CN104788292B - A kind of synthetic method of hindered phenol compound antioxidant 330 - Google Patents
A kind of synthetic method of hindered phenol compound antioxidant 330 Download PDFInfo
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- CN104788292B CN104788292B CN201510121181.8A CN201510121181A CN104788292B CN 104788292 B CN104788292 B CN 104788292B CN 201510121181 A CN201510121181 A CN 201510121181A CN 104788292 B CN104788292 B CN 104788292B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000010189 synthetic method Methods 0.000 title claims abstract description 28
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical group FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000003377 acid catalyst Substances 0.000 claims description 20
- 239000002041 carbon nanotube Substances 0.000 claims description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 230000020477 pH reduction Effects 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- OKIIEJOIXGHUKX-UHFFFAOYSA-L Cadmium iodide Inorganic materials [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 8
- 229920002866 paraformaldehyde Polymers 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- PHQFMPNZCIHSPC-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)-2,4,6-trimethylbenzene Chemical compound CC1=C(CCl)C(C)=C(CCl)C(C)=C1CCl PHQFMPNZCIHSPC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- -1 sucking filtration Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 claims description 3
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 11
- 230000003078 antioxidant effect Effects 0.000 abstract description 11
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000011835 investigation Methods 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BFIMMTCNYPIMRN-UHFFFAOYSA-N 1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- BHMKRPFWTKJXKI-UHFFFAOYSA-N 3,5-ditert-butyl-4-(hydroxymethyl)phenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1CO BHMKRPFWTKJXKI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- SPLWDHARILMLDE-UHFFFAOYSA-N cerium;trifluoromethanesulfonic acid Chemical compound [Ce].OS(=O)(=O)C(F)(F)F SPLWDHARILMLDE-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- AXXFVUWEFGKYBC-UHFFFAOYSA-N samarium;trifluoromethanesulfonic acid Chemical compound [Sm].OS(=O)(=O)C(F)(F)F AXXFVUWEFGKYBC-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OGEJCBGPTKTKHE-UHFFFAOYSA-N terbium;trifluoromethanesulfonic acid Chemical compound [Tb].OS(=O)(=O)C(F)(F)F OGEJCBGPTKTKHE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 description 1
- HLRHYHUGSPVOED-UHFFFAOYSA-N trifluoromethanesulfonic acid;ytterbium Chemical compound [Yb].OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F HLRHYHUGSPVOED-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/18—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving halogen atoms of halogenated compounds
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
- B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides the synthetic method of a kind of hindered phenol compound antioxidant 330, described method includes: at ternary complex catalyst and certain concentration in the presence of the diluted hydrochloric acid aqueous solution with consumption, lower formula (I) compound reacts in a solvent with lower formula (II) compound, thus obtain described antioxidant 330
Description
Technical field
The present invention relates to the synthetic method of a kind of antioxidant, relate more particularly to a kind of Hinered phenols antioxidant i.e. antioxidant
The synthetic method of 330, belongs to organic chemical synthesis technical field.
Background technology
Antioxidant is for one of reagent preventing material aging, owing to macromolecular material is producing, storing and use
During oxidative resistance difference and frequently result in the instability of properties of product or be remarkably decreased, thus the use of antioxidant is day by day
Most attention by people.
Up to now, methods have been developed multiple antioxidant, wherein hindered phenol compound such as antioxidant 330 is one
Class purposes antioxidant widely, its entitled 1,3,5-trimethyl-2 of chemistry, 4,6-tri-(3,5-di-t-butyl-4-hydroxyl benzyls
Base) benzene (wherein t-Bu is the tert-butyl group, lower same), its structural formula is as follows:
This antioxidant is developed in nineteen sixty by Shell Co. Ltd of the U.S. and is promoted, be a kind of efficiently, environmental protection, antioxygenic property excellent
Different antioxidant, gram is widely used in the macromolecules such as the thermoplastic polyester such as polyolefin, PET, PBT, polyamide, styrene resin
In material.
Just because of such excellent properties of this antioxidant 330, people have carried out substantial amounts of research, mesh to its synthetic route
Till before, the preparation technology/synthetic method about antioxidant 330 has had many to be seen in report, such as:
The patent applications report of US3026264A is a kind of with concentrated sulphuric acid for catalyst mesitylene and the tertiary fourth of 2,6-bis-
The method that base-4-hydroxy-benzyl alcohol prepares antioxidant 330, but this handicraft product yield is low, spent acid surplus is relatively big and be unfavorable for industry
Produce.
The patent applications report of US5292669 is a kind of with sulphuric acid or methanesulfonic acid for catalyst mesitylene and 2,6-bis-
Tertiary butyl-4-hydroxy benzylalcohol prepares the method for antioxidant 330, but the yield of the method is the highest and seriously polluted, post processing
Difficulty, has greater environmental impacts.
The patent application of CN102399136A discloses a kind of with rare-earth dust for catalyst equal three
Benzene and 2, the method that 6-di-t-butyl-4-hydroxy-benzyl alcohol prepares antioxidant 330, it prepares target through two step alkylated reactions and produces
Thing, and reaction is gentle, the repeatable utilization of catalyst.
Li Chunhua etc. (" study on the synthesis of antioxidant 330 ", plastic additive, 2006,6,29-31,47) disclose a kind of with
Dimethylamine is the method that catalyst prepares antioxidant 330, but its reaction temperature is relatively low and there is harsh the asking of process conditions
Topic, product yield is only 75% simultaneously, it is impossible to be applied to large-scale production.
Although as it has been described above, vast research worker has been developed for the synthetic method of multiple hindered phenol antioxygen 330, but this
A little methods remain that many defects, such as reaction yield have much room for improvement, reaction process needs to be simplified, catalyst type needs
The problems such as developing.
In view of this, the present inventor is intended to the investigation by existing document and experimental exploring and develops a kind of hindered phenol and resist
The Novel synthesis technology of oxygen agent 330, thus the problem that can exist efficiently against prior art, substantially reduce technological process,
And then fully meet the polymeric material field widespread demand to antioxidant, there is good industrial applications potentiality and promotion price
Value.
Summary of the invention
For the problems of above-mentioned existence, the present inventor is paying after substantial amounts of creative experiments explores, Jing Guoshen
Enter research and propose the synthetic method of a kind of hindered phenol antioxygen 330, thus complete the present invention.Specifically, the present invention
Relate to following aspects.
First aspect, the invention provides the synthetic method of a kind of hindered phenol compound antioxidant 330, described method
Including: in the presence of ternary complex catalyst and diluted hydrochloric acid aqueous solution, lower formula (I) compound is with formula (II) compound in a solvent
React, thus obtain described antioxidant 330,
Wherein, upper formula (I) compound is 1,3,5-trichloromethyl-2,4,6-trimethylbenzenes, and upper formula (II) compound is i.e.
For 2,6 di t butyl phenol.
In the described synthetic method of the present invention, described ternary complex catalyst be fluoroform sulphonate, 3,4,7,8-tetra-
Methyl isophthalic acid, 10-phenanthrolene and CdI2Mixture, wherein fluoroform sulphonate, 3,4,7,8-tetramethyl-1,10-neighbour two
Aza-phenanthrenes and CdI2Mass ratio be 1:0.1-0.3:0.04-0.06, preferably 1:0.2:0.05.
Wherein, described fluoroform sulphonate is selected from Yb (OTf)3(Ytterbiumtriflate), Sm (OTf)3(trifluoromethanesulfonic acid
Samarium), Tb (OTf)3(trifluoromethanesulfonic acid terbium) or Ce (OTf)3(trifluoromethanesulfonic acid cerium), most preferably Yb (OTf)3(trifluoromethanesulfonic acid
Ytterbium).
In the described synthetic method of the present invention, the mass percent concentration of described diluted hydrochloric acid aqueous solution is 3-5%, such as
Can be 3%, 4% or 5%.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of formula (II) compound:
3.2-3.6, such as, can be 1:3.2,1:3.3,1:3.4,1:3.5 or 1:3.6.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mass ratio of ternary complex catalyst:
0.03-0.08, the i.e. quality of formula (I) compound are 1:0.03-0.08 with the ratio of the quality sum of three kinds of components in catalyst, example
As being 1:0.03,1:0.04,1:0.05,1:0.06,1:0.07 or 1:0.08.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mass ratio of diluted hydrochloric acid aqueous solution:
0.5-0.8, such as, can be 1:0.5,1:0.6,1:0.7 or 1:0.8.
In the described synthetic method of the present invention, described solvent be volume ratio be the mixture of component A and component B of 5:1,
Any one during wherein component A is chloroform, carbon tetrachloride or dichloromethane, most preferably carbon tetrachloride；Component B is 15-crown-
Any one in 5 or 18-crown-s 6.
There is no particular limitation for the consumption of described solvent, such as can according to being prone to so that reaction is smoothed out, and be prone to into
Row post processing and select suitable consumption, it is appropriately selected and true that this is that those skilled in the art can be carried out according to routine techniques means
Fixed.
In the described synthetic method of the present invention, reaction temperature is 50-70 DEG C, such as, can be 50 DEG C, 60 DEG C or 70 DEG C.
In the described synthetic method of the present invention, the response time is 6-10 hour, such as, can be that 6 hours, 8 hours or 10 are little
Time.
In the described synthetic method of the present invention, the post processing after having reacted is specific as follows: after reaction terminates, mistake while hot
Filter, fully washs filtrate 2-3 time with deionized water, separates organic facies, and by its concentrating under reduced pressure, residue petroleum ether is heavily tied
Crystalline substance, thus obtain purpose product antioxidant 330.
Second aspect, the invention still further relates to described formula (I) compound that is 1,3,5-trichloromethyl-2,4,6-trimethylbenzenes
Preparation method (the most described formula (I) compound is prepared as follows): depositing of carbon nanotube loaded acid catalyst
Under, sym-trimethylbenzene., mass percent concentration be 37% concentrated hydrochloric acid and paraformaldehyde at 40-50 DEG C, react 1-2 hour, instead
Should terminate to be down to room temperature, separate out solid, add in petroleum ether after solid is dried and reflux 40-80 minute, then natural cooling
Separate out solid, sucking filtration, deionized water wash, vacuum drying, obtain described formula (I) compound that is 1,3,5-trichloromethyl-2,4,
6-trimethylbenzene.
Wherein, sym-trimethylbenzene., mass percent concentration are the concentrated hydrochloric acid (in terms of HCl) of 37%, paraformaldehyde is (with formaldehyde
Meter) mol ratio be 1:4-4.4:5-6, i.e. sym-trimethylbenzene., the concentrated hydrochloric acid that mass percent concentration is 37% in terms of HCl, with
The mol ratio of this three of paraformaldehyde of formaldehyde meter is 1:4-4.4:5-6, preferably 1:4.2:5.5.
Wherein, described sym-trimethylbenzene. is 100:1-3 with the mass ratio of carbon nanotube loaded acid catalyst, such as, can be 100:
1,100:2 or 100:3.
Wherein, there is no particular limitation for the consumption of petroleum ether used, and those skilled in the art can be according to routine techniques means
Suitably select or determine.
Wherein, described carbon nanotube loaded acid catalyst is prepared as follows, and its preparation method is such as in other words
Under:
S1: joined in enough concentrated nitric acids by CNT, is heated to reflux 30-40 minute, filter, abundant with deionized water
Completely, vacuum drying oven is dried, thus obtains acidification CNT in washing；
S2: acidification CNT step S1 obtained joins in dehydrated alcohol, is sufficiently stirred for, until being formed outstanding
Till supernatant liquid；
S3: dropping adds tetraisopropyl titanate Ti (OC in the suspension that step S2 obtains3H7)4, continue while dropping
Stirring, until becoming colloidal sol shape, the most fully dry, pulverize and obtaining powder；
S4: powder step S3 obtained joins in the aqueous sulfuric acid of 1.2mol/l, impregnates 8-10 hour, after filtration
At 100 DEG C, completely, then with 8-12 DEG C/min, the heating rate of most preferably 10 DEG C/min is warming up to 500 DEG C in vacuum drying,
Roasting 1.5-2.5 hour, finally naturally cools to room temperature, obtains carbon nanotube loaded acid catalyst.
In step sl, described CNT can be any commercially available prod, the mass percent concentration of described concentrated nitric acid
For >=80%.
In step s 2, described acidification CNT is 1:3-5g/ml with the mass volume ratio of dehydrated alcohol, will
Every 1g acidification CNT joins in the dehydrated alcohol of 3-5ml, such as, can be 1:3g/ml, 1:4g/ml or 1:5g/ml.
In step s3, described acidification CNT is 1:0.1-0.3 with the mass ratio of tetraisopropyl titanate, such as
Can be 1:0.1,1:0.2 or 1:0.3.
In step s 4, the mass volume ratio of described powder and aqueous sulfuric acid is 1:8-12g/ml, will every 1g powder
Join in the aqueous sulfuric acid of 8-12ml, such as, can be 1:8g/ml, 1:10 g/ml or 1:12g/ml.
As it has been described above, the invention provides the synthesis of a kind of antioxidant 330 and as 1,3,5-trichlorines of wherein raw material
The preparation method of methyl-2,4,6-trimethylbenzene.The present inventor, on the basis of furtheing investigate substantial amounts of document, passes through
Specifically chosen and/or the combination of suitable catalyst, solvent etc. in reaction system, thus avoid the use of highly acid material, subtract
The light burden of equipment, thus obtained antioxidant 330 with good productivity, simultaneously to 1,3,5-trichloromethyl-2,4,6-
In the Study of synthesis method of trimethylbenzene, by the use of unique carbon nanotube loaded acid catalyst, and obtain with good yield
This compound.
In sum, technical scheme has plurality of advantages, thus has in industrialized production and application aspect
Good application potential and prospect.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, and not the real protection scope to the present invention constitutes any type of any restriction, more non-general
Protection scope of the present invention is confined to this.
Preparation example 1: the preparation of carbon nanotube loaded acid catalyst
S1: joined by CNT in the concentrated nitric acid that enough mass percent concentrations are 90%, is heated to reflux 35 minutes,
Filtering, fully wash with deionized water completely, vacuum drying oven is dried, thus obtains acidification CNT；
S2: acidification CNT step S1 obtained joins in dehydrated alcohol, is sufficiently stirred for, until being formed outstanding
Till supernatant liquid；Wherein said acidification CNT is 1:4g/ml with the mass volume ratio of dehydrated alcohol；
S3: dropping adds tetraisopropyl titanate Ti (OC in the suspension that step S2 obtains3H7)4, continue while dropping
Stirring, until becoming colloidal sol shape, the most fully dry, pulverize and obtaining powder；Wherein said acidification CNT (i.e. step
The acidification CNT that S1 obtains) it is 1:0.2 with the mass ratio of tetraisopropyl titanate；
S4: powder step S3 obtained joins in the aqueous sulfuric acid of 1.2mol/l, impregnates 9 hours, after filtration in
At 100 DEG C, vacuum drying completely, is then warming up to 500 DEG C with the programming rate of 10 DEG C/min, and roasting 2 hours is the coldest
But to room temperature, carbon nanotube loaded acid catalyst is obtained, by its named T1；Wherein said powder and the quality of aqueous sulfuric acid
Volume ratio is 1:10g/ml.
Preparation example 2: the preparation of carbon nanotube loaded acid catalyst
In addition to not carrying out the acidification of step S1, to have carried out preparation example 2 with the identical embodiment of preparation example 1, i.e.
CNT is carried out acidification without concentrated nitric acid, but directly carries out the process of step S2, gained is carbon nanotube loaded
The named T2 of acid catalyst.
Preparation example 3-8: the preparation of carbon nanotube loaded acid catalyst
In addition to the heating rate changed in step S4, other is the most constant, carries out with the identical embodiment with preparation example 1
Preparation example 3-8, by carbon nanotube loaded for the gained the most named T3-T8 of acid catalyst；Wherein heating rate, gained catalyst are shown in
Shown in table 1 below:
The carbon nanotube loaded acid catalyst obtained under the different heating rate of table 1.
The synthesis of Material synthesis example 1:1,3,5-trichloromethyl-2,4,6-trimethylbenzene
Under room temperature, in reactor, add concentrated hydrochloric acid and paraformaldehyde that sym-trimethylbenzene., mass percent concentration are 37%,
The mol ratio of three be 1:4.2:5.5 (wherein mass percent concentration be the concentrated hydrochloric acid of 37% in terms of HCl, paraformaldehyde is with first
Aldehyde meter), it is subsequently adding carbon nanotube loaded acid catalyst T1 (sym-trimethylbenzene. is 100:2 with the mass ratio of T1)；Then heat to
Reacting 90 minutes at 45 DEG C, room temperature is down in reaction end, separates out solid, adds in enough petroleum ether and reflux after being dried by solid
60 minutes, then natural cooling separated out solid, sucking filtration, deionized water wash, vacuum drying, obtains formula (I) chemical combination of the present invention
Thing that is 1,3,5-trichloromethyl-2,4,6-trimethylbenzenes, productivity is 98.9%.
The synthesis of Material synthesis example 2-8:1,3,5-trichloromethyl-2,4,6-trimethylbenzene
In addition to respectively carbon nanotube loaded acid catalyst T1 is replaced with T2-T8, other is the most constant, with Material synthesis example
The identical embodiment of 1 has carried out Material synthesis example 2-8, and the carbon nanotube loaded acid catalyst, the products collection efficiency that are used see below
Shown in table 2, but for the sake of becoming apparent from, the result of Material synthesis example 1 is together listed:
The impact of the different carbon nanotube loaded acid catalyst of table 2.
As seen from the above table, when using the carbon nanotube loaded acid catalyst of the present invention, it is possible to obtain excellent productivity；And
When CNT does not carries out acidification, productivity is caused to have certain reduction；Additionally, also, it was found that constant temperature in step S4
Heating rate before roasting has significant impact for the catalytic performance of catalyst, when heating rate is 8-12 DEG C/min,
Good productivity, especially heating rate can be obtained when being 10 DEG C/min, there is best effect, when heating rate does not exists
Time in the range of Gai, productivity has and significantly reduces.
Wherein, in following all embodiments, formula (I) compound and formula (II) compound are the change in generation referred to below
Compound:
Embodiment 1
Under room temperature in the appropriate mixed solvent of the carbon tetrachloride that volume ratio is 5:1 and 15-crown-5, add 100mmol formula
(I) compound and 320mmol (II) compound, is subsequently adding ternary complex catalyst (for Yb (OTf)3, 3,4,7,8-tetramethyl
Base-1,10-phenanthrolene and CdI2Mixture, the mass ratio of three is 1:0.2:0.05, formula (I) compound and this ternary
The quality of composite catalyst is 1:0.03) and diluted hydrochloric acid aqueous solution that mass percent concentration is 3% (formula (I) compound with should
The mass ratio of diluted hydrochloric acid aqueous solution is 1:0.5)；Then it is warming up to 50 DEG C under stirring, and reaction 10 hours at such a temperature.
After reaction terminates, filtered while hot, filtrate is fully washed 2-3 time with deionized water, separates organic facies, reduced pressure
Concentrating, residue petroleum ether recrystallization, thus obtain purpose product antioxidant 330, productivity is 99.5%, and its characterization parameter is such as
Under:
Fusing point: 239.4-241.6 DEG C.
1H NMR(CDCl3,400MHz):δ1.32-1.35(s,54H),2.23-2.26(s,9H), 3.95-3.97(s,
6H),6.96-6.99(s,6H),7.37-7.39(s,3H)。
Embodiment 2
Under room temperature in the appropriate mixed solvent of the carbon tetrachloride that volume ratio is 5:1 and 18-crown-6, add 100mmol formula
(I) compound and 340mmol (II) compound, is subsequently adding ternary complex catalyst (for Yb (OTf)3, 3,4,7,8-tetramethyl
Base-1,10-phenanthrolene and CdI2Mixture, the mass ratio of three is 1:0.2:0.05, formula (I) compound and this ternary
The quality of composite catalyst is 1:0.05) and diluted hydrochloric acid aqueous solution that mass percent concentration is 4% (formula (I) compound with should
The mass ratio of diluted hydrochloric acid aqueous solution is 1:0.6)；Then it is warming up to 60 DEG C under stirring, and reaction 8 hours at such a temperature.
After reaction terminates, filtered while hot, filtrate is fully washed 2-3 time with deionized water, separates organic facies, reduced pressure
Concentrating, residue petroleum ether recrystallization, thus obtain purpose product antioxidant 330, productivity is 99.3%, characterizes data with real
Execute example 1.
Embodiment 3
Under room temperature in the appropriate mixed solvent of the carbon tetrachloride that volume ratio is 5:1 and 15-crown-5, add 100mmol formula
(I) compound and 360mmol (II) compound, is subsequently adding ternary complex catalyst (for Yb (OTf)3, 3,4,7,8-tetramethyl
Base-1,10-phenanthrolene and CdI2Mixture, the mass ratio of three is 1:0.2:0.05, formula (I) compound and this ternary
The quality of composite catalyst is 1:0.08) and diluted hydrochloric acid aqueous solution that mass percent concentration is 5% (formula (I) compound with should
The mass ratio of diluted hydrochloric acid aqueous solution is 1:0.7)；Then it is warming up to 80 DEG C under stirring, and reaction 6 hours at such a temperature.
After reaction terminates, filtered while hot, filtrate is fully washed 2-3 time with deionized water, separates organic facies, reduced pressure
Concentrating, residue petroleum ether recrystallization, thus obtain purpose product antioxidant 330, productivity is 99.1%, characterizes data with real
Execute example 1.
Embodiment 4
Under room temperature in the appropriate mixed solvent of the carbon tetrachloride that volume ratio is 5:1 and 18-crown-6, add 100mmol formula
(I) compound and 330mmol (II) compound, is subsequently adding ternary complex catalyst (for Yb (OTf)3, 3,4,7,8-tetramethyl
Base-1,10-phenanthrolene and CdI2Mixture, the mass ratio of three is 1:0.2:0.05, formula (I) compound and this ternary
The quality of composite catalyst is 1:0.04) and diluted hydrochloric acid aqueous solution that mass percent concentration is 3% (formula (I) compound with should
The mass ratio of diluted hydrochloric acid aqueous solution is 1:0.8)；Then it is warming up to 70 DEG C under stirring, and reaction 7 hours at such a temperature.
After reaction terminates, filtered while hot, filtrate is fully washed 2-3 time with deionized water, separates organic facies, reduced pressure
Concentrating, residue petroleum ether recrystallization, thus obtain purpose product antioxidant 330, productivity is 99.4%, characterizes data with real
Execute example 1.
Embodiment 5-10: the investigation of catalytic component
In addition to using different catalytic components as shown in following table 2-1, other is all identical with corresponding embodiment, and
Being carried out example 5-10, used catalyst, corresponding embodiment and products collection efficiency see table shown in 2-1:
The impact of table 2-1: different catalysts
Note: wherein " √ " represents existence, "--" represents and does not exists.
From upper table 2-1, when deleting any one of ternary complex catalyst of the present invention or any two group
Timesharing, all will cause reacting and not occur or productivity is greatly lowered.This demonstrate that only three kinds components exist simultaneously, Cai Nengfa
Wave collaborative catalytic action, and then obtain the excellent productivity of the present invention.
Embodiment 11-18: the investigation of solvent composition A
Embodiment 11-14: respectively the carbon tetrachloride in embodiment 1-4 is replaced with the chloroform of same amount, and carries out
Embodiment 11-14.
Embodiment 15-18: respectively the carbon tetrachloride in embodiment 1-4 is replaced with the dichloromethane of same amount, and enters
Go embodiment 15-18.
Used solvent composition A and products collection efficiency see table shown in 3:
Table 3: the impact of solvent composition A
From upper table 3, solvent composition A for productivity by a certain degree of impact, even if being all halogenated alkane, but four
Chlorination carbon has best effect, and the productivity of chloroform and dichloromethane all has a certain degree of significantly reducing.
Embodiment 19-22: the investigation of concentration of hydrochloric acid
In addition to concentration of hydrochloric acid therein is replaced with the concentration in table 4 below, other the most constant and with the phase with embodiment 1-4
Implementing embodiment 19-22 with mode, the mass percent concentration of used hydrochloric acid, corresponding embodiment and products collection efficiency see table
Shown in 4:
Table 4: the impact of concentration of hydrochloric acid
As can be seen here, the concentration of hydrochloric acid has appreciable impact equally for reaction, when concentration is less than 2% or higher than 6%
Time, productivity reduces notable.
Embodiment 23-26: the investigation of fluoroform sulphonate
Except by Yb therein (OTf)3Replace with outside other fluoroform sulphonate in table 5 below, other the most constant and with
The same way of embodiment 1-4 implements embodiment 23-26, used fluoroform sulphonate, corresponding embodiment and products collection efficiency
See table shown in 5:
Table 5: the impact of fluoroform sulphonate
From upper table 5, catalytic effect is had by the kind of the fluoroform sulphonate in ternary complex catalyst of the present invention
Certain impact, the wherein Yb (OTf) of the present invention3There is best effect, and other fluoroform sulphonate all causes productivity
Decrease to some degree.
Embodiment 27-31: use investigation during single solvent
In addition to double solvents therein is replaced with the single solvent in table 6 below, other the most constant and with embodiment 1-4
Same way implement embodiment 27-31, the single solvent that used, corresponding embodiment and products collection efficiency see table shown in 6:
Table 6: use impact during single solvent
From upper table 6, when being used alone the one-component forming double solvents of the present invention, products collection efficiency is by significantly dropping
Low, only chloroform can obtain the productivity of 89.4%, and other is all greatly lowered.This demonstrate that employing double solvents of the present invention
Unobviousness and the unexpected property of effect.
In sum, the present invention is by creatively using ternary complex catalyst and the mixed solvent with optimal choice
Concerted catalysis assistant system, be effectively improved product yield, additionally, the constituent species of catalyst system and catalyzing is also carried out by the present invention
Experiment screening, thus drawn the system combinations of optimum, there is quite varied prospects for commercial application.
Should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents having read the present invention, the present invention can be made respectively by those skilled in the art
Planting change, amendment and/or modification, all these equivalent form of value falls within the guarantor that the application appended claims is limited equally
Within the scope of protecting.
Claims (9)
1. a synthetic method for hindered phenol compound antioxidant 330, described method includes: at ternary complex catalyst and dilute
In the presence of aqueous hydrochloric acid solution, lower formula (I) compound reacts in a solvent with lower formula (II) compound, thus obtains described anti-
Oxygen agent 330,
Described ternary complex catalyst is fluoroform sulphonate, 3,4,7,8-tetramethyl-1,10-phenanthrolene and CdI2Mixed
Compound, wherein fluoroform sulphonate, 3,4,7,8-tetramethyl-1,10-phenanthrolene and CdI2Mass ratio be 1:0.1-
0.3:0.04-0.06；
The mass percent concentration of described diluted hydrochloric acid aqueous solution is 3-5%；
Described solvent be volume ratio be the mixture of component A and component B of 5:1, wherein component A is chloroform, carbon tetrachloride or two
Any one in chloromethanes；Component B is any one in 15-crown-5 or 18-crown-6.
Synthetic method the most according to claim 1, it is characterised in that: fluoroform sulphonate, 3,4,7,8-tetramethyl-1,
10-phenanthrolene and CdI2Mass ratio be 1:0.2:0.05.
Synthetic method the most according to claim 1, it is characterised in that: described formula (I) compound and formula (II) compound
Mol ratio is 1:3.2-3.6.
Synthetic method the most according to claim 1, it is characterised in that: described formula (I) compound and ternary complex catalyst
Mass ratio be 1:0.03-0.08.
Synthetic method the most according to claim 1, it is characterised in that: described formula (I) compound and diluted hydrochloric acid aqueous solution
Mass ratio is 1:0.5-0.8.
Synthetic method the most according to claim 1, it is characterised in that: component A of described solvent is carbon tetrachloride.
7. according to the synthetic method described in any one of claim 1-6, it is characterised in that: described formula (I) compound is according to such as
Prepared by lower section method: in the presence of carbon nanotube loaded acid catalyst, sym-trimethylbenzene., mass percent concentration be 37% dense
Hydrochloric acid and paraformaldehyde react 1-2 hour at 40-50 DEG C, and room temperature is down in reaction end, separates out solid, adds after being dried by solid
Enter in petroleum ether and reflux 40-80 minute, then natural cooling precipitation solid, sucking filtration, deionized water wash, vacuum drying, i.e.
Obtain described formula (I) compound i.e. 1,3,5-trichloromethyl-2,4,6-trimethylbenzene；
Described carbon nanotube loaded acid catalyst is prepared as follows:
S1: joined in enough concentrated nitric acids by CNT, is heated to reflux 30-40 minute, filters, fully washs with deionized water
Completely, vacuum drying oven is dried, thus obtains acidification CNT；
S2: acidification CNT step S1 obtained joins in dehydrated alcohol, is sufficiently stirred for, until forming suspension
Till；
S3: dropping adds tetraisopropyl titanate Ti (OC in the suspension that step S2 obtains3H7)4, persistently stir while dropping
Mix, until becoming colloidal sol shape, the most fully dry, pulverize and obtaining powder；
S4: powder step S3 obtained joins in the aqueous sulfuric acid of 1.2mol/l, impregnates 8-10 hour, after filtration in
At 100 DEG C, completely, then with 8-12 DEG C/min, the heating rate of most preferably 10 DEG C/min is warming up to 500 DEG C in vacuum drying, roasting
Burn 1.5-2.5 hour, finally naturally cool to room temperature, obtain described carbon nanotube loaded acid catalyst.
Synthetic method the most according to claim 7, it is characterised in that: sym-trimethylbenzene., mass percent concentration in terms of HCl
It is that the concentrated hydrochloric acid of 37%, the mol ratio of this three of paraformaldehyde counted with formaldehyde are as 1:4-4.4:5-6.
Synthetic method the most according to claim 8, it is characterised in that: sym-trimethylbenzene., mass percent concentration in terms of HCl
It is that the concentrated hydrochloric acid of 37%, the mol ratio of this three of paraformaldehyde counted with formaldehyde are as 1:4.2:5.5.
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