CN110201724A - A kind of hollow microsphere carried heteropoly acid catalyst and its application in preparation high viscosity cellulose acetate propionate - Google Patents
A kind of hollow microsphere carried heteropoly acid catalyst and its application in preparation high viscosity cellulose acetate propionate Download PDFInfo
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- CN110201724A CN110201724A CN201910416150.3A CN201910416150A CN110201724A CN 110201724 A CN110201724 A CN 110201724A CN 201910416150 A CN201910416150 A CN 201910416150A CN 110201724 A CN110201724 A CN 110201724A
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- acid catalyst
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- hollow microsphere
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229920008347 Cellulose acetate propionate Polymers 0.000 title claims abstract description 26
- 239000004005 microsphere Substances 0.000 title claims abstract description 24
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920002678 cellulose Polymers 0.000 claims abstract description 30
- 239000001913 cellulose Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000003377 acid catalyst Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000007524 organic acids Chemical class 0.000 claims description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- -1 bromine alkane Chemical class 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- PKDCQJMRWCHQOH-UHFFFAOYSA-N triethoxysilicon Chemical compound CCO[Si](OCC)OCC PKDCQJMRWCHQOH-UHFFFAOYSA-N 0.000 claims description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical group CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 claims 1
- 229920006218 cellulose propionate Polymers 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 5
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000009972 noncorrosive effect Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002895 organic esters Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 206010016590 Fibrin deposition on lens postoperative Diseases 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
Abstract
The invention discloses a kind of hollow microsphere carried heteropoly acid catalyst and its applications in preparation high viscosity cellulose acetate propionate.The present invention first activates cellulose, then liquid acid catalyst is added to be esterified with hollow microsphere carried heteropoly acid catalyst and acid anhydrides, after esterification, it is recycled and reused by separating hollow microsphere carried heteropoly acid catalyst, then precipitating, washing, drying and other steps obtain ideal degree of substitution, highly viscous cellulose acetate propionate.The present invention uses hollow microsphere carried heteropoly acid catalyst catalytic esterification to synthesize cellulose acetate propionate for the first time.Polyacid is acid strong and non-corrosive in the catalyst, and product can prepare partially substituted cellulose acetate propionate without hydrolysis；Reduce the hydrolysis of cellulose；Constructing for hollow spherical structure solves the problems, such as that catalytic inner cannot be with the more contact of cellulose；Greatly reduce reaction time and sulfuric acid usage amount, the cellulose acetate propionate with high viscosity performance can be prepared.
Description
Technical field
The invention belongs to cellulose esters synthesis technical field, in particular to a kind of hollow microsphere carried heteropoly acid catalyst and
Its application in preparation high viscosity cellulose acetate propionate.
Background technique
Cellulose organic ester is the fiber for reacting generation in the presence of a catalyst with organic acid and acid anhydrides by cellulose
Plain derivative.There are cellulose acetate, cellulose acetate propionate and acetylbutyrylcellulose using more at present.Acetate propionate is fine
Dimension element has the advantages that good gas permeability, thermal stability, water resistance, impact resilience, is widely used in painting, plastics, membrane material,
Petroleum, food, the industries such as textile.
Currently, preparing cellulose organic ester makees catalyst using the concentrated sulfuric acid mostly, using the concentrated sulfuric acid do catalyst exist with
Lower disadvantage (1) concentrated sulfuric acid acidity is very strong, has corrosivity to production equipment, therefore certain time needs replacing equipment, increases life
Produce cost；(2) concentrated sulfuric acid and fibrin reaction process are violent, can degraded cellulose, reduction molecular weight of product and viscosity；Side reaction
It is more, it is easily reduced product stability；(3) after the reaction was completed, operation need to be hydrolyzed to obtain ideal degree of substitution product, and hydrolyze
The ester group hydrolyses of process a large amount of cellulose esters primary carbons position, influence product dissolubility, the process is cumbersome and not easy to control.It is based on
The above sulphuric acid catalysis cellulose esterification disadvantage finds non-corrosive, selectivity height, without hydrolysis operation and repeatable benefit
Solid acid catalyst is the hot spot of current fibre element esterification research.
Although traditional inoganic solids acid catalyst be able to solve catalyst recycle the problem of, cellulose be by
Glucose group at macromolecular polysaccharide, intramolecular and intermolecular there are a large amount of hydrogen bonds, inoganic solids acid catalyst cannot be with fiber
Element comes into full contact with.High molecular polymer is similar to cellulosic structure, has good contact, but catalyst itself with cellulose
Still remain some problems.Such as: although having obtained high-specific surface area macromolecule carrier, it is contemplated that cellulose esterification process
Mainly the reaction of substrate and catalyst surface progress, solid construction make catalytic inner active component and cellulose contact
Difference, the specific surface that catalyst is contacted with substrate is low, and carrier lacks the regulation on pattern.Consider how catalyst amount not
Increase contact of the cellulose with catalyst surface on the basis of change, wherein preparing hollow microsphere material is one to solve the above problems
Item available strategy.
Summary of the invention
In view of the above problems, the present invention provides a kind of hollow microsphere carried heteropoly acid catalyst and its high in preparation
Application in viscosity cellulose acetate propionate.Hollow microsphere carried heteropoly acid catalyst preparation of the invention is simple, wherein passing through
Hybrid inorganic-organic hollow ball made from inorganic material is introduced, inorganic material realizes the Morphological control of catalyst, hollow chou
Constructing for structure solves the problems, such as that catalytic inner active component cannot be with the more contact of cellulose；When greatly reducing reaction simultaneously
Between and sulfuric acid usage amount, polyacid acidity strong and non-corrosive, non-degradable cellulose, after the reaction was completed, catalyst separation be easy,
Recyclable recycling, product is without hydrolysis.Total degree of substitution range 2.4-2.7 of obtained cellulose acetate propionate, acetyl
Base content is 20-30%, propionyl content 10-25%.
Hollow microsphere carried heteropoly acid catalyst of the present invention the preparation method comprises the following steps:
(a) in 330-370K, N after N- [3- (triethoxy silicon substrate) propyl] bis- hydrogen imidazoles of -4,5- being mixed with bromine alkane2It protects
Shield is lower to react 10-30h；After reaction, it is cooled to room temperature, revolving removes volatile component, then is washed with pentane, and revolving is dry
It is dry；
(b) styrene is added to the in the mixed solvent of dehydrated alcohol and deionized water, PVP dissolution, magnetic force is then added
Under stirring and nitrogen protection, it is warming up to 60-90 DEG C, AIBN is added and reacts 10-15h, with dehydrated alcohol centrifuge washing, vacuum is dry
It is dry；
(c) product of step (b) is added to absolute ethanol ultrasonic disperse, it is 0.1-0.5mol/L's that concentration, which is then added,
CTAB solution is stirred at room temperature 0.5-3 hours；PH to 9-10 is adjusted with ammonium hydroxide, TEOS is added and is added after stirring 0.5-1 hours
Product made from step (a), is stirred at room temperature 5-20h, is then transferred to 60-100 DEG C of hydro-thermal reaction 30-50h in reaction kettle, centrifugation
Washing is added to 50-70 DEG C of back flow reaction 3-5h in THF after dry, with ethanol washing product；
(d) in deionized water by the product dispersion of step (c), polyacid being then added, 40-80 DEG C is stirred to react 8-20h,
Deionized water centrifuge washing is dried to obtain hollow microsphere carried heteropoly acid catalyst.
The bromine alkane is 1- bromooctane.
The polyacid is phosphotungstic acid.
By the hollow microsphere carried heteropoly acid catalyst of above-mentioned preparation answering in preparation high viscosity cellulose acetate propionate
With.Concrete operation step are as follows:
(1) cellulose and organic acid mixing, are activated 0.5-5h at room temperature；
(2) cellulose and liquid acid catalyst, hollow microsphere carried heteropoly acid catalyst, organic acid anhydride after being activated
Esterifying agent mixing, reacts 0.5-5 hours at 30-60 DEG C, hollow microsphere carried heteropoly acid catalyst and liquid acid catalyst
Total dosage is the 0.005-5wt% of reaction solution total amount；
(3) reaction solution is separated after the reaction was completed, is repeated after the washing recycling of hollow microsphere carried heteropoly acid catalyst
It utilizes, the water precipitating then measured with 5-10 times, filters, washing is dried to obtain cellulose acetate propionate.
The organic acid includes acetic acid and propionic acid.
The mass ratio of the organic acid and cellulose is 4:1-10:1.
The liquid acid catalyst is sulfuric acid.
The organic acid anhydride esterifying agent is the mixed liquor of acetic anhydride and propionic andydride.
The organic acid anhydride esterifying agent and cellulose mass ratio is 0.5:1-5:1.
Present invention has an advantage that
(1) liquid acid catalyst is substituted with hollow microsphere carried heteropoly acid catalyst, greatly reduces the corrosion to equipment,
The generation for reducing acid waste water, reduces production cost.
(2) gained cellulose acetate propionate eliminates industrial hydrolysing step, and viscosity is high, reaches 320mpas.
(3) after reaction, product is scattered in liquid phase, and catalyst exists in solid form, can by simply separating
Catalyst is recycled, recycling is reached.
(4) solve the problems, such as cannot be with the more contact of cellulose inside solid catalyst for hollow sphere catalyst.
Detailed description of the invention
Fig. 1 is PS/C8-SiO2-PW12Catalyst synthesis processes schematic diagram.
Fig. 2 is PS/C8-SiO2-PW12Catalyst TEM figure.
Fig. 3 is PS/C8-SiO2-PW12Catalyst solid nuclear-magnetism29Si spectrogram.
Fig. 4 is PS/C8-SiO2-PW12Influence of the catalyst circulation number to CAP viscosity and degree of substitution.
Specific embodiment
To make those skilled in the art more fully understand technical solution of the present invention, below with reference to embodiment to the present invention
A kind of application of the hollow microsphere carried heteropoly acid catalyst provided in preparation high viscosity cellulose acetate propionate carries out detailed
Description.
Embodiment 1
Prepare PS/C8-SiO2Catalyst:
(1) by the double hydrogen imidazoles of 25mmol (6.861g) N- [3- (triethoxy silicon substrate) propyl] -4,5- and 75mmol 1- bromine
In 353K, N after octane mixing2The lower reaction of protection is for 24 hours.Reaction terminates, and is cooled to room temperature, and revolving removes volatile component.With n- penta
After alkane washing, revolving is dried to obtain IL-C8；
(2) styrene of 10g is added in 95g dehydrated alcohol and the mixed solution of 5g deionized water.The PVP of 2g is molten
Solution is in the above solution.Magnetic agitation and inflated with nitrogen are warming up to 70 DEG C, and the AIBN of 0.1g is added, and react 12h.Centrifugation obtains white
Color solid, is washed with dehydrated alcohol, 50 DEG C of vacuum drying.；
(3) 68mL dehydrated alcohol ultrasonic disperse 30min is added in the PS for weighing 0.5g, and being added to 50mL concentration is 0.14mol/
It is stirred at room temperature in the CTAB solution of L one hour.PH to 10 is adjusted with the ammonium hydroxide of 25wt%, 2.68mL TEOS is added.After half an hour
The IL-C of 0.05-0.1mol is added8(x=nIL/(nTEOS+nIL)), 10h is stirred at room temperature, it is anti-to be transferred to 80 DEG C of hydro-thermals in reaction kettle
Answer 48h.Centrifugation obtains white products and is washed with water three times, 60 DEG C of dryings.It is added to 60 DEG C of reflux in 200mL THF solution later
It flows back after 4h, obtains PS/C with ethanol washing8-SiO2。
(4) PS/C of 1g8-SiO2It is dispersed in 30mL deionized water, the phosphotungstic acid of 0.06-0.12mol is added, 60 DEG C are stirred
It mixes centrifugation after 12h and is washed with deionized and be dried to obtain PS/C8-SiO2-PW12。
Prepare cellulose acetate propionate:
Cellulose after weighing 2g drying, is added 10g acetic acid and 10g propionic acid mixed liquor, activates 1h at room temperature；It is warming up to
The mixed liquor of 10g acetic anhydride and 10g propionic andydride is added after 40 DEG C, adds 10 μ L sulfuric acid and 25mg PS/C8-SiO2-PW12It urges
Agent is reacted 2 hours at 40 DEG C, centrifugation, PS/C8-SiO2-PW12It is reused after catalyst detergent recycling, adds 5 times
The water precipitating of amount filters, and washs, dry, obtains cellulose acetate propionate.
Obtained total degree of substitution~2.68 of cellulose acetate propionate ester, the viscosity of cellulose acetate propionate are 320mpas.
Comparative example 1
Cellulose after weighing 2g drying, is added 10g acetic acid and 10g propionic acid mixed liquor, activates 1h at room temperature；It is warming up to
The mixed liquor of 10g acetic anhydride and 10g propionic andydride is added after 45 DEG C, adds 10 μ L sulfuric acid, is reacted 2 hours at 40 DEG C, is centrifuged,
The water precipitating of 5 times of amounts is added, is filtered, is washed, it is dry, obtain cellulose acetate propionate.
The obtained total degree of substitution of cellulose acetate propionate ester is 2.92, viscosity 175mpas.
Embodiment 2
Cellulose after weighing 2g drying, is added 10g acetic acid and 10g propionic acid mixed liquor, activates 1h at room temperature；It is warming up to
The mixed liquor of 10g acetic anhydride and 10g propionic andydride is added after 50 DEG C, adds 10 μ L sulfuric acid and 25mg PS/C8-SiO2-PW12It urges
Agent is reacted 2 hours at 50 DEG C, centrifugation, PS/C8-SiO2-PW12It is reused after catalyst detergent recycling, adds 5 times
The water precipitating of amount filters, and washs, dry, obtains cellulose acetate propionate.
Obtained total degree of substitution~2.7 of cellulose acetate propionate ester, the viscosity of cellulose acetate propionate are 280mpas.
Example of the invention is explained in detail above in conjunction with embodiment, but the present invention is not limited to examples detailed above,
All any improvement and modification made for the present invention belong to the protection scope of the claims in the present invention.
Claims (10)
1. a kind of preparation method of hollow microsphere carried heteropoly acid catalyst, which is characterized in that the specific steps of the preparation method
Are as follows:
(a) in 330-370 K, N after N- [3- (triethoxy silicon substrate) propyl] bis- hydrogen imidazoles of -4,5- being mixed with bromine alkane2Under protection
React 10-30h；After reaction, it is cooled to room temperature, revolving removes volatile component, then is washed with pentane, rotates drying；
(b) styrene is added to the in the mixed solvent of dehydrated alcohol and deionized water, PVP dissolution, magnetic agitation is then added
And under nitrogen protection, it is warming up to 60-90 DEG C, AIBN is added and reacts 10-15h, with dehydrated alcohol centrifuge washing, vacuum drying；
(c) product of step (b) is added to absolute ethanol ultrasonic disperse, the CTAB that concentration is 0.1-0.5mol/L is then added
Solution is stirred at room temperature 0.5-3 hours；PH to 9-10 is adjusted with ammonium hydroxide, TEOS is added and step is added after stirring 0.5-1 hours
(a) product made from, is stirred at room temperature 5-20h, is then transferred to 60-100 DEG C of hydro-thermal reaction 30-50h, centrifugation in reaction kettle and washes
It washs, 50-70 DEG C of back flow reaction 3-5h in THF is added to after dry, with ethanol washing product；
(d) in deionized water by the dispersion of the product of step (c), polyacid is then added, 40-80 DEG C is stirred to react 8-20h, go from
Sub- water centrifuge washing, is dried to obtain hollow microsphere carried heteropoly acid catalyst.
2. preparation method according to claim 1, which is characterized in that the bromine alkane is 1- bromooctane.
3. preparation method according to claim 1, which is characterized in that the polyacid is phosphotungstic acid.
4. the hollow microsphere carried heteropoly acid catalyst that the method according to claim 11 is prepared is in preparation high viscosity vinegar
Application in sour cellulose propionate.
5. a kind of preparation method of high viscosity cellulose acetate propionate, which is characterized in that the specific steps of the preparation method are as follows:
(1) cellulose and organic acid mixing, are activated 0.5-5h at room temperature；
(2) cellulose and liquid acid catalyst, hollow microsphere carried heteropoly acid catalyst, organic acid anhydride after being activated are esterified
Agent mixing, reacts 0.5-5 hours, total use of hollow microsphere carried heteropoly acid catalyst and liquid acid catalyst at 30-60 DEG C
Amount is the 0.005-5wt% of reaction solution total amount；
(3) reaction solution is separated after the reaction was completed, is reused after the washing recycling of hollow microsphere carried heteropoly acid catalyst,
Then the water precipitating measured with 5-10 times filters, and washing is dried to obtain cellulose acetate propionate.
6. preparation method according to claim 5, which is characterized in that the organic acid includes acetic acid and propionic acid.
7. preparation method according to claim 5, which is characterized in that the mass ratio of the organic acid and cellulose is 4:
1-10:1。
8. preparation method according to claim 5, which is characterized in that the liquid acid catalyst is sulfuric acid.
9. preparation method according to claim 5, which is characterized in that the organic acid anhydride esterifying agent is acetic anhydride and third
The mixed liquor of acid anhydrides.
10. preparation method according to claim 5, which is characterized in that the organic acid anhydride esterifying agent and cellulose material
Amount is than being 0.5:1-5:1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706396A (en) * | 2014-01-06 | 2014-04-09 | 北京化工大学 | Preparation method of polydivinylbenzene-ionic liquid-polyacid catalysts and application thereof |
| CN104130332A (en) * | 2014-07-16 | 2014-11-05 | 北京化工大学 | Method for catalysing cellulose ester synthesis by using 1-butyl-3-methylimidazolium hydrogen sulphate |
| CN105802662A (en) * | 2016-05-16 | 2016-07-27 | 辽宁大学 | Oxidative desulfurization method implemented through Janus-based acidic catalyst |
| CN109400718A (en) * | 2018-09-28 | 2019-03-01 | 江苏瑞佳新材料有限公司 | A kind of preparation method of cellulose acetate propionate |
| CN109400719A (en) * | 2018-09-28 | 2019-03-01 | 江苏瑞佳新材料有限公司 | The preparation method of cellulose acetate propionate |
-
2019
- 2019-05-20 CN CN201910416150.3A patent/CN110201724B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706396A (en) * | 2014-01-06 | 2014-04-09 | 北京化工大学 | Preparation method of polydivinylbenzene-ionic liquid-polyacid catalysts and application thereof |
| CN104130332A (en) * | 2014-07-16 | 2014-11-05 | 北京化工大学 | Method for catalysing cellulose ester synthesis by using 1-butyl-3-methylimidazolium hydrogen sulphate |
| CN105802662A (en) * | 2016-05-16 | 2016-07-27 | 辽宁大学 | Oxidative desulfurization method implemented through Janus-based acidic catalyst |
| CN109400718A (en) * | 2018-09-28 | 2019-03-01 | 江苏瑞佳新材料有限公司 | A kind of preparation method of cellulose acetate propionate |
| CN109400719A (en) * | 2018-09-28 | 2019-03-01 | 江苏瑞佳新材料有限公司 | The preparation method of cellulose acetate propionate |
Non-Patent Citations (1)
| Title |
|---|
| SAI AN ET AL.: "Self-Organization of Ionic Liquid-Modified Organosilica HollowNanospheres and Heteropolyacids:Efficient Preparationof 5-HMF Under Mild Conditions", 《CHEMCATCHEM》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114367311A (en) * | 2022-01-14 | 2022-04-19 | 北京化工大学 | Method for preparing micron-sized monodisperse polymer microsphere supported heteropolyacid catalyst by suspension polymerization method and application |
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