline cellulose, M metal in SalenMX is one of transition metal elements Mn, Co, Cr, Fe and V, and X is one of Cl and O.
Step (1) cellulose and SOCl2The mass ratio is as follows: 1:1 to 1: 3.
The mass ratio of the chlorinated cellulose to the ethylenediamine or polyene polyamine compound in the step (2) is 1: 1-1: 4.
The polyene polyamine compound in the step (2) is diethylenetriamine or triethylene tetramine.
The mass ratio of the modified cellulose to the SalenMX in the step (3) is 1: 1-1: 3.
SalenMX in the process of the invention is prepared by conventional methods, for example in patent application 201410137775.3.
Characterization of the resulting product by Fourier transform Infrared Spectroscopy (FTIR) revealed that-CH was found2-Cl and-CH2-NH-CH2-CH2-NH2Present on the cellulose backbone; x-ray photoelectron spectroscopy (XPS) characterization can find that-M-NH-exists, and the successful loading is proved.
The invention also aims to apply the modified cellulose supported SalenMX catalyst prepared by the method for preparing the catalyst by using the modified cellulose supported SalenMX in α -pinene epoxidation reaction, namely adding α -pinene, acetonitrile, the modified cellulose supported SalenMX catalyst and a cocatalyst into a container, uniformly mixing, and continuously filling O2Reacting for 1-5 h at the reaction temperature of 10-30 ℃ to obtain the epoxy pinane, wherein α -pinene, acetonitrile and the modified cellulose load SalenMX catalystAnd the molar ratio of the cocatalyst is 3-5: 20: 1-3: 0.5-1.
The cocatalyst is isobutyraldehyde or trimethylacetaldehyde.
Compared with the prior art, the invention has the following advantages:
(1) the invention uses SalenMX to load on modified cellulose in a coordination mode for the first time;
(2) the invention adopts the modified cellulose load SalenMX as the catalyst to epoxidize the natural monoterpenes, thereby not only improving the conversion rate, but also improving the selectivity of the product and reducing the isomerization of the product;
(3) the invention adopts the modified cellulose load SalenMX as the catalyst to epoxidize the natural monoterpenes, has the advantages of relatively mild reaction temperature, greatly shortened reaction time, easy operation, good environment, high repeated utilization rate and the like, and is beneficial to catalyzing the industrial production of olefin epoxidation.
Drawings
FIG. 1 is a Fourier transform Infrared Spectroscopy (FTIR) plot of the chlorinated cellulose prepared in example 1;
FIG. 2 is a Fourier transform Infrared Spectroscopy (FTIR) plot of the modified cellulose prepared in example 4;
FIG. 3 is a graph of supported SalenMX Fourier transform infrared spectroscopy (FTIR) prepared in example 6;
FIG. 4 is an X-ray photoelectron spectroscopy (XPS) plot of supported SalenMX prepared in example 5.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1:
(1) adding 100mL of DMF and 5.0004g of microcrystalline cellulose into a 250mL three-neck flask, and uniformly mixing; 5.0011g of SOCl was added dropwise to a three-necked flask2(purity is 99.5%), the reaction temperature is 90 ℃, the reaction is carried out for 2 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, and the withered yellow precipitate is filtered and mixed with waterWashing with ammonia water for 3 times, and washing with water to neutral; placing the washed precipitate at room temperature, and vacuum drying for 8h to obtain 5.5996g of chlorinated cellulose; the resulting product was characterized by Fourier transform Infrared Spectroscopy (FTIR) as shown in FIG. 1, with a visible-CH2-Cl is present on the main chain of the cellulose;
(2) 5.5996g of chlorinated cellulose and 100mL of DMSO are added into a three-neck flask at the same time and mixed uniformly; 5.6007g of ethylenediamine (with the purity of 99%) is added into a three-neck flask drop by drop, after the mixture is continuously stirred and reacts for 12 hours at the temperature of 80 ℃, water is added into the three-neck flask to be cooled overnight, orange-yellow precipitate is obtained, after filtration, the three-neck flask is alternately washed by water and acetone for 4 times, and finally the acetone is washed away by water; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 6.1022g of orange powder, namely modified cellulose;
(3) 6.1022g of modified cellulose and 6.1017g of SalenMnCl are added into DMSO, the mixture is continuously stirred at the temperature of 40 ℃ to react for 36h, a brown precipitate is obtained by filtration, the mixture is alternately washed by water and ethanol for 3 times, and the washed precipitate is placed at room temperature for vacuum drying for 12h to obtain 6.4234g of a supported SalenMnCl catalyst; the catalyst loading was 4.9%;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenMnCl catalyst and a cocatalyst (isobutyraldehyde) are added into a flask according to the molar ratio of 3:20:1:0.5, oxygen is introduced for reaction for 3h, normal hexane is used for extracting and collecting products, and the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 99.8%, and the selectivity is 85.6%.
Example 2:
(1) adding 100mL of mixed solution of LDMF and 3.1384g of nano microcrystalline cellulose into a 250mL three-neck flask, and uniformly mixing; 9.4149g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 100 ℃, the reaction is carried out for 3 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, water and ammonia water are used for washing for 4 times after filtration, and finally the product is washed to be neutral by water; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 3.8293g of chlorinated cellulose;
(2) 3.8293g of chlorinated cellulose and 100mL of DMSO are added into a three-neck flask at the same time and mixed uniformly; 7.6592g of ethylenediamine (with the purity of 99%) is added into a three-neck flask drop by drop, after continuous stirring reaction at 100 ℃ for 18h, water is added into the three-neck flask for cooling overnight to obtain orange precipitate, the orange precipitate is filtered and washed with water and acetone for 3 times, and finally the acetone is washed away with water; placing the washed precipitate at room temperature, and vacuum drying for 24h to obtain 4.4360g of orange powder, namely modified cellulose;
(3) 4.4360g of modified cellulose and 8.8783g of SalenCrCl are added into DMSO and mixed uniformly, after continuous stirring reaction at 50 ℃ for 30h, brown precipitate is obtained by filtration, water and ethanol are used for washing for 4 times in sequence, and the washed precipitate is placed at room temperature for vacuum drying for 24h, so that 4.8217g of supported SalenCrCl catalyst is obtained. The catalyst loading was 8.0%;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenCrCl catalyst and a cocatalyst (trimethylacetaldehyde) are added into a flask according to the molar ratio of 5:20:1:1, oxygen is introduced for reaction for 1h, n-hexane is used for extracting and collecting products, and the conversion rate of α -pinene is 61.2% and the selectivity is 72.91% through Gas Chromatography (GC) (Cr is not high in catalytic conversion rate of epoxidation).
Example 3:
(1) adding 100mL of mixed solution of LDMF and 5.1783g of cellulose (microcrystalline cellulose and nano microcrystalline cellulose =1: 1) into a 250mL three-neck flask, and mixing uniformly; 10.3523g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 70 ℃, the reaction is carried out for 5 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, the precipitate is filtered, washed for 5 times by water and ammonia water, and finally washed to be neutral by water; placing the washed precipitate at room temperature, and vacuum drying for 16h to obtain 5.5734g of chlorinated cellulose;
(2) 5.5734g of chlorinated cellulose and 100mL of DMSO are added into a three-neck flask at the same time and mixed uniformly; 16.7264g of ethylenediamine (with the purity of 99%) is added into a three-neck flask drop by drop, after the reaction is continuously stirred at the temperature of 90 ℃ for 24 hours, water is added into the three-neck flask to be cooled overnight, an orange precipitate is obtained, the orange precipitate is filtered and washed with water and acetone for 6 times, and finally the acetone is washed away with water; placing the washed precipitate at room temperature, and vacuum drying for 24h to obtain 6.3844g of orange powder, namely modified cellulose;
(3) 6.3844g of modified cellulose and 6.3852g of SalenCoCl are added into DMSO, the mixture is continuously stirred at 60 ℃ to react for 36h, a brown precipitate is obtained by filtration, the mixture is sequentially washed by water and ethanol for 5 times, and the washed precipitate is placed at room temperature and dried in vacuum for 24h to obtain 6.7775g of a supported SalenCoCl catalyst. The catalyst loading was 5.9%;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenCoCl catalyst and a cocatalyst are added into a flask according to the molar ratio of 4:20:2:1, oxygen is introduced for reaction for 2 hours, products are extracted and collected, and the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 93.2%, and the selectivity is 86.1%.
Example 4:
(1) 100mL of mixed solution of sodium hydroxide and 3.5273g of microcrystalline cellulose are added into a 250mL three-neck flask; 10.5830g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 80 ℃, the reaction is carried out for 4 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, the precipitate is filtered, washed with water and ammonia water for 4 times, and finally washed with water to be neutral; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 3.9173g of chlorinated cellulose;
(2) 3.9173g of chlorinated cellulose and 100mL of DMSO were added simultaneously to a three-necked flask; 11.7523g of ethylenediamine (with the purity of 99%) is added into a three-neck flask drop by drop, after the reaction is continuously stirred at 90 ℃ for 24 hours, water is added for cooling overnight, an orange precipitate is obtained, the orange precipitate is filtered and washed with water and acetone for 4 times, and finally the acetone is washed away with water; the washed precipitate was dried under vacuum at room temperature for 18h to give 4.6186g of an orange powder, i.e., modified cellulose. The resulting product was characterized by Fourier transform Infrared Spectroscopy (FTIR) as shown in FIG. 2, showing-CH2-NH-CH2-CH2-NH2Present on the cellulose backbone;
(3) 4.6186g of modified cellulose and 9.2371g of SalenCoCl are added into DMSO, and after the mixture is continuously stirred and reacts for 24 hours at the temperature of 70 ℃, brown precipitate is obtained by filtration and is sequentially washed for 3 times by water and ethanol; and (3) placing the washed precipitate at room temperature for vacuum drying for 12h to obtain 4.9609g of supported SalenCoCl catalyst. The catalyst loading was 6.9%;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenCoCl catalyst and a cocatalyst are added into a flask according to the molar ratio of 3:20:3:1, oxygen is introduced for reaction for 3h, products are extracted and collected, the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 98.7%, and the selectivity is 87.1%.
Example 5:
(1) 50mL of mixed solution (MFF) and 1.2831g of nano microcrystalline cellulose are added into a 100mL three-neck flask; 1.2847g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 100 ℃, the reaction is carried out for 3 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, the precipitate is filtered, washed for 5 times by water and ammonia water, and finally washed to be neutral by water; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 1.4277g of chlorinated cellulose;
(2) 1.4277g of chlorinated cellulose and 50mL of DMSO were added simultaneously to a three-necked flask; 4.2836g of ethylenediamine (with the purity of 99%) is added into a three-neck flask drop by drop, the mixture is stirred continuously at 100 ℃ for reaction for 12 hours, water is added for cooling overnight, orange-yellow precipitate is obtained, the mixture is filtered, washed with water and acetone for 5 times, and finally the acetone is washed away with water; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 1.5840g of orange powder, namely modified cellulose;
(3) 1.5840g of modified cellulose and 3.1685g of SalenMnCl are added into DMSO, the mixture is continuously stirred at 70 ℃ to react for 24h, a brown precipitate is obtained by filtration, the mixture is sequentially washed by water and ethanol for 3 times, and the washed precipitate is placed at room temperature to be dried in vacuum for 12h, so that 1.7602g of the supported SalenMnCl catalyst is obtained. The catalyst loading was 9.2%. The results obtained by characterization with X-ray photoelectron spectroscopy (XPS) are shown in FIG. 4, and it can be seen that SalenMnCl is successfully loaded on modified cellulose;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenMnCl catalyst and a cocatalyst are added into a flask according to the molar ratio of 4:20:2:1, oxygen is introduced for reaction for 4 hours, products are extracted and collected, the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 99.9%, and the selectivity is 87.1%.
Example 6:
(1) 50mL of mixed solution of sodium hydroxide and 1.0008g of cellulose are added into a 100mL three-neck flask; 2.0010g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 100 ℃, the reaction is carried out for 2 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, the precipitate is filtered, washed for 3 times by water and ammonia water, and finally washed to be neutral by water; placing the washed precipitate at room temperature, and vacuum drying for 18h to obtain 1.1275g of chlorinated cellulose;
(2) 1.1275g of chlorinated cellulose and 50mL of DMSO were added simultaneously to a three-necked flask; adding 2.2559g of diethylenetriamine into a three-neck flask drop by drop, continuously stirring at 100 ℃ for reaction for 12h, adding water, cooling overnight to obtain an orange precipitate, filtering, washing with water and acetone for 5 times, and finally washing away the acetone with water; placing the washed precipitate at room temperature, and vacuum drying for 18h to obtain 1.4021g of orange powder, namely modified cellulose;
(3) 1.4021g of modified cellulose and 1.4021g of SalenMnCl are added into DMSO, the mixture is continuously stirred at 50 ℃ to react for 32h, a brown precipitate is obtained by filtration, the mixture is sequentially washed by water and ethanol for 4 times, and the washed precipitate is placed at room temperature for vacuum drying for 18h to obtain 1.5172g of the supported SalenMnCl catalyst. The catalyst loading was 4.9%. The product obtained was characterized by Fourier transform Infrared Spectroscopy (FTIR) and is shown in FIG. 3, showing that Mn-N is present in the main chain of the cellulose;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenMnCl catalyst and a cocatalyst are added into a flask according to the molar ratio of 4:20:2:1, oxygen is introduced for reaction for 5 hours, products are extracted and collected, and the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 99.9%, and the selectivity is 79.7%.
Example 7:
(1) 50mL of mixed solution of sodium hydroxide and 1.5580g of cellulose are added into a 100mL three-neck flask; 4.6738g of SOCl was added dropwise to a three-necked flask2(purity is 99.5 percent) and the reaction temperature is 90 ℃, the mixture is continuously stirred and reacted for 5 hours, then is naturally cooled and cooled, and the product is poured into ice water and stirredObtaining a withered yellow precipitate, filtering, washing with water and ammonia water for 3 times, and finally washing with water to be neutral; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 5.1337g of chlorinated cellulose;
(2) 5.1337g of chlorinated cellulose and 50mL of DMSO were added simultaneously to a three-necked flask; adding 20.5349g of ethylenediamine into a three-neck flask dropwise, continuously stirring at 90 ℃ for reaction for 12h, adding water, cooling overnight to obtain an orange precipitate, filtering, washing with water and acetone for 3 times, and finally washing with water to remove acetone; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 5.5849g of orange powder, namely modified cellulose;
(3) 5.5849g of modified cellulose and 11.1697g of SalenMnCl are added into DMSO, the mixture is continuously stirred at 50 ℃ to react for 24 hours, a brown precipitate is obtained by filtration, the mixture is sequentially washed by water and ethanol for 5 times, and the washed precipitate is placed at room temperature for vacuum drying for 18 hours, so that 6.0904g of the supported SalenMnCl catalyst is obtained. The catalyst loading was 8.3%;
(4) α -pinene, acetonitrile, a modified cellulose loaded SalenMX catalyst and a cocatalyst are added into a flask according to the molar ratio of 4:20:3:0.5, oxygen is introduced for reaction for 2 hours, products are extracted and collected, and the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 83.3%, and the selectivity is 80.5%.
Example 8:
(1) 50mL of mixed solution of sodium hydroxide and 1.5330g of cellulose are added into a 100mL three-neck flask; 1.5355g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 80 ℃, the reaction is carried out for 3 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, the precipitate is filtered, washed for 3 times by water and ammonia water, and finally washed to be neutral by water; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 1.7228g of chlorinated cellulose;
(2) 1.7228g of chlorinated cellulose and 50mL of DMSO were added simultaneously to a three-necked flask; 1.7472g of ethylenediamine is dropwise added into a three-neck flask, continuously stirred at 90 ℃ for reaction for 18h, water is added for cooling overnight to obtain orange-yellow precipitate, the orange-yellow precipitate is filtered and washed with water and acetone for 4 times, and finally the acetone is washed away with water; placing the washed precipitate at room temperature, and vacuum drying for 18h to obtain 1.8037g of orange powder, namely modified cellulose;
(3) 1.8037g of modified cellulose and 5.4109g of SalenMnO are added into DMSO, the mixture is continuously stirred and reacted for 24 hours at the temperature of 60 ℃, a brown precipitate is obtained by filtration, the mixture is sequentially washed for 4 times by water and ethanol, and the washed precipitate is placed at room temperature and dried for 24 hours in vacuum, so that 1.9026g of a supported SalenMnO catalyst is obtained; the catalyst loading was 5.3%;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenMnO catalyst and a cocatalyst are added into a flask according to the molar ratio of 5:20:2:1, oxygen is introduced for reaction for 1h, products are extracted and collected, and the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 70.4%, and the selectivity is 72.2%.
Example 9:
(1) 50mL of mixed solution of sodium hydroxide and 1.5330g of microcrystalline cellulose are added into a 100mL three-neck flask; 1.5355g of SOCl was added dropwise to a three-necked flask2(the purity is 99.5%), the reaction temperature is 80 ℃, the reaction is carried out for 3 hours under continuous stirring, the mixture is naturally cooled, the product is poured into ice water and stirred to obtain withered yellow precipitate, water and ammonia water are used for washing for 3 times after filtration, and finally the product is washed to be neutral by water; placing the washed precipitate at room temperature, and vacuum drying for 12h to obtain 1.7228g of chlorinated cellulose;
(2) 1.7228g of chlorinated cellulose and 50mL of DMSO were added simultaneously to a three-necked flask; adding 1.7472g of triethylene tetramine into a three-neck flask drop by drop, continuously stirring at 90 ℃ for reacting for 18h, adding water, cooling overnight to obtain orange precipitate, filtering, washing with water and acetone for 4 times, and finally washing with water to remove acetone; placing the washed precipitate at room temperature, and vacuum drying for 18h to obtain 2.2148g of orange powder, namely modified cellulose;
(3) 2.2148g of modified cellulose and 6.6445g of SalenFeO are added into DMSO, the mixture is continuously stirred at 60 ℃ to react for 24 hours, a brown precipitate is obtained by filtration, the mixture is sequentially washed by water and ethanol for 4 times, and the washed precipitate is placed at room temperature for vacuum drying for 24 hours, so that 2.3363g of a supported SalenFeO catalyst is obtained; the catalyst loading was 5.2%;
(4) α -pinene, acetonitrile, a modified cellulose supported SalenFeO catalyst and a cocatalyst are added into a flask according to the molar ratio of 5:20:2:1, oxygen is introduced for reaction for 1h, products are extracted and collected, and the conversion rate of α -pinene obtained by Gas Chromatography (GC) is 70.4%, and the selectivity is 72.2%.
Example 10. the process for the preparation of a modified cellulose supported SalenMnCl catalyst is the same as in example 3 except that the supported catalyst is recycled a second time and α -pinene is added in the same proportion for epoxidation, the conversion of α -pinene is 94.1% by gas chromatography analysis and the selectivity is 80.3%, the supported catalyst is recycled a third time and α -pinene is added in the same proportion for epoxidation, the conversion of α -pinene is 90.7% by gas chromatography analysis and the selectivity is 79.8%.
Example 11 a modified cellulose supported salenmcl catalyst was prepared as in example 5, except that the supported catalyst was recycled a second time, α -pinene was added in the same ratio for epoxidation, the conversion of α -pinene was 95.0%, the selectivity was 81.1%, the supported catalyst was recycled a third time, α -pinene was added in the same ratio for epoxidation, the conversion of α -pinene was 92.2%, the selectivity was 80.6%, the fourth time was recycled, the conversion of α -pinene was added in the same ratio for epoxidation, the conversion of α -pinene was 90.1%, the selectivity was 77.6%, the fifth time was recycled, the conversion of α -pinene was added in the same ratio for epoxidation, and the conversion of α -pinene was 82.1%, and the selectivity was 73.2%.
Example 12. the method of preparing a modified cellulose supported SalenCoCl catalyst is the same as example 4 except that the supported catalyst is recycled for the second time, α -pinene is added according to the same ratio for epoxidation, the conversion of α -pinene is 92.1%, the selectivity is 86.3%, the supported catalyst is recycled for the third time, α -pinene is added according to the same ratio for epoxidation, the conversion of α -pinene is 90.5%, the selectivity is 83.7%, the fourth time is recycled, α -pinene is added according to the same ratio for epoxidation, the conversion of α -pinene is 90.1%, the selectivity is 80.6%, the fifth time is recycled, the para- α -pinene is added according to the same ratio for epoxidation, and the conversion of α -pinene is 86.3% and the selectivity is 78.1%.
Claims (7)
1. A method for preparing a catalyst by using modified cellulose loaded SalenMX is characterized by comprising the following steps:
(1) sequentially adding cellulose and DMF into a three-neck flask and uniformly mixing; adding SOCl with the purity of 99.5 percent2Dropwise adding the mixture into a three-neck flask, continuously stirring at 70-100 ℃ for reacting for 2-5 hours, naturally cooling, pouring the product into ice water, stirring to generate a precipitate, filtering, washing the precipitate for 3-5 times by using water and ammonia water alternately, and washing the precipitate to be neutral by using water; placing the washed precipitate at room temperature, and drying in vacuum for 8-24 h to obtain chlorinated cellulose;
(2) adding the chlorinated cellulose and the DMSO into a three-neck flask simultaneously and uniformly mixing; dropwise adding an ethylenediamine or polyene polyamine compound with the purity of 99% into a three-neck flask, stirring and reacting at the temperature of 80-100 ℃ for 12-24 hours, adding water into the three-neck flask, cooling overnight to obtain a precipitate, filtering, washing the precipitate with water and acetone for 4-6 times alternately, and finally washing the acetone with water; placing the washed precipitate at room temperature, and drying in vacuum for 12-24 h to obtain modified cellulose;
(3) adding modified cellulose and SalenMX into DMSO, uniformly mixing, stirring at 40-70 ℃ for 24-36 h for reaction, filtering to obtain a precipitate, alternately washing with water and ethanol for 3-5 times, and vacuum drying the washed precipitate at room temperature for 12-24 h to obtain a supported SalenMX catalyst;
m metal in SalenMX is one of transition metal elements Mn, Co, Cr, Fe and V, and X is one of Cl and O;
the polyene polyamine compound is diethylenetriamine or triethylene tetramine.
2. The process for the preparation of a catalyst supporting salemx in a modified cellulose according to claim 1, wherein: the cellulose is microcrystalline cellulose and/or nano microcrystalline cellulose.
3. The process for the preparation of a catalyst supporting salemx in a modified cellulose according to claim 2, wherein: step (1) cellulose and SOCl2The mass ratio is 1: 1-1: 3.
4. The process for the preparation of a catalyst supporting salemx in a modified cellulose according to claim 1, wherein: the mass ratio of the chlorinated cellulose to the ethylenediamine or polyene polyamine compound in the step (2) is 1: 1-1: 4.
5. The process for the preparation of a catalyst supporting salemx in a modified cellulose according to claim 1, wherein: the mass ratio of the modified cellulose to the SalenMX in the step (3) is 1: 1-1: 3.
6. The use of the modified cellulose supported SalenMX catalyst prepared by the method for preparing a catalyst by using the modified cellulose supported SalenMX catalyst of any one of claims 1-5 in the epoxidation of α -pinene, wherein α -pinene, acetonitrile, the modified cellulose supported SalenMX catalyst and the cocatalyst are added into a container, mixed uniformly, and continuously filled with O2And reacting for 1-5 h at the reaction temperature of 10-30 ℃ to obtain the epoxy pinane, wherein the molar ratio of α -pinene, acetonitrile, the modified cellulose loaded SalenMX catalyst to the cocatalyst is 3-5: 20: 1-3: 0.5-1.
7. Use according to claim 6, characterized in that: the cocatalyst is isobutyraldehyde or trimethylacetaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710425339.XA CN107233921B (en) | 2017-06-08 | 2017-06-08 | Method for preparing catalyst by using modified cellulose loaded SalenMX and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710425339.XA CN107233921B (en) | 2017-06-08 | 2017-06-08 | Method for preparing catalyst by using modified cellulose loaded SalenMX and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107233921A CN107233921A (en) | 2017-10-10 |
| CN107233921B true CN107233921B (en) | 2020-04-07 |
Family
ID=59986214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710425339.XA Active CN107233921B (en) | 2017-06-08 | 2017-06-08 | Method for preparing catalyst by using modified cellulose loaded SalenMX and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107233921B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097314B (en) * | 2017-11-15 | 2020-11-17 | 昆明理工大学 | Preparation method and application of dialdehyde cellulose SalenMX catalyst |
| CN108586623B (en) * | 2018-03-23 | 2020-08-25 | 昆明理工大学 | Cellulose-based Schiff base catalyst and preparation method and application thereof |
| CN113751069A (en) * | 2021-09-27 | 2021-12-07 | 吉首大学 | Cellulose-loaded nano-silver composite material, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07145157A (en) * | 1993-11-24 | 1995-06-06 | Sumitomo Chem Co Ltd | Production of optically active epoxide |
| CN103934029A (en) * | 2014-04-08 | 2014-07-23 | 昆明理工大学 | Polyaniline derivative-loaded salen catalyst as well as preparation method and application of catalyst |
| CN104030975A (en) * | 2014-06-25 | 2014-09-10 | 福州大学 | Mn(III)-Salen catalyst as well as preparation method and application thereof |
| CN105013532A (en) * | 2015-07-09 | 2015-11-04 | 华南理工大学 | Nitrogenous ligand hemicelluloses-palladium catalyst as well as preparation method and application thereof |
-
2017
- 2017-06-08 CN CN201710425339.XA patent/CN107233921B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07145157A (en) * | 1993-11-24 | 1995-06-06 | Sumitomo Chem Co Ltd | Production of optically active epoxide |
| CN103934029A (en) * | 2014-04-08 | 2014-07-23 | 昆明理工大学 | Polyaniline derivative-loaded salen catalyst as well as preparation method and application of catalyst |
| CN104030975A (en) * | 2014-06-25 | 2014-09-10 | 福州大学 | Mn(III)-Salen catalyst as well as preparation method and application thereof |
| CN105013532A (en) * | 2015-07-09 | 2015-11-04 | 华南理工大学 | Nitrogenous ligand hemicelluloses-palladium catalyst as well as preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| "Enantioselective Epoxidation of Unfunctionalized Olefins with Molecular Oxygen and Aldehyde Catalyzed by Optically Active Manganese(III) Complexes";Yamada Tohru et al;《Chemistry Letters》;19921231;第21卷(第11期);第2231–2234页 * |
| "salen-Mn配合物催化空气环氧化烯烃反应";刘艳华等;《石油化工》;20041231;第33卷(第9期);第816–819页 * |
| "Synthesis and characterization of novel chiral sulfonato–salen–manganese(III) complex in a zinc–aluminium LDH host";Samiran Bhattacharjee et al;《Chemical Communication》;20040204;第554–555页 * |
| "纤维素二乙烯三胺负载钯配合物的制备及对Heck反应的催化性能";许英等;《高分子学报》;20100331(第3期);前言和第1.2节 * |
| "纳米纤维素固载Salen催化剂的合成及催化性能研究";范吉理等;《第九届全国环境催化与环境材料学术会议——助力两型社会快速发展的环境催化与环境材料会议论文集（2015）》;20151130;第187页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107233921A (en) | 2017-10-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107233921B (en) | Method for preparing catalyst by using modified cellulose loaded SalenMX and application | |
| CN102827312B (en) | Ethylidene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof | |
| CN107442177B (en) | Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural | |
| CN110013877B (en) | Schiff base ligand covalent grafting carbon nanotube loaded late transition metal olefin polymerization catalyst and preparation method thereof | |
| CN105949129A (en) | Imidazolium bromide ionic liquid containing amine groups and preparation method and application of ionic liquid | |
| CN108586623B (en) | Cellulose-based Schiff base catalyst and preparation method and application thereof | |
| CN106631762A (en) | Method for preparing pyrovinic acid through catalysis of itaconic acid for hydrogenation by ruthenium carbon catalyst after carbon thermal reduction | |
| CN108239050A (en) | Biomass saccharide compound is converted into the method for 5 hydroxymethyl furfural using solid acid as catalyst | |
| CN113117747A (en) | Interfacial ionic liquid supported catalyst for synthesizing cyclic carbonate from carbon dioxide | |
| CN100545167C (en) | The Mn catalyst of oxine derivative and the application in alkene epoxidation thereof | |
| Altava et al. | Polymerisation vs. grafting in the preparation of polymer-supported aluminium catalysts for the Diels-Alder reaction: The role of the polymeric backbone | |
| CN109438153B (en) | Method for preparing 2, 6-dimethyl-2-heptene through citronellal selective decarbonylation reaction | |
| CN101157028A (en) | Platinum carbon nanometer tube catalyzer for synthesizing citronellal | |
| CN108097314B (en) | Preparation method and application of dialdehyde cellulose SalenMX catalyst | |
| CN114436809B (en) | Method for preparing diethyl maleate by carrying out depolymerization on lignin under catalysis of iron oxide loaded by USY molecular sieve | |
| CN110773228B (en) | Preparation method of catalyst and application of catalyst in preparation of beta-isophorone | |
| CN109420519B (en) | Synthetic method of hydroquinone monomethyl ether and preparation method of catalyst | |
| CN109956978B (en) | Phenanthrenequinone-based asymmetric alpha-diimine nickel catalyst and preparation method and application thereof | |
| CN105080527A (en) | Composite catalyst and preparation method thereof and lignin depolymerization method | |
| CN112824361A (en) | Method for preparing p-xylene by efficiently catalyzing 4-methyl-3-cyclohexene formaldehyde conversion by nickel-iron bimetallic catalyst | |
| CN114751880B (en) | Synthesis method of maleic anhydride | |
| CN114160194B (en) | Preparation method and application of eutectic solvent for catalyzing alcohol dehydration | |
| CN108636456A (en) | A kind of salen metal complex catalysts and its preparation method and application | |
| JP2022519453A (en) | Process for the production of oxidized wood products | |
| CN103739435B (en) | Method of turpentine heterogeneous preparation of camphene |
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 | ||
| CB03 | Change of inventor or designer information |
Inventor after: Shan Shaoyun Inventor after: Deng Xuefan Inventor after: Jiu Yingju Inventor after: Jia Qingming Inventor after: Su Hongying Inventor before: Jia Qingming Inventor before: Deng Xuefan Inventor before: Jiu Yingju Inventor before: Shan Shaoyun Inventor before: Su Hongying |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |