CN104788292A - Synthesis method for hindered phenolic compound antioxidant 330 - Google Patents
Synthesis method for hindered phenolic compound antioxidant 330 Download PDFInfo
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- CN104788292A CN104788292A CN201510121181.8A CN201510121181A CN104788292A CN 104788292 A CN104788292 A CN 104788292A CN 201510121181 A CN201510121181 A CN 201510121181A CN 104788292 A CN104788292 A CN 104788292A
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- 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 24
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- 150000002989 phenols Chemical class 0.000 title abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- 239000002041 carbon nanotube Substances 0.000 claims description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 38
- 238000010189 synthetic method Methods 0.000 claims description 26
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical group FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 22
- 239000003377 acid catalyst Substances 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 230000015572 biosynthetic process Effects 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
- 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 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
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- -1 suction filtration Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 238000013019 agitation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000011206 ternary composite Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000011835 investigation Methods 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 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 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 0 Cc1c(*)c(C)c(*)c(C)c1* Chemical compound Cc1c(*)c(C)c(*)c(C)c1* 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-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
- WVDDGKGOMKODPV-UHFFFAOYSA-N benzyl alcohol Substances OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 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 2
- 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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 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
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- OGEJCBGPTKTKHE-UHFFFAOYSA-N terbium;trifluoromethanesulfonic acid Chemical compound [Tb].OS(=O)(=O)C(F)(F)F OGEJCBGPTKTKHE-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method for a hindered phenolic compound antioxidant 330; the method comprises the following steps: in the presence of a ternary composite catalyst and a diluted hydrochloric acid aqueous solution with specific concentration and amount, a compound represented by the following formula (I) and a compound represented by the following formula (II) are subjected to a reaction in a solvent, and thus the antioxidant 330 is obtained. In the synthesis method, through suitable selection and combination of a catalyst system and a solvent system, the target product is obtained with high yield; and the synthesis method is quite suitable for industrialization large-scale production and application and has a quite broad market prospect.
Description
Technical field
The present invention relates to a kind of synthetic method of oxidation inhibitor, relate more particularly to the synthetic method of a kind of Hinered phenols antioxidant and antioxidant 330, belong to organic chemical synthesis technical field.
Background technology
Antioxidant is for one of reagent preventing material aging, due to macromolecular material produce, store and use procedure in scale resistance difference and usually cause the instability of product performance or significantly decline, thus the use of antioxidant is subject to the most attention of people day by day.
Up to now, methods have been developed multiple oxidation inhibitor, wherein hindered phenol compound such as antioxidant 330 is class purposes oxidation inhibitor widely, its chemistry by name 1,3,5-trimethylammonium-2, (wherein t-Bu is the tertiary butyl to 4,6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, lower same), its structural formula is as follows:
This oxidation inhibitor to be developed by Shell Co. Ltd of the U.S. in nineteen sixty and is promoted, be the oxidation inhibitor of a kind of efficient, environmental protection, antioxidant property excellence, gram be widely used in the macromolecular materials such as the thermoplastic polyester such as polyolefine, PET, PBT, polymeric amide, styrene resin.
Just because of the excellent properties like this of this antioxidant 330, people have carried out large quantifier elimination to its synthetic route, and so far, the preparation technology/synthetic method about antioxidant 330 has had and is manyly seen in report, such as:
The patent applications report of US3026264A is a kind of is the method that catalyst mesitylene and 2,6-di-t-butyl-4-hydroxy-benzyl alcohol prepare antioxidant 330 with the vitriol oil, but this handicraft product yield is low, spent acid surplus is comparatively large and be unfavorable for industrial production.
The patent applications report of US5292669 a kind of with sulfuric acid or methylsulfonic acid for catalyst mesitylene and 2,6-di-t-butyl-4-hydroxy-benzyl alcohol prepares the method for antioxidant 330, but the yield of the method is still not high and seriously polluted, aftertreatment difficulty, has greater environmental impacts.
The one that application discloses of CN102399136A is catalyst mesitylene and 2 with rare-earth dust, 6-di-t-butyl-4-hydroxy-benzyl alcohol prepares the method for antioxidant 330, it obtains target product through two step alkylated reactions, and reaction temperature and, catalyzer can reuse.
Li Chunhua etc. (" study on the synthesis of antioxidant 330 "; additives for plastics; 2006; 6; 29-31,47) to disclose a kind of take dimethylamine as the method that catalyst prepares antioxidant 330; but its temperature of reaction is lower and there is the problem of processing condition harshness, and product yield is only 75%, can not be applied to large-scale production simultaneously.
As mentioned above, although numerous researchists have developed the synthetic method of multiple hindered phenol antioxygen 330, but these methods still also exist many defects, such as reaction yield has much room for improvement, reaction process needs simplification, catalyst type needs the problems such as developing.
In view of this, the present inventor is intended to be developed by the investigation of existing document and experimental exploring a kind of hindered phenol antioxygen 330
novelsynthesis technique, thus can effectively overcome prior art Problems existing, substantially reduce technical process, and then fully meet the widespread demand of polymeric material field to oxidation inhibitor, there is good industrial applications potentiality and promotional value.
Summary of the invention
For the problems of above-mentioned existence, the present inventor, after having paid a large amount of creative experiments explorations, proposes a kind of synthetic method of hindered phenol antioxygen 330, thus completes the present invention through further investigation.Specifically, the present invention relates to following several aspect.
First aspect, the invention provides a kind of synthetic method of hindered phenol compound antioxidant 330, described method comprises: under ternary complex catalyst and diluted hydrochloric acid aqueous solution exist, following formula (I) compound and formula (II) compound react in a solvent, thus obtain described antioxidant 330
Wherein, above formula (I) compound is 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, and above formula (II) compound is 2,6 di t butyl phenol.
In described synthetic method of the present invention, described ternary complex catalyst is fluoroform sulphonate, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mixture, wherein fluoroform sulphonate, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mass ratio be 1:0.1-0.3:0.04-0.06, be 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 is Yb (OTf)
3(Ytterbiumtriflate).
In 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 described synthetic method of the present invention, the mol ratio of described formula (I) compound and formula (II) compound is 1:3.2-3.6, such as, can be 1:3.2,1:3.3,1:3.4,1:3.5 or 1:3.6.
In described synthetic method of the present invention, the mass ratio of described formula (I) compound and ternary complex catalyst is 1:0.03-0.08, namely the quality of formula (I) compound is 1:0.03-0.08 with the ratio of the quality sum of three kinds of components in catalyzer, such as, can be 1:0.03,1:0.04,1:0.05,1:0.06,1:0.07 or 1:0.08.
In described synthetic method of the present invention, the mass ratio of described formula (I) compound and diluted hydrochloric acid aqueous solution is 1:0.5-0.8, such as, can be 1:0.5,1:0.6,1:0.7 or 1:0.8.
In described synthetic method of the present invention, described solvent is volume ratio is the component A of 5:1 and the mixture of B component, and wherein component A is any one in chloroform, tetracol phenixin or methylene dichloride, most preferably is tetracol phenixin; B component be 15-hat-5 or 18-hat-6 in any one.
There is no particular limitation for the consumption of described solvent, and such as reaction can be carried out smoothly according to being easy to, and be easy to carry out aftertreatment and select suitable consumption, this is that those skilled in the art can carry out suitable selection according to routine techniques means and determine.
In described synthetic method of the present invention, temperature of reaction is 50-70 DEG C, such as, can be 50 DEG C, 60 DEG C or 70 DEG C.
In described synthetic method of the present invention, the reaction times is 6-10 hour, such as, can be 6 hours, 8 hours or 10 hours.
In described synthetic method of the present invention, the aftertreatment after having reacted is specific as follows: after reaction terminates, filtered while hot, filtrate is fully washed 2-3 time with deionized water, is separated organic phase, by its concentrating under reduced pressure, residue sherwood oil recrystallization, thus obtain object product antioxidant 330.
Second aspect, the invention still further relates to described formula (I) compound that is 1, 3, 5-trichloromethyl-2, 4, preparation method's (namely described formula (I) compound is prepared as follows) of 6-Three methyl Benzene: under the existence of carbon nanotube loaded acid catalyst, sym-trimethylbenzene, mass percent concentration be 37% concentrated hydrochloric acid and paraformaldehyde at 40-50 DEG C, react 1-2 hour, room temperature is down in reaction end, separate out solid, to add in sherwood oil and the 40-80 minute that refluxes after solid is dried, then naturally cooling separates out solid, suction filtration, deionized water wash, vacuum-drying, obtain described formula (I) compound that is 1, 3, 5-trichloromethyl-2, 4, 6-Three methyl Benzene.
Wherein, sym-trimethylbenzene, mass percent concentration are the concentrated hydrochloric acid (in HCl) of 37%, the mol ratio of paraformaldehyde (in formaldehyde) is 1:4-4.4:5-6, namely sym-trimethylbenzene, in the mass percent concentration of HCl be 37% concentrated hydrochloric acid, in the mol ratio of this three of paraformaldehyde of formaldehyde for 1:4-4.4:5-6, be preferably 1:4.2:5.5.
Wherein, the mass ratio of described sym-trimethylbenzene and carbon nanotube loaded acid catalyst is 100:1-3, such as, can be 100:1,100:2 or 100:3.
Wherein, there is no particular limitation for the consumption of sherwood oil used, and those skilled in the art can carry out suitable selection according to routine techniques means or determine.
Wherein, described carbon nanotube loaded acid catalyst is prepared as follows, and its preparation method is as follows in other words:
S1: joined by carbon nanotube in enough concentrated nitric acids, reflux 30-40 minute, filters, fully washs completely with deionized water, and vacuum drying oven is dry, thus obtains acidification carbon nanotube;
S2: the acidification carbon nanotube obtained by step S1 joins in dehydrated alcohol, fully stirs, till formation suspension;
S3: add titanium isopropylate Ti (OC in the suspension that step S2 obtains
3h
7)
4, Keep agitation while dropping, until become colloidal sol shape, then fully dry, pulverize and obtains powder;
S4: the powder obtained by step S3 joins in the aqueous sulfuric acid of 1.2mol/l, dipping 8-10 hour, after filtration, at 100 DEG C, vacuum-drying is complete, then with 8-12 DEG C/min, most preferably the temperature rise rate of 10 DEG C/min is warming up to 500 DEG C, roasting 1.5-2.5 hour, finally naturally cools to room temperature, obtains carbon nanotube loaded acid catalyst.
In step sl, described carbon nanotube can be any commercially available prod, and the mass percent concentration of described concentrated nitric acid is >=80%.
In step s 2, the mass volume ratio of described acidification carbon nanotube and dehydrated alcohol is 1:3-5g/ml, joins in the dehydrated alcohol of 3-5ml, such as, can be 1:3g/ml, 1:4g/ml or 1:5g/ml by every 1g acidification carbon nanotube.
In step s3, the mass ratio of described acidification carbon nanotube and titanium isopropylate is 1:0.1-0.3, such as, can be 1:0.1,1:0.2 or 1:0.3.
In step s 4 which, the mass volume ratio of described powder and aqueous sulfuric acid is 1:8-12g/ml, joins in the aqueous sulfuric acid of 8-12ml, such as, can be 1:8g/ml, 1:10 g/ml or 1:12g/ml by every 1g powder.
As mentioned above, the invention provides the preparation method of a kind of synthesis of antioxidant 330 and 1,3,5-trichloromethyl-2,4, the 6-Three methyl Benzene as its Raw.The present inventor is on the basis furtherd investigate a large amount of documents, by concrete selection and/or the combination of suitable catalyst, solvent etc. in reaction system, thus avoid the use of strongly-acid material, alleviate the burden of equipment, thus obtain antioxidant 330 with good productive rate, simultaneously to 1,3, in the Study of synthesis method of 5-trichloromethyl-2,4,6-Three methyl Benzene, by the use of the carbon nanotube loaded acid catalyst of uniqueness, and obtain this compound with good yield.
In sum, technical scheme of the present invention has plurality of advantages, thus has good application potential and prospect in suitability for industrialized production and application aspect.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Preparation example 1: the preparation of carbon nanotube loaded acid catalyst
S1: carbon nanotube being joined enough mass percent concentrations is in the concentrated nitric acid of 90%, reflux 35 minutes, filters, fully washs completely with deionized water, and vacuum drying oven is dry, thus obtains acidification carbon nanotube;
S2: the acidification carbon nanotube obtained by step S1 joins in dehydrated alcohol, fully stirs, till formation suspension; The mass volume ratio of wherein said acidification carbon nanotube and dehydrated alcohol is 1:4g/ml;
S3: add titanium isopropylate Ti (OC in the suspension that step S2 obtains
3h
7)
4, Keep agitation while dropping, until become colloidal sol shape, then fully dry, pulverize and obtains powder; Wherein said acidification carbon nanotube (i.e. step S1 obtain acidification carbon nanotube) is 1:0.2 with the mass ratio of titanium isopropylate;
S4: the powder obtained by step S3 joins in the aqueous sulfuric acid of 1.2mol/l, flood 9 hours, after filtration, at 100 DEG C, vacuum-drying is complete, then 500 DEG C are warming up to the heat-up rate of 10 DEG C/min, roasting 2 hours, finally naturally cool to room temperature, obtain carbon nanotube loaded acid catalyst, by its called after T1; The mass volume ratio of wherein said powder and aqueous sulfuric acid is 1:10g/ml.
Preparation example 2: the preparation of carbon nanotube loaded acid catalyst
Except not carrying out the acidification of step S1, to have carried out preparation example 2 with the identical embodiment of preparation example 1, carry out acidification by carbon nanotube without concentrated nitric acid, but directly carry out the process of step S2, by carbon nanotube loaded for gained acid catalyst called after T2.
Preparation example 3-8: the preparation of carbon nanotube loaded acid catalyst
Except the temperature rise rate changed in step S4, other is all constant, to have carried out preparation example 3-8 with the identical embodiment of preparation example 1, by carbon nanotube loaded for gained acid catalyst called after T3-T8 in turn; Wherein temperature rise rate, gained catalyzer are shown in
following table 1shown in:
table 1. the carbon nanotube loaded acid catalyst obtained under different temperature rise rate
The synthesis of Material synthesis example 1:1,3,5-trichloromethyl-2,4,6-Three methyl Benzene
Under room temperature, in reactor, add sym-trimethylbenzene, mass percent concentration be 37% concentrated hydrochloric acid and paraformaldehyde, the mol ratio of three is that (wherein mass percent concentration is that the concentrated hydrochloric acid of 37% is in HCl to 1:4.2:5.5, paraformaldehyde is in formaldehyde), then add carbon nanotube loaded acid catalyst T1 (mass ratio of sym-trimethylbenzene and T1 is 100:2); Then react 90 minutes at being warming up to 45 DEG C, room temperature is down in reaction end, separates out solid, to add in enough sherwood oils and reflux 60 minutes after being dried by solid, then naturally cooling separates out solid, suction filtration, deionized water wash, vacuum-drying, obtain formula of the present invention (I) compound that is 1,3,5-trichloromethyl-2,4,6-Three methyl Benzene, productive rate is 98.9%.
The synthesis of Material synthesis example 2-8:1,3,5-trichloromethyl-2,4,6-Three methyl Benzene
Replace with respectively except T2-T8 except by carbon nanotube loaded acid catalyst T1, other is all constant, and to have carried out Material synthesis example 2-8 with the identical embodiment of Material synthesis example 1, the carbon nanotube loaded acid catalyst used, products collection efficiency are shown in
following table 2shown in, but for the purpose of clearer, the result of Material synthesis example 1 is together listed:
table 2. the impact of different carbon nanotube loaded acid catalyst
By
upper tablevisible, when adopting carbon nanotube loaded acid catalyst of the present invention, excellent productive rate can be obtained; And when carbon nanotube does not carry out acidification, cause productive rate to have certain reduction; In addition, same discovery, temperature rise rate before constant temperature calcining in step S4 has significant impact for the catalytic performance of catalyzer, when temperature rise rate is 8-12 DEG C/min, good productive rate can be obtained, when especially temperature rise rate is 10 DEG C/min, there is best effect, when temperature rise rate is not within the scope of this, productive rate has and significantly reduces.
Wherein, in all embodiments below, the compound referred to below formula (I) compound and formula (II) compound are:
Embodiment 1
Be that the tetracol phenixin of 5:1 and 15-are preced with in the appropriate mixed solvent of-5 to volume ratio under room temperature, add 100mmol formula (I) compound and 320mmol (II) compound, then adding ternary complex catalyst (is Yb (OTf)
3, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mixture, the mass ratio of three is 1:0.2:0.05, and the quality of formula (I) compound and this ternary complex catalyst is 1:0.03) and mass percent concentration be 3% diluted hydrochloric acid aqueous solution (mass ratio of formula (I) compound and this diluted hydrochloric acid aqueous solution is 1:0.5); Then be warming up to 50 DEG C under stirring, and react 10 hours at such a temperature.
After reaction terminates, filtered while hot, fully washs filtrate 2-3 time with deionized water, is separated organic phase, by its concentrating under reduced pressure, and residue sherwood oil recrystallization, thus obtain object product antioxidant 330, productive rate is 99.5%, and its characterization parameter is as follows:
Fusing point: 239.4-241.6 DEG C.
1H NMR(CDCl
3,400MHz):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
Be that the tetracol phenixin of 5:1 and 18-are preced with in the appropriate mixed solvent of-6 to volume ratio under room temperature, add 100mmol formula (I) compound and 340mmol (II) compound, then adding ternary complex catalyst (is Yb (OTf)
3, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mixture, the mass ratio of three is 1:0.2:0.05, and the quality of formula (I) compound and this ternary complex catalyst is 1:0.05) and mass percent concentration be 4% diluted hydrochloric acid aqueous solution (mass ratio of formula (I) compound and this diluted hydrochloric acid aqueous solution is 1:0.6); Then be warming up to 60 DEG C under stirring, and react 8 hours at such a temperature.
After reaction terminates, filtered while hot, fully washs filtrate 2-3 time with deionized water, is separated organic phase, by its concentrating under reduced pressure, and residue sherwood oil recrystallization, thus obtain object product antioxidant 330, productive rate is 99.3%, and characterization data is with embodiment 1.
Embodiment 3
Be that the tetracol phenixin of 5:1 and 15-are preced with in the appropriate mixed solvent of-5 to volume ratio under room temperature, add 100mmol formula (I) compound and 360mmol (II) compound, then adding ternary complex catalyst (is Yb (OTf)
3, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mixture, the mass ratio of three is 1:0.2:0.05, and the quality of formula (I) compound and this ternary complex catalyst is 1:0.08) and mass percent concentration be 5% diluted hydrochloric acid aqueous solution (mass ratio of formula (I) compound and this diluted hydrochloric acid aqueous solution is 1:0.7); Then be warming up to 80 DEG C under stirring, and react 6 hours at such a temperature.
After reaction terminates, filtered while hot, fully washs filtrate 2-3 time with deionized water, is separated organic phase, by its concentrating under reduced pressure, and residue sherwood oil recrystallization, thus obtain object product antioxidant 330, productive rate is 99.1%, and characterization data is with embodiment 1.
Embodiment 4
Be that the tetracol phenixin of 5:1 and 18-are preced with in the appropriate mixed solvent of-6 to volume ratio under room temperature, add 100mmol formula (I) compound and 330mmol (II) compound, then adding ternary complex catalyst (is Yb (OTf)
3, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mixture, the mass ratio of three is 1:0.2:0.05, and the quality of formula (I) compound and this ternary complex catalyst is 1:0.04) and mass percent concentration be 3% diluted hydrochloric acid aqueous solution (mass ratio of formula (I) compound and this diluted hydrochloric acid aqueous solution is 1:0.8); Then be warming up to 70 DEG C under stirring, and react 7 hours at such a temperature.
After reaction terminates, filtered while hot, fully washs filtrate 2-3 time with deionized water, is separated organic phase, by its concentrating under reduced pressure, and residue sherwood oil recrystallization, thus obtain object product antioxidant 330, productive rate is 99.4%, and characterization data is with embodiment 1.
Embodiment 5-10: the investigation of catalyst component
Except as
following table 2use outside different catalyst components shown in-1, other is all identical with corresponding embodiment, and has carried out embodiment 5-10, use catalyzer, corresponding embodiment and products collection efficiency to see
following table 2shown in-1:
table 2-1: the impact of different catalysts
Note: wherein " √ " represents to exist, "--" represents not exist.
By
upper table 2-1 is visible, when any one of deleting in ternary complex catalyst of the present invention or any two kinds of components, all will cause reacting and not occur or productive rate significantly reduces.This demonstrate that and only have three kinds of components to exist simultaneously, the katalysis that competence exertion is collaborative, and then obtain excellent productive rate of the present invention.
Embodiment 11-18: the investigation of solvent composition A
Embodiment 11-14: the chloroform respectively tetracol phenixin in embodiment 1-4 being replaced with same amount, and carried out embodiment 11-14.
Embodiment 15-18: the methylene dichloride respectively tetracol phenixin in embodiment 1-4 being replaced with same amount, and carried out embodiment 15-18.
Use solvent composition A and products collection efficiency to see
following table 3shown in:
table 3: the impact of solvent composition A
By
upper table 3visible, solvent composition A is for productive rate by impact to a certain degree, even if be all halogenated alkane, but tetracol phenixin has best effect, and the productive rate of chloroform and methylene dichloride all has remarkable reduction to a certain degree.
Embodiment 19-22: the investigation of concentration of hydrochloric acid
Except concentration of hydrochloric acid is wherein replaced with
following table 4in concentration outside, other all constant and with implement embodiment 19-22 with the same way of embodiment 1-4, use the mass percent concentration of hydrochloric acid, corresponding embodiment and products collection efficiency to see
following table 4shown in:
table 4: the impact of concentration of hydrochloric acid
As can be seen here, the concentration of hydrochloric acid has remarkably influenced equally for reaction, when concentration lower than 2% or higher than 6% time, productive rate reduces significantly.
Embodiment 23-26: the investigation of fluoroform sulphonate
Remove Yb (OTf) wherein
3replace with
following table 5in other fluoroform sulphonate outside, other is all constant and to implement embodiment 23-26 with the same way of embodiment 1-4, use fluoroform sulphonate, corresponding embodiment and products collection efficiency to see
following table 5shown in:
table 5: the impact of fluoroform sulphonate
By
upper table 5visible, the kind of the fluoroform sulphonate in ternary complex catalyst of the present invention has certain impact to catalytic effect, wherein Yb of the present invention (OTf)
3there is best effect, and other fluoroform sulphonate all causes productive rate decrease to some degree.
Embodiment 27-31: use investigation during single solvent
Except double solvents is wherein replaced with
following table 6in single solvent outside, other is all constant and to implement embodiment 27-31 with the same way of embodiment 1-4, the single solvent used, corresponding embodiment and products collection efficiency are shown in
following table 6shown in:
table 6: use impact during single solvent
By
upper table 6visible, when being used alone the one-component forming double solvents of the present invention, products collection efficiency, by significantly reducing, only has chloroform can obtain the productive rate of 89.4%, and other all has and significantly reduces.This demonstrate that the unexpected property adopting the unobviousness of double solvents of the present invention and effect.
In sum, the present invention has the ternary complex catalyst of optimal selection and the concerted catalysis assistant system of mixed solvent by creatively using, effectively improve product yield, in addition, the present invention has also carried out experiment screening to the constituent species of catalyst system, thus drawn optimum system combinations, there is prospects for commercial application very widely.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the synthetic method of a hindered phenol compound antioxidant 330, described method comprises: under ternary complex catalyst and diluted hydrochloric acid aqueous solution exist, following formula (I) compound and following formula (II) compound react in a solvent, thus obtain described antioxidant 330
2. synthetic method according to claim 1, is characterized in that: described ternary complex catalyst is fluoroform sulphonate, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mixture, wherein fluoroform sulphonate, 3,4,7,8-tetramethyl--1,10-phenanthrolene and CdI
2mass ratio be 1:0.1-0.3:0.04-0.06, be preferably 1:0.2:0.05.
3. synthetic method according to claim 1 and 2, is characterized in that: the mass percent concentration of described diluted hydrochloric acid aqueous solution is 3-5%.
4. the synthetic method according to any one of claim 1-3, is characterized in that: the mol ratio of described formula (I) compound and formula (II) compound is 1:3.2-3.6.
5. the synthetic method according to any one of claim 1-4, is characterized in that: the mass ratio of described formula (I) compound and ternary complex catalyst is 1:0.03-0.08.
6. the synthetic method according to any one of claim 1-5, is characterized in that: the mass ratio of described formula (I) compound and diluted hydrochloric acid aqueous solution is 1:0.5-0.8.
7. the synthetic method according to any one of claim 1-6, it is characterized in that: described solvent is volume ratio is the component A of 5:1 and the mixture of B component, wherein component A is any one in chloroform, tetracol phenixin or methylene dichloride, most preferably is tetracol phenixin; B component be 15-hat-5 or 18-hat-6 in any one.
8. the synthetic method according to any one of claim 1-7, it is characterized in that: described formula (I) compound is prepared as follows: under the existence of carbon nanotube loaded acid catalyst, sym-trimethylbenzene, mass percent concentration be 37% concentrated hydrochloric acid and paraformaldehyde at 40-50 DEG C, react 1-2 hour, room temperature is down in reaction end, separate out solid, to add in sherwood oil and the 40-80 minute that refluxes after solid is dried, then naturally cooling separates out solid, suction filtration, deionized water wash, vacuum-drying, obtain described formula (I) compound that is 1, 3, 5-trichloromethyl-2, 4, 6-Three methyl Benzene.
9. synthetic method according to claim 8, is characterized in that: sym-trimethylbenzene, in the mass percent concentration of HCl be 37% concentrated hydrochloric acid, in the mol ratio of this three of paraformaldehyde of formaldehyde for 1:4-4.4:5-6, be preferably 1:4.2:5.5.
10. synthetic method according to claim 8 or claim 9, is characterized in that: described carbon nanotube loaded acid catalyst is prepared as follows:
S1: joined by carbon nanotube in enough concentrated nitric acids, reflux 30-40 minute, filters, fully washs completely with deionized water, and vacuum drying oven is dry, thus obtains acidification carbon nanotube;
S2: the acidification carbon nanotube obtained by step S1 joins in dehydrated alcohol, fully stirs, till formation suspension;
S3: add titanium isopropylate Ti (OC in the suspension that step S2 obtains
3h
7)
4, Keep agitation while dropping, until become colloidal sol shape, then fully dry, pulverize and obtains powder;
S4: the powder obtained by step S3 joins in the aqueous sulfuric acid of 1.2mol/l, dipping 8-10 hour, after filtration, at 100 DEG C, vacuum-drying is complete, then with 8-12 DEG C/min, most preferably the temperature rise rate of 10 DEG C/min is warming up to 500 DEG C, roasting 1.5-2.5 hour, finally naturally cools to room temperature, obtains described carbon nanotube loaded acid catalyst.
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