CN107233921A - The methods and applications that SalenMX prepares catalyst are loaded with modified cellulose - Google Patents
The methods and applications that SalenMX prepares catalyst are loaded with modified cellulose Download PDFInfo
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- CN107233921A CN107233921A CN201710425339.XA CN201710425339A CN107233921A CN 107233921 A CN107233921 A CN 107233921A CN 201710425339 A CN201710425339 A CN 201710425339A CN 107233921 A CN107233921 A CN 107233921A
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- salenmx
- catalyst
- modified cellulose
- cellulose
- water
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 87
- 239000001913 cellulose Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000001556 precipitation Methods 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 44
- 238000003756 stirring Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000768 polyamine Polymers 0.000 claims abstract description 5
- 150000004291 polyenes Chemical class 0.000 claims abstract description 5
- 235000010980 cellulose Nutrition 0.000 claims description 81
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- 238000005660 chlorination reaction Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 238000006735 epoxidation reaction Methods 0.000 claims description 18
- 239000003426 co-catalyst Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 6
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910006124 SOCl2 Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000013081 microcrystal Substances 0.000 claims description 4
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 4
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical group CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 235000004237 Crocus Nutrition 0.000 abstract description 17
- 241000596148 Crocus Species 0.000 abstract description 17
- 239000002244 precipitate Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 5
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002118 epoxides Chemical class 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 15
- 238000004587 chromatography analysis Methods 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 238000004064 recycling Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000005201 scrubbing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 4
- 239000001293 FEMA 3089 Substances 0.000 description 4
- 150000002171 ethylene diamines Chemical class 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 241000675108 Citrus tangerina Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- -1 Monoterpene alkenes Chemical class 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910018648 Mn—N Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
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- 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 method that SalenMX prepares catalyst is loaded with modified cellulose the invention discloses a kind of；The OH activity that the OH of No. 6 positions of cellulose is substituted by Cl, 2, No. 3 positions by this method is relatively low, it will not be substituted, after then addition ethylenediamine or polyamines polyene class compound are reacted at 80 ~ 100 DEG C, add water and obtain crocus precipitation, precipitation obtains modified cellulose through filtering, washing, drying at room temperature；SalenMX and modified cellulose are added in dimethyl sulfoxide (DMSO) simultaneously, after stirring reaction, brown precipitate is filtrated to get, with ethanol, water cyclic washing, drying at room temperature obtains support type SalenMX catalyst；SalenMX is loaded the present invention relates to modified cellulose, there is good application prospect in fields such as catalyzing expoxidation of olefines, the copolymerization of epoxide, its preparation method is simple, reaction temperature is gentle, repeatable utilization rate still has greater activity more than 5 times, and carrier is renewable, yield height, selectivity is good, is conducive to catalyzing expoxidation of olefines industrialized production.
Description
Technical field
It is specifically a kind of use the present invention relates to thermoplasticity and degradable polymer high polymer material supported catalyst technology
Modified cellulose load SalenMX prepares the methods and applications of catalyst.
Background technology
SalenMX catalyst is due to high catalytic efficiency, narrow molecular weight distribution, it is easy to which the advantages of modifying has turned into recent years
Carry out a class catalyst of most study.SalenMX can be used for the epoxidation of olefines, the copolymerization of epoxide etc., but
SalenMX catalyst is often dissolved in solvent during the course of the reaction, it is difficult to recycle, and easily dimerization of the generation with oxygen bridge even
Body μ-oxo-Mn（Ⅵ）Deng causing catalyst inactivation.Therefore, researcher start to study emphatically SalenMX is carried on it is various
On carrier, to realize heterogeneousization.Ma Aihua etc. prepares support type SalenMnCl catalyst using microwave method, uses low concentration mistake
Fluoroacetic acid is used as oxygen source, CH3Cl3For solvent, [Ma Aihua, Hu Tingwei, Shan continue cloud yield, wait NaY molecules up to 91.6%
Sieve carried metal Salen catalyst australene epoxidation [J] chemistry of forest product and industry, 2014,34 (5):
115.].In addition, the also polyaniline-Salen [patent No.s：CN201410137775.3], polypyrrole-Salen etc., it is born
Carrier aircraft reason is mainly carrier and provides electronics pair, with Salen catalyst centers metal formation coordinate bond；But above-mentioned carrier can not be again
Raw or degraded, with certain toxicity, cost is higher, the problems such as recycling rate of waterused is not high, makes it difficult to industrialization.So, seek
A kind of reproducible carrier of new green environment protection is looked for turn into a study hotspot.
The energy that global plant synthesizes through photosynthesis is 40 times of mankind's total energy consumption.China is big as agricultural
State, the annual production of agricultural crop straw is higher than 700,000,000 tons, but true utilization rate is only 3%.The exploitation of agricultural crop straw in recent years
Cause the extensive attention of people, but be due to stalk processing cost it is too high, scientific and technological conversion dynamics not enough, have more than every year
70% stalk is still used as fuel or directly burned in field, not only destroys the ecological balance, and cause environmental pollution.
Natural plant fibre is renewable resource most abundant on the earth, and it is widely present in straw in a variety of forms, and it is led
It is cellulose to want composition.Cellulose can be grafted by coupling agent and Salen catalyst, reach load effect, but exist cost compared with
Height, catalyst effect is not high, the problems such as recycling number of times is less [Mohammadinezhad. A, Nasseri M
A, Salimi M. Cellulose as an efficient support for Mn (salen)Cl:application
for catalytic oxidation of sulfides to sulfoxides[J]. Rsc Advances, 2014, 4
(75)：39870].It is secondary hydroxyl group to be respectively provided with each basic ring of cellulose macromolecule on three alcoholic extract hydroxyl groups, C2, C3 position,
On C6 positions is primary hydroxyl group, and the presence of these hydroxyls can make cellulose occur oxidation, etherificate, swollen, graft copolymerization etc.
Reaction.When these hydroxyls are substituted, as the various properities cellulosic cpd different with effect, i.e. modified cellulose.
The renewable forest resources of China is enriched, wherein synthesis of the natural products-turpentine oil available for spices, paint solvent,
Agrochemical.Except extracting turpentine oil from rosin, with pine stump pine torch organic solvent soaking extraction, the needle dry distillation of wood some
Method can also obtain turpentine oil.It is rich in turpentine oilα- firpene carries out the epoxypinane of epoxidation reaction generation, is a class weight
Medicine, the fragrance intermediates wanted, application value and economic value are higher.
At present, the report of technical scheme related to the present invention is had no.
The content of the invention
It is an object of the invention to provide a kind of method for preparing catalyst with modified cellulose load SalenMX, and with
Australene is that raw material carries out the performance that epoxidation carrys out proof load type SalenMX catalyst.
The present invention loads the method that SalenMX prepares catalyst with modified cellulose, comprises the following steps that：
（1）Cellulose, DMF are added sequentially to mix in three-necked flask；By the SOCl that purity is 99.5%2It is added dropwise to three mouthfuls of burnings
In bottle, continue at 70 ~ 100 DEG C after 2 ~ 5h of stirring reaction, natural cooling cooling, it is withered and yellow that product is poured into stirring generation in frozen water
Color is precipitated, after filtering, precipitation water and ammoniacal liquor alternately washing 3 ~ 5 times, is finally washed with water to neutrality；Precipitation after washing is placed in
8 ~ 24h is dried in vacuo at room temperature, that is, obtains chlorination；
（2）Chlorination and DMSO are added in three-necked flask simultaneously and mixed；Purity is more for 99% ethylenediamine or polyenoid
Aminated compounds is added dropwise in three-necked flask, at 80 ~ 100 DEG C after 12 ~ 24h of stirring reaction, is added water in three-necked flask
Cool overnight, obtains crocus precipitation, crosses alternately washing 4 ~ 6 times of filter cake water and acetone, acetone is finally washed with water；Will
Precipitation after washing is placed in 12 ~ 24h of vacuum drying at room temperature, obtains modified cellulose；
（3）Modified cellulose and SalenMX are added in DMSO, at 40 ~ 70 DEG C after 24 ~ 36h of stirring reaction, palm fibre is filtrated to get
Color is precipitated, and is washed successively 3 ~ 5 times with water and ethanol, and the precipitation after washing is placed in into 12 ~ 24h of vacuum drying at room temperature, that is, obtained
Support type SalenMX catalyst.
The cellulose is that the M metals in microcrystalline cellulose and/or nano micro crystal cellulose, SalenMX are transition metal
One kind in element M n, Co, Cr, Fe, V, X is one kind in Cl, O.
Step（1）Cellulose and SOCl2Mass ratio is：1:1~1:3.
Step（2）Chlorination is 1 with ethylenediamine or the mass ratio of polyamines polyene class compound:1~1:4.
Step（2）Polyamines polyene class compound is diethylenetriamine or triethylene tetramine.
Step（3）Modified cellulose and SalenMX mass ratio 1:1~1:3.
SalenMX is made with reference to conventional method in the inventive method, such as method in patent application 201410137775.3
It is made.
Use fourier transform infrared spectroscopy（FTIR）Characterize products obtained therefrom, it is possible to find-CH2- Cl and-CH2-NH-CH2-
CH2-NH2In the presence of in cellulosic backbone；X-ray photoelectron power spectrum（XPS）Sign can find that-M-NH- is present, it was demonstrated that load into
Work(.
The present invention is another object is that above-mentioned prepared with modified cellulose load SalenMX is changed made from the method for catalyst
Property cellulose load SalenMX catalyst apply in australene epoxidation reaction, i.e., by australene, acetonitrile, modified cellulose
Load SalenMX catalyst, co-catalyst are added in container and mixed, and are persistently filled with O2, reaction temperature is at 10 ~ 30 DEG C, reaction 1
~ 5h obtains epoxypinane, wherein australene, acetonitrile, modified cellulose load SalenMX catalyst, the mol ratio of co-catalyst
For 3 ~ 5:20:1~3:0.5~1.
The co-catalyst is isobutylaldehyde or trimethyl-acetaldehyde.
Compared with present technology, the invention has the advantages that：
（1）The present invention is loaded on modified cellulose with SalenMX in the way of being coordinated first；
（2）The present invention, as catalyst, epoxidation is carried out to Monoterpene alkenes using modified cellulose support type SalenMX,
Conversion ratio is not only increased, and improves the selectivity of product, the isomerization of product is reduced；
（3）The present invention, as catalyst, epoxidation is carried out to Monoterpene alkenes using modified cellulose support type SalenMX,
Have reaction temperature relatively mild, greatly shorten the reaction time, operation easily, environment it is good, the advantages of high recycling rate, have
Help catalyzing expoxidation of olefines industrialized production.
Brief description of the drawings
Fig. 1 is the chlorination fourier transform infrared spectroscopy prepared by embodiment 1（FTIR）Figure；
Fig. 2 is the modified cellulose fourier transform infrared spectroscopy prepared by embodiment 4（FTIR）Figure；
Fig. 3 is the support type SalenMX fourier transform infrared spectroscopies prepared by embodiment 6（FTIR）Figure；
Fig. 4 is the x-ray photoelectron power spectrum of the support type SalenMX prepared by embodiment 5（XPS）Figure.
Embodiment
The present invention is described in further detail below by drawings and examples, but protection scope of the present invention is not limited to
In the content.
Embodiment 1：
（1）100mL DMF and 5.0004g microcrystalline cellulose is added in 250mL three-necked flask to mix；Dripped into three-necked flask
Plus 5.0011g SOCl2（Purity is 99.5%）, reaction temperature is 90 DEG C, is continued after stirring reaction 2h, and natural cooling cooling will
Product is poured into stirred in frozen water after, obtain withered yellow precipitation, after filtering, with alternately washing 3 times of water and ammoniacal liquor, be finally washed with water to
It is neutral；Precipitation after washing is placed in and is dried in vacuo 8h at room temperature, that is, obtains chlorination 5.5996g；Use Fourier transformation
Infrared spectroscopy（FTIR）Characterize products obtained therefrom result and see Fig. 1, it is seen that-CH2- Cl is present on the main chain of cellulose；
（2）5.5996g chlorinations and 100mL DMSO are added in three-necked flask simultaneously and mixed；By 5.6007g second two
Amine（Purity is 99%）It is added dropwise in three-necked flask, continues at 80 DEG C after stirring reaction 12h, add water in three-necked flask
Cool overnight, obtains crocus precipitation, and with alternately washing 4 times of water and acetone after filtering, acetone is finally washed with water；After washing
Precipitation be placed in and be dried in vacuo 12h at room temperature, obtain crocus powder 6.1022g, i.e. modified cellulose；
（3）6.1022g modified celluloses and 6.1017g SalenMnCl are added in DMSO, reaction is continuously stirred at 40 DEG C
After 36h, brown precipitate is filtrated to get, with water and ethanol alternately washing 3 times, the precipitation after washing is placed in and is dried in vacuo at room temperature
12h, that is, obtain support type SalenMnCl catalyst 6.4234g；Catalyst loadings 4.9%；
（4）By australene, acetonitrile, modified cellulose load SalenMnCl catalyst, co-catalyst（Isobutylaldehyde）According to mol ratio
For 3:20:1:0.5 ratio is added in flask, is passed through oxygen reaction 3h, and product is collected with n-hexane extraction；Pass through gas phase color
Analysis of spectrum（GC）The conversion ratio for obtaining australene is 99.8%, and selectivity is 85.6%.
Embodiment 2：
（1）100mLDMF and 3.1384g nano micro crystal celluloses are added in 250mL three-necked flask to mix；To three-necked flask
Middle dropwise addition 9.4149g SOCl2（Purity is 99.5%）, reaction temperature is 100 DEG C, is continued after stirring reaction 3h, natural cooling drop
Temperature, product is poured into after being stirred in frozen water, obtains withered yellow precipitation, is finally used with alternately washing 4 times of water and ammoniacal liquor again after filtering
It is washed to neutrality；Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, that is, obtains chlorination 3.8293g；
（2）3.8293g chlorinations and 100mL DMSO are added in three-necked flask simultaneously and mixed；By 7.6592g second two
Amine（Purity is 99%）It is added dropwise in three-necked flask, continues at 100 DEG C after stirring reaction 18h, add water in three-necked flask
Cool overnight, obtains crocus precipitation, is washed 3 times with water and acetone after filtering, acetone is finally washed with water；Will be heavy after washing
Shallow lake is placed in is dried in vacuo 24h at room temperature, obtains crocus powder 4.4360g, i.e. modified cellulose；
（3）4.4360g modified celluloses and 8.8783g SalenCrCl are added in DMSO and mixed, is continuously stirred at 50 DEG C
React after 30h, be filtrated to get brown precipitate, washed successively 4 times with water and ethanol, the precipitation after washing is placed in vacuum at room temperature
24h is dried, that is, obtains support type SalenCrCl catalyst 4.8217g.Catalyst loadings 8.0%；
（4）By australene, acetonitrile, modified cellulose load SalenCrCl catalyst, co-catalyst（Trimethyl-acetaldehyde）According to rubbing
You are than being 5:20:1:1 is added in flask, is passed through oxygen reaction 1h, and product is collected with n-hexane extraction；Pass through gas-chromatography point
Analysis（GC）The conversion ratio for obtaining australene is 61.2%, and selectivity is 72.91%（Cr is not high for epoxidised catalytic conversion）.
Embodiment 3：
（1）100mLDMF and 5.1783g celluloses are added in 250mL three-necked flask（Microcrystalline cellulose and nano microcrystalline are fine
Dimension element=1:1）Mix；10.3523g SOCl are added dropwise into three-necked flask2（Purity is 99.5%）, reaction temperature is 70 DEG C, is continued
After stirring reaction 5h, natural cooling cooling pours into product after being stirred in frozen water, obtains withered yellow precipitation, after filtering, with water and
Ammonia scrubbing 5 times, is finally washed with water to neutrality；Precipitation after washing is placed in and is dried in vacuo 16h at room temperature, that is, obtains chloro fine
Tie up element 5.5734g；
（2）5.5734g chlorinations and 100mL DMSO are added in three-necked flask simultaneously and mixed；By 16.7264g second two
Amine（Purity is 99%）It is added dropwise in three-necked flask, continues at 90 DEG C after stirring reaction 24h, add water in three-necked flask
Cool overnight, obtains crocus precipitation, is washed 6 times with water and acetone after filtering, acetone is finally washed with water；Will be heavy after washing
Shallow lake is placed in is dried in vacuo 24h at room temperature, obtains crocus powder 6.3844g, i.e. modified cellulose；
（3）6.3844g modified celluloses and 6.3852g SalenCoCl are added in DMSO, reaction is continuously stirred at 60 DEG C
After 36h, brown precipitate is filtrated to get, is washed successively 5 times with water and ethanol, the precipitation after washing is placed in and is dried in vacuo at room temperature
24h, that is, obtain support type SalenCoCl catalyst 6.7775g.Catalyst loadings 5.9%；
（4）It is 4 that australene, acetonitrile, modified cellulose are loaded into SalenCoCl catalyst, co-catalyst according to mol ratio:20:
2:1 is added in flask, is passed through oxygen reaction 2h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain australene
Conversion ratio is 93.2%, and selectivity is 86.1%.
Embodiment 4：
（1）100mLDMF and 3.5273g microcrystalline celluloses are added in 250mL three-necked flask；It is added dropwise into three-necked flask
10.5830gSOCl2（Purity is 99.5%）, reaction temperature is 80 DEG C, is continued after stirring reaction 4h, and natural cooling cooling will be produced
Thing is poured into stirred in frozen water after, obtain withered yellow precipitation, be finally washed with water to neutrality with water and ammonia scrubbing 4 times again after filtering；
Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, that is, obtains chlorination 3.9173g；
（2）3.9173g chlorinations and 100mL DMSO are added in three-necked flask simultaneously；By 11.7523g ethylenediamines
（Purity is 99%）It is added dropwise in three-necked flask, continues at 90 DEG C after stirring reaction 24h, add water cool overnight, obtains tangerine
Yellow mercury oxide, is washed 4 times with water and acetone after filtering, acetone is finally washed with water；Precipitation after washing is placed in true at room temperature
Sky dries 18h, obtains crocus powder 4.6186g, i.e. modified cellulose.Use fourier transform infrared spectroscopy（FTIR）Characterize
Products obtained therefrom result is shown in Fig. 2, it is seen that-CH2-NH-CH2-CH2-NH2In the presence of in cellulosic backbone；
（3）4.6186g modified celluloses and 9.2371g SalenCoCl are added in DMSO, reaction is continuously stirred at 70 DEG C
After 24h, brown precipitate is filtrated to get, is washed successively 3 times with water and ethanol；Precipitation after washing is placed in and is dried in vacuo at room temperature
12h, that is, obtain support type SalenCoCl catalyst 4.9609g.Catalyst loadings 6.9%；
（4）It is 3 that australene, acetonitrile, modified cellulose are loaded into SalenCoCl catalyst, co-catalyst according to mol ratio:20:
3:1 is added in flask, is passed through oxygen reaction 3h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain australene
Conversion ratio is 98.7%, and selectivity is 87.1%.
Embodiment 5：
（1）50mLDMF and 1.2831g nano micro crystal celluloses are added in 100mL three-necked flask；It is added dropwise into three-necked flask
1.2847gSOCl2（Purity is 99.5%）, reaction temperature is 100 DEG C, is continued after stirring reaction 3h, and natural cooling cooling will be produced
Thing is poured into stirred in frozen water after, obtain withered yellow precipitation, be finally washed with water to neutrality with water and ammonia scrubbing 5 times again after filtering；
Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, that is, obtains chlorination 1.4277g；
（2）1.4277g chlorinations and 50mL DMSO are added in three-necked flask simultaneously；By 4.2836g ethylenediamines（It is pure
Spend for 99%）It is added dropwise in three-necked flask, continues at 100 DEG C after stirring reaction 12h, add water cool overnight, obtains orange
Color is precipitated, and is washed 5 times with water and acetone after filtering, acetone is finally washed with water；Precipitation after washing is placed in vacuum at room temperature
12h is dried, crocus powder 1.5840g, i.e. modified cellulose is obtained；
（3）1.5840g modified celluloses and 3.1685g SalenMnCl are added in DMSO, reaction is continuously stirred at 70 DEG C
After 24h, brown precipitate is filtrated to get, is washed successively 3 times with water and ethanol, the precipitation after washing is placed in and is dried in vacuo at room temperature
12h, that is, obtain support type SalenMnCl catalyst 1.7602g.Catalyst loadings 9.2%.Use x-ray photoelectron power spectrum
（XPS）Characterize acquired results and see Fig. 4, it is seen that SalenMnCl is successfully supported on modified cellulose；
（4）It is 4 that australene, acetonitrile, modified cellulose are loaded into SalenMnCl catalyst, co-catalyst according to mol ratio:20:
2:1 is added in flask, is passed through oxygen reaction 4h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain australene
Conversion ratio is 99.9%, and selectivity is 87.1%.
Embodiment 6：
（1）50mLDMF and 1.0008g celluloses are added in 100mL three-necked flask；It is added dropwise into three-necked flask
2.0010gSOCl2（Purity is 99.5%）, reaction temperature is 100 DEG C, is continued after stirring reaction 2h, and natural cooling cooling will be produced
Thing is poured into stirred in frozen water after, obtain withered yellow precipitation, be finally washed with water to neutrality with water and ammonia scrubbing 3 times again after filtering；
Precipitation after washing is placed in and is dried in vacuo 18h at room temperature, that is, obtains chlorination 1.1275g；
（2）1.1275g chlorinations and 50mL DMSO are added in three-necked flask simultaneously；By 2.2559g diethylenetriamines
It is added dropwise in three-necked flask, continues at 100 DEG C after stirring reaction 12h, add water cool overnight, obtains crocus precipitation,
Washed 5 times with water and acetone after filtering, acetone is finally washed with water；Precipitation after washing is placed in and is dried in vacuo 18h at room temperature,
Obtain crocus powder 1.4021g, i.e. modified cellulose；
（3）1.4021g modified celluloses and 1.4021g SalenMnCl are added in DMSO, reaction is continuously stirred at 50 DEG C
After 32h, brown precipitate is filtrated to get, is washed successively 4 times with water and ethanol, the precipitation after washing is placed in and is dried in vacuo at room temperature
18h, that is, obtain support type SalenMnCl catalyst 1.5172g.Catalyst loadings 4.9%.Use Fourier transform infrared spectroscopy
Learn（FTIR）Characterize products obtained therefrom result and see Fig. 3, it is seen that Mn-N is present on the main chain of cellulose；
（4）It is 4 that australene, acetonitrile, modified cellulose are loaded into SalenMnCl catalyst, co-catalyst according to mol ratio:20:
2:1 is added in flask, is passed through oxygen reaction 5h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain australene
Conversion ratio is 99.9%, and selectivity is 79.7%.
Embodiment 7：
（1）50mLDMF and 1.5580g celluloses are added in 100mL three-necked flask；It is added dropwise into three-necked flask
4.6738gSOCl2（Purity is 99.5%）, reaction temperature is 90 DEG C, is continued after stirring reaction 5h, natural cooling cooling, by product
Pour into after being stirred in frozen water, obtain withered yellow precipitation, be finally washed with water to neutrality with water and ammonia scrubbing 3 times again after filtering；Will
Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, that is, obtains chlorination 5.1337g；
（2）5.1337g chlorinations and 50mL DMSO are added in three-necked flask simultaneously；By 20.5349g ethylenediamines by
It is added dropwise into three-necked flask, continues at 90 DEG C after stirring reaction 12h, add water cool overnight, obtains crocus precipitation, filtering
Washed 3 times with water and acetone afterwards, acetone is finally washed with water；Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, is obtained
Crocus powder 5.5849g, i.e. modified cellulose；
（3）5.5849g modified celluloses and 11.1697g SalenMnCl are added in DMSO, reaction is continuously stirred at 50 DEG C
After 24h, brown precipitate is filtrated to get, is washed successively 5 times with water and ethanol, the precipitation after washing is placed in and is dried in vacuo at room temperature
18h, that is, obtain support type SalenMnCl catalyst 6.0904g.Catalyst loadings 8.3%；
（4）It is 4 that australene, acetonitrile, modified cellulose are loaded into SalenMX catalyst, co-catalyst according to mol ratio:20:3:
0.5 is added in flask, is passed through oxygen reaction 2h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain australene
Conversion ratio is 83.3%, and selectivity is 80.5%.
Embodiment 8：
（1）50mLDMF and 1.5330g celluloses are added in 100mL three-necked flask；It is added dropwise into three-necked flask
1.5355gSOCl2（Purity is 99.5%）, reaction temperature is 80 DEG C, is continued after stirring reaction 3h, natural cooling cooling, by product
Pour into after being stirred in frozen water, obtain withered yellow precipitation, be finally washed with water to neutrality with water and ammonia scrubbing 3 times again after filtering；Will
Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, that is, obtains chlorination 1.7228g；
（2）1.7228g chlorinations and 50mL DMSO are added in three-necked flask simultaneously；By 1.7472g ethylenediamines dropwise
Add into three-necked flask, continue at 90 DEG C after stirring reaction 18h, add water cool overnight, crocus precipitation is obtained, after filtering
Washed with water and acetone 4 times, acetone is finally washed with water；Precipitation after washing is placed in and is dried in vacuo 18h at room temperature, tangerine is obtained
Yellow powder 1.8037g, i.e. modified cellulose；
（3）1.8037g modified celluloses and 5.4109g SalenMnO are added in DMSO, reaction is continuously stirred at 60 DEG C
After 24h, brown precipitate is filtrated to get, is washed successively 4 times with water and ethanol, the precipitation after washing is placed in and is dried in vacuo at room temperature
24h, that is, obtain support type SalenMnO catalyst 1.9026g；Catalyst loadings 5.3%；
（4）It is 5 that australene, acetonitrile, modified cellulose are loaded into SalenMnO catalyst, co-catalyst according to mol ratio:20:2:
1 is added in flask, is passed through oxygen reaction 1h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain turning for australene
Rate is 70.4%, and selectivity is 72.2%.
Embodiment 9:
（1）50mLDMF and 1.5330g microcrystalline celluloses are added in 100mL three-necked flask；It is added dropwise into three-necked flask
1.5355gSOCl2（Purity is 99.5%）, reaction temperature is 80 DEG C, is continued after stirring reaction 3h, natural cooling cooling, by product
Pour into after being stirred in frozen water, obtain withered yellow precipitation, be finally washed with water again with alternately washing 3 times of water and ammoniacal liquor into after filtering
Property；Precipitation after washing is placed in and is dried in vacuo 12h at room temperature, that is, obtains chlorination 1.7228g；
（2）1.7228g chlorinations and 50mL DMSO are added in three-necked flask simultaneously；By 1.7472g triethylene tetramines
It is added dropwise in three-necked flask, continues at 90 DEG C after stirring reaction 18h, add water cool overnight, obtains crocus precipitation, mistake
Washed 4 times with water and acetone after filter, acetone is finally washed with water；Precipitation after washing is placed in and is dried in vacuo 18h at room temperature, is obtained
To crocus powder 2.2148g, i.e. modified cellulose；
（3）2.2148g modified celluloses and 6.6445g SalenFeO are added in DMSO, reaction is continuously stirred at 60 DEG C
After 24h, brown precipitate is filtrated to get, is washed successively 4 times with water and ethanol, the precipitation after washing is placed in and is dried in vacuo at room temperature
24h, that is, obtain support type SalenFeO catalyst 2.3363g；Catalyst loadings 5.2%；
（4）It is 5 that australene, acetonitrile, modified cellulose are loaded into SalenFeO catalyst, co-catalyst according to mol ratio:20:2:
1 is added in flask, is passed through oxygen reaction 1h, and product is collected in extraction；Pass through gas chromatographic analysis（GC）Obtain turning for australene
Rate is 70.4%, and selectivity is 72.2%.
Embodiment 10：The method be the same as Example 3 that modified cellulose loads SalenMnCl catalyst is prepared, difference is
Second of recycling of loaded catalyst, and added according to same ratio to australene epoxidation, pass through gas-chromatography point
The conversion ratio that analysis obtains australene is 94.1%.Selectivity is 80.3%.Third time is reused, and is added according to same ratio
To australene epoxidation, the conversion ratio for obtaining australene by gas chromatographic analysis is 90.7%.Selectivity is 79.8%.
Embodiment 11：The method be the same as Example 5 that modified cellulose loads SalenMnCl catalyst is prepared, difference is
Second of recycling of loaded catalyst, and added according to same ratio to australene epoxidation, pass through gas-chromatography point
The conversion ratio that analysis obtains australene is 95.0%.Selectivity is 81.1%.Third time is reused, and is added according to same ratio
To australene epoxidation, the conversion ratio for obtaining australene by gas chromatographic analysis is 92.2%.Selectivity is 80.6%.4th time
Recycling, and added according to same ratio to australene epoxidation, the conversion of australene is obtained by gas chromatographic analysis
Rate is 90.1%, and selectivity is 77.6%.5th recycling, and added according to same ratio to australene epoxidation, lead to
It is 82.1% to cross gas chromatographic analysis and obtain the conversion ratio of australene, and selectivity is 73.2%.
Embodiment 12：The method be the same as Example 4 that modified cellulose loads SalenCoCl catalyst is prepared, difference is
Second of recycling of loaded catalyst, and added according to same ratio to australene epoxidation, pass through gas-chromatography point
The conversion ratio that analysis obtains australene is 92.1%.Selectivity is 86.3%.Third time is reused, and is added according to same ratio
To australene epoxidation, the conversion ratio for obtaining australene by gas chromatographic analysis is 90.5%.Selectivity is 83.7%.4th time
Recycling, and added according to same ratio to australene epoxidation, the conversion of australene is obtained by gas chromatographic analysis
Rate is 90.1%, and selectivity is 80.6%.5th recycling, and added according to same ratio to australene epoxidation, lead to
It is 86.3% to cross gas chromatographic analysis and obtain the conversion ratio of australene, and selectivity is 78.1%.
Claims (8)
1. a kind of load the method that SalenMX prepares catalyst with modified cellulose, it is characterised in that comprises the following steps that：
（1）Cellulose, DMF are added sequentially to mix in three-necked flask；By the SOCl that purity is 99.5%2It is added dropwise to three-necked flask
In, continue at 70 ~ 100 DEG C after 2 ~ 5h of stirring reaction, natural cooling cooling, product is poured into stirring in frozen water produces precipitation,
After filtering, precipitation is washed with water to neutrality after alternately being washed 3 ~ 5 times with water and ammoniacal liquor；Precipitation after washing is placed in vacuum at room temperature
8 ~ 24h is dried, that is, obtains chlorination；
（2）Chlorination and DMSO are added in three-necked flask simultaneously and mixed；Purity is more for 99% ethylenediamine or polyenoid
Aminated compounds is added dropwise in three-necked flask, at 80 ~ 100 DEG C after 12 ~ 24h of stirring reaction, is added water in three-necked flask
Cool overnight, is precipitated, and crosses alternately washing 4 ~ 6 times of filter cake water and acetone, acetone is finally washed with water；After washing
Precipitation be placed at room temperature vacuum drying 12 ~ 24h, obtain modified cellulose；
（3）Modified cellulose and SalenMX are added in DMSO and mixed, at 40 ~ 70 DEG C after 24 ~ 36h of stirring reaction, is filtered
To precipitation, with water and ethanol alternately washing 3 ~ 5 times, the precipitation after washing is placed in 12 ~ 24h of vacuum drying at room temperature, that is, obtained
Support type SalenMX catalyst.
2. according to claim 1 load the method that SalenMX prepares catalyst with modified cellulose, it is characterised in that：
Cellulose is microcrystalline cellulose and/or nano micro crystal cellulose, the M metals in SalenMX are transition metal Mn, Co, Cr,
One kind in Fe, V, X is one kind in Cl, O.
3. according to claim 2 load the method that SalenMX prepares catalyst with modified cellulose, it is characterised in that：
Step（1）Cellulose and SOCl2Mass ratio is 1:1~1:3.
4. according to claim 1 load the method that SalenMX prepares catalyst with modified cellulose, it is characterised in that：
Step（2）Chlorination is 1 with ethylenediamine or the mass ratio of polyamines polyene class compound:1~1:4.
5. according to claim 4 load the method that SalenMX prepares catalyst with modified cellulose, it is characterised in that：
Step（2）Polyamines polyene class compound is diethylenetriamine or triethylene tetramine.
6. according to claim 1 load the method that SalenMX prepares catalyst with modified cellulose, it is characterised in that：
Step（3）Modified cellulose and SalenMX mass ratio 1:1~1:3.
7. being prepared with modified cellulose load SalenMX described in claim any one of 1-6 changes made from the method for catalyst
Property application of the cellulose load SalenMX catalyst in australene epoxidation reaction, it is characterised in that：By australene, acetonitrile,
Modified cellulose load SalenMX catalyst, co-catalyst are added in container and mixed, and are persistently filled with O2, reaction temperature 10 ~
30 DEG C, 1 ~ 5h of reaction obtains epoxypinane, wherein australene, acetonitrile, modified cellulose load SalenMX catalyst, co-catalysis
The mol ratio of agent is 3 ~ 5:20:1~3:0.5~1.
8. apply according to claim 7, it is characterised in that：Co-catalyst is isobutylaldehyde or trimethyl-acetaldehyde.
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