CN108467406A - 168 new technique for synthesizing route of antioxidant - Google Patents
168 new technique for synthesizing route of antioxidant Download PDFInfo
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- CN108467406A CN108467406A CN201810298321.2A CN201810298321A CN108467406A CN 108467406 A CN108467406 A CN 108467406A CN 201810298321 A CN201810298321 A CN 201810298321A CN 108467406 A CN108467406 A CN 108467406A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 title description 17
- 230000003078 antioxidant effect Effects 0.000 title description 16
- 230000002194 synthesizing effect Effects 0.000 title description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 90
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 21
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 17
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims abstract description 13
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical class CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 11
- 238000005292 vacuum distillation Methods 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 abstract description 16
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 abstract description 7
- 238000011020 pilot scale process Methods 0.000 abstract description 5
- 238000012805 post-processing Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 17
- 239000012467 final product Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001953 recrystallisation Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- -1 2,4- di-tert-butyl-phenyl Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 0 C=*1C2CCC1CC2 Chemical compound C=*1C2CCC1CC2 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of organic synthesis antioxidant 168, i.e., the method for three (2,4 di-tert-butyl-phenyl) phosphite esters, the method comprises the steps of：Using the mixed solution of methanol and toluene as solvent, with 2, 4 di-tert-butylphenols and phosphorus trichloride are reactant, by the present invention in that with loaded catalyst, and adjust carrier and the activated centre of catalyst, reaction is set to carry out more thorough, finally obtained efficiency of pcr product and purity are all greatly improved, yield highest may be up to 97.8%, purity may be up to 98.9%, existing level will be apparently higher than, and it is provided by the invention to prepare three (2, 4 di-tert-butyl-phenyls) phosphite ester reacting middle catalyst dosage it is few, reaction temperature is low, products therefrom post-processing is simple, pilot scale yield, which is carried out, using synthetic method provided by the invention is still up to 90% or more.
Description
Technical field
The present invention relates to field of chemical technology, more particularly to a kind of antioxidant three (2,4- di-tert-butyl-phenyl) is sub-
The methodology of organic synthesis of phosphate.
Background technology
Antioxidant is a kind of can to inhibit or delay high polymer and other organic compounds thermal oxide has in air
Machine synthetic, it is usually highly effective as long as the antioxidant that 1% such small concentrations are added.For example, food is easy oxidation deterioration, it can
With the storage time that a small amount of antioxidant is added to extend them.The high molecular materials such as plastics, synthetic fibers and rubber are easy hair
Heat oxygen degradation reaction, antioxidant, which is added, can keep the excellent performance of high molecular material, prolong the service life, antioxidant
Addition to be made an appointment closer to digestion period, such as before polymer is dried to powder.
Three (2,4- di-tert-butyl-phenyl) phosphite esters, i.e. antioxidant 168, molecular formula are：C42H63O3P, molecular weight are：
646.92, molecular structural formula (A) is：
Three (2,4- di-tert-butyl-phenyl) phosphite esters are a kind of excellent phosphite antioxidants, and appearance is white
Powder is soluble in the organic solvents such as benzene, chloroform, hexamethylene, is slightly soluble in ethyl alcohol, acetone, and not soluble in water, alcohol isopolarity solvent is micro-
It is dissolved in esters.Toxicity is low, and volatility is low, and thermal stability is high, and water resistance is excellent, can effectively decompose polymeric material hot-working
The hydroperoxides generated in journey.With hindered amines antioxidant and with there is good synergistic effect, polymeric material heat can be improved
Process or sad stability.It is several up to ten with the preparation of phenol antioxidant compounding, it is widely used in polyolefin
(such as polyethylene, polypropylene) and olefin copolymer.Polyamide, makrolon, PS resins, PVC, engineering plastics, rubber and stone
The high molecular materials such as oil product, ABS resin.Compound also useful binders, natural or synthetic binder resin etc..General dosage is
0.1-1.0%.Oxidant 168 and resin have a very high compatibility, and with very low, high-fire resistance, resistance to extractable and
Do not pollute the features such as non-discolouring, be current domestic classic processing stabilizers, it can effectively prevent polymer (polyethylene,
Polypropylene etc.) thermal degradation in squeezing out injection moulding process is that polymer produces original mechanical performance and ageing-resistant performance.
In recent years since domestic large-scale ethylene joint production is gone into operation in succession, the demand of plastics antioxidant constantly increases
Add, and the production of domestic antioxidant is started late, and be there is very big gap between the demand of processing industry, is both affected plastics
Fabricated product enters international market, also affects the development of ethylene industry；Therefore, the exploitation of antioxidant synthesis technology has weight
Want meaning.The production technology of China's antioxidant is mainly with reference to some external outmoded production methods, generally with liquid nitrogen at present
Catalyst, consumption of raw materials amount is big, and production cost is high, and environmental pollution is serious.It there is now to improve original synthetic method and grind
Studying carefully personnel uses basic species as catalyst, for producing antioxidant.The yield of antioxidant 168 has reached in existing report
89%, but this yield is yield prepared by laboratory, the yield in pilot scale can only achieve 65-70%, so providing one
The method that kind improves 168 yield of pilot scale synthetized oxidation preventive agent is extremely urgent.
Invention content
To solve the above-mentioned problems, the present invention is intended to provide a kind of catalyst amount is few, and catalyst is cheap and easy to get, reaction
Temperature is low, and products therefrom purity is high, pilot scale yield up to 90% or more methodology of organic synthesis.
Technical scheme is as follows：
Organic synthesis three (2,4- di-tert-butyl-phenyl) phosphite ester, described three (2,4- di-tert-butyl-phenyl) phosphite ester
Organic structure (A) be：
The method for synthesizing described three (2,4- di-tert-butyl-phenyl) phosphite esters, the method includes following synthesis path formulas
(I)：
It the described method comprises the following steps：
(1) suitable 2,4- di-tert-butylphenols, a certain amount of catalyst and a certain amount of molten is added in three-necked flask first
In agent, rotor is added afterwards, and reflux condensing tube, thermometer and dropping funel are fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath and is slowly heated up, temperature is made to rise to
40-45 DEG C, obtain reaction solution；
(3) suitable phosphorus trichloride is added dropwise into the reaction solution of step (2), control drop speed makes its 10-15min drip
Finish, is continuously heating to 90-100 DEG C, insulation reaction 30-40min, vacuum distillation removes solvent, is recrystallized with n-hexane, i.e.,
Obtain product.
Solvent is the mixed solution of methanol and toluene in above-mentioned steps (1), and the ratio of both volumes is 1: 0.01-60.
The mass volume ratio of 2,4- di-tert-butylphenols and solvent is 1: 40-60 (g/mL) in above-mentioned steps (1).
In some embodiments, solvent for use is that methanol that volume ratio is 1: 0.01 and toluene mixing are molten in step (1)
Liquid.
In other embodiments, solvent for use is that methanol that volume ratio is 1: 60 and toluene mixing are molten in step (1)
Liquid.
In some preferred embodiments, solvent for use is methanol that volume ratio is 1: 30 and toluene mixing in step (1)
Solution.
The ratio between the amount of substance of above-mentioned steps (1) and raw material 2 in step (3), 4- di-tert-butylphenols and phosphorus trichloride is 1-
1.5∶0.5。
Slowly heating rate is to increase 3-5 degrees Celsius in every ten minutes to above-mentioned steps (2)；Preferably, 5 are increased within every ten minutes to take the photograph
Family name's degree.
Phosphorus trichloride described in above-mentioned steps (3) is dissolved using toluene, is added in the dropping funel on three-necked flask.
The addition of catalyst is the 0.15-0.2% of 2,4- di-tert-butylphenol quality in above-mentioned steps (1).
Used catalyst is support type basic catalyst in above-mentioned steps (1)；
Wherein, the carrier can be selected from diatomite, SiO2-Al2O3, zeolite molecular sieve and one kind or several in atlapulgite
Kind；
Preferably, the carrier can be selected from one or more of diatomite, zeolite molecular sieve and atlapulgite.
The activated centre can be selected from DMF, hexamethylene, triphenyl phosphorus, n,N-Dimethylaniline, DMAP and pyridine
It is one or more of；
Preferably, above-mentioned activated centre can be selected from hexamethylene, triphenyl phosphorus, n,N-Dimethylaniline, DMAP and pyridine
One or more；
It is further preferred that above-mentioned activated centre can be selected from triphenyl phosphorus, n,N-Dimethylaniline, DMAP and pyridine
It is one or more of；
The preparation method of loaded catalyst is method commonly used in the art.
Three (2,4- di-tert-butyl-phenyls) Asia can be improved using loaded catalyst by being found surprisingly that during the reaction
Reaction efficiency in phosphate preparation process improves reaction speed on the basis of reducing catalyst use, makes raw product yield
It improves.
Beneficial effects of the present invention are as follows：
The present invention is by the required solvent of the type and reaction that adjust catalysts, in the base for reducing catalyst amount
Reaction efficiency is substantially increased on plinth, and can improve the yield and purity of reaction product, and yield is still up to 90% in pilot scale
More than, keep reaction product post-processing step simple, not will produce contamination gas and pollutant, be conducive to environmental protection.It is three (2,4-
Di-tert-butyl-phenyl) large-scale industrial production of phosphite ester provides possibility.
Specific embodiment
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 1
The specific steps are：
(1) the DMF catalyst of 2,4- di-tert-butylphenols 4.12g, tripolite loading is added in three-necked flask first
In 6.19mg and methanol and toluene mixed solution 200mL, it is added rotor afterwards, and by reflux condensing tube, thermometer and dropping funel
It is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 40 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 2.06g of 50mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 10min is added dropwise, is continuously heating to 90 DEG C, insulation reaction 30min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 95.2%, purity 98.3%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 2
The specific steps are：
(1) the triphenyl phosphorus catalyst of 2,4- di-tert-butylphenols 6.18g, tripolite loading is added in three-necked flask first
In 11.1mg and methanol and toluene mixed solution 200mL, it is added rotor afterwards, and by reflux condensing tube, thermometer and dropping funel
It is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 45 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 3.09g of 50mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 10min is added dropwise, is continuously heating to 90 DEG C, insulation reaction 35min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 96.5%, purity 98.6%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 3
The specific steps are：
(1) the triphenyl phosphorus catalyst of 2,4- di-tert-butylphenols 7.34g, tripolite loading is added in three-necked flask first
In 13.3mg and methanol and toluene mixed solution 220mL, it is added rotor afterwards, and by reflux condensing tube, thermometer and dropping funel
It is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 40 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 3.71g of 40mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 10min is added dropwise, is continuously heating to 95 DEG C, insulation reaction 38min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 96.8%, purity 98.9%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 4
The specific steps are：
(1) 2,4- di-tert-butylphenols 6.18g is added in three-necked flask first, the triphenyl phosphorus of zeolite molecular sieve load is urged
In agent 11.1mg and methanol and toluene mixed solution 250mL, it is added rotor afterwards, and by reflux condensing tube, thermometer and dropping liquid
Funnel is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 45 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 3.09g of 35mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 12min is added dropwise, is continuously heating to 90 DEG C, insulation reaction 40min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 97.2%, purity 98.6%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 5
The specific steps are：
(1) 2,4- di-tert-butylphenols 9.27g is added in three-necked flask first, the triphenyl phosphorus of zeolite molecular sieve load is urged
In agent 13.9mg and methanol and toluene mixed solution 380mL, it is added rotor afterwards, and by reflux condensing tube, thermometer and dropping liquid
Funnel is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 40 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 4.64g of 50mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 15min is added dropwise, is continuously heating to 90 DEG C, insulation reaction 35min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 97.5%, purity 98.8%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 6
The specific steps are：
(1) 2,4- di-tert-butylphenols 7.34g is added in three-necked flask first, the DMAP catalyst that zeolite molecular sieve loads
In 13.3mg and methanol and toluene mixed solution 350mL, it is added rotor afterwards, and by reflux condensing tube, thermometer and dropping funel
It is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 45 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 3.71g of 30mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 10min is added dropwise, is continuously heating to 95 DEG C, insulation reaction 35min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 97.4%, purity 98.4%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 7
The specific steps are：
(1) 2,4- di-tert-butylphenols 11.0g is added in three-necked flask first, the pyridine catalyst that zeolite molecular sieve loads
In 22mg and methanol and toluene mixed solution 450mL, rotor is added afterwards, and reflux condensing tube, thermometer and dropping funel are consolidated
It is scheduled on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 35 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 5.57g of 40mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 12min is added dropwise, is continuously heating to 95 DEG C, insulation reaction 30min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 97.8%, purity 98.9%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 8
The specific steps are：
(1) 2,4- di-tert-butylphenols 4.12g, active clay loaded N, N- dimethyl benzenes is added in three-necked flask first
In amine catalyst 6.19mg and methanol and toluene mixed solution 200mL, be added rotor afterwards, and by reflux condensing tube, thermometer and
Dropping funel is fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 35 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 2.06g of 10mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 12min is added dropwise, is continuously heating to 95 DEG C, insulation reaction 30min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 97.5%, purity 98.2%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of embodiment 9
The specific steps are：
(1) the pyridine catalyst 22mg of 2,4- di-tert-butylphenols 11.0g, tripolite loading is added in three-necked flask first
In methanol and toluene mixed solution 400mL, rotor is added afterwards, and reflux condensing tube, thermometer and dropping funel are fixed on
On three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath with every ten minutes 5 degrees Celsius of speed
Rate heats up, and so that temperature is risen to 40 DEG C, obtains reaction solution；
(3) phosphorus trichloride with the dissolved 5.57g of 30mL toluene is added dropwise into the reaction solution of step (2), control drop is fast,
So that its 15min is added dropwise, is continuously heating to 95 DEG C, insulation reaction 30min, vacuum distillation removes solvent, is carried out with n-hexane
Recrystallization is to get to product.
The yield of final product is 98.3%, purity 98.9%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of comparative example 1
With embodiment 9 difference lies in：Solvent used in step (1) is single methanol solution, other steps and
It operates same as Example 9.
The yield of final product is 80.2%, purity 78.6%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of comparative example 2
With embodiment 9 difference lies in：Solvent used in step (1) is single toluene solution, other steps and
It operates same as Example 9.
The yield of final product is 88.2%, purity 89.9%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of comparative example 3
With embodiment 9 difference lies in：Solvent used in step (1) is：The methanol and toluene of volume ratio 10: 1 are molten
Liquid, other steps and operations are same as Example 9.
The yield of final product is 81.5%, purity 84.2%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of comparative example 4
With embodiment 9 difference lies in：In step (1) plus 2,4- di-tert-butylphenols and phosphorus trichloride substance amount it
Than being 1: 2, other steps and operations are same as Example 9.
The yield of final product is 79.5%, purity 78.0%.
A kind of method of three (2, the 4- di-tert-butyl-phenyl) phosphite esters of synthesis of comparative example 5
With embodiment 9 difference lies in：Added catalyst is ethanol amine, other steps and operations and implementation in step (1)
Example 9 is identical.
The yield of final product is 88.2%, purity 89.5%.
As a result it tests
It can be obtained using the preparation method provided by the invention for preparing antioxidant 168, production by above-mentioned experimental result
Product yield may be up to 95% or more, and purity may be up to 98% or more.In the present invention by adjusting the type of catalyst, using negative
Supported catalyst, and by using currently preferred carrier and activated centre, improper remark activity is made to greatly increase, promote reaction
Progress, the present invention also had adjusted in implementation process solvent type make reaction carry out more thoroughly；By the number of comparative example
According to can be seen that when changing the solvent type in the present invention (comparative example 1-3), apparent drop all has occurred in yield and purity
It is low；When changing reactant 2, when the ratio between the amount of substance of 4- di-tert-butylphenols and phosphorus trichloride (comparative example 4), the yield of product and
Purity can be also substantially reduced；The catalyst used in the embodiment of the present invention is loaded catalyst, and this hair is used in combination
Bright disclosed solvent, can significantly improve the yield and purity of antioxidant 168, and the catalysis used in comparative example 5
Agent is conventional base catalysts, and finally obtained product yield can only achieve 88.2%, and purity liquid is compared with the embodiment of the present invention
It reduces, can only achieve 89.5%.
The pilot experiment of antioxidant 168 is carried out according to the method provided in 1-9 of the embodiment of the present invention, it is finally obtained
For the yield of antioxidant 168 still 90% or more, purity is up to 98% or more, is higher than existing level, is the work of antioxidant
Industryization produces the possibility provided in enormous quantities.
Only as described above, only the preferred embodiments of the invention, when the model that cannot limit implementation of the invention with this
It encloses, i.e., generally according to simple equivalent changes and modifications made by the content recorded in the claims in the present invention and description of the invention,
All it is still covered by the claims of the invention.It is searched in addition, abstract part and title are intended merely to auxiliary patent document
It seeks and being used, not be used for limiting the interest field of the present invention.
Claims (10)
1. a kind of method of three (2,4- di-tert-butyl-phenyl) phosphite esters of synthesis, it is characterised in that：The method includes following
Step：
(1) 2,4- di-tert-butylphenols, catalysts and solvents are added in three-necked flask first, are added rotor afterwards, and by returned cold
Solidifying pipe, thermometer and dropping funel are fixed on three-necked flask；
(2) three-necked flask that reactant is housed in step (1) is placed under the conditions of oil bath and is slowly heated up, temperature is made to rise to 40-45
DEG C, obtain reaction solution；
(3) phosphorus trichloride is added dropwise into the reaction solution of step (2), control drop speed makes its 10-15min be added dropwise, continues to heat up
To 90-100 DEG C, insulation reaction 30-40min, vacuum distillation removes solvent, is recrystallized to get to product with n-hexane.
2. preparation method according to claim 1, it is characterised in that：It is 1: 0.01- that solvent, which is the ratio of volume, in step (1)
60 methanol and the mixed solution of toluene.
3. preparation method according to claim 1, it is characterised in that：2,4- di-tert-butylphenols and solvent in step (1)
Mass volume ratio is g/mL: 1: 40-60.
4. preparation method according to claim 1, it is characterised in that：It is 1 that solvent for use, which is volume ratio, in step (1):
0.01 methanol and toluene mixed solution.
5. preparation method according to claim 1, it is characterised in that：It is 1: 60 that solvent for use, which is volume ratio, in step (1)
Methanol and toluene mixed solution.
6. preparation method according to claim 1, it is characterised in that：It is 1: 30 that solvent for use, which is volume ratio, in step (1)
Methanol and toluene mixed solution.
7. preparation method according to claim 1, it is characterised in that：Step (1) and raw material 2 in step (3), bis- tertiary fourths of 4-
The ratio between amount of substance of base phenol and phosphorus trichloride is 1-1.5: 0.5.
8. preparation method according to claim 1, it is characterised in that：Slowly heating rate is to rise for every ten minutes to step (2)
It is 3-5 degrees Celsius high.
9. preparation method according to claim 1, it is characterised in that：The addition of catalyst is 2,4- bis- in step (1)
The 0.15-0.2% of tert-butyl phenol quality.
10. preparation method according to claim 1, it is characterised in that：Used catalyst is support type alkalinity in step (1)
Catalyst；
The carrier of the loaded catalyst is diatomite, SiO2-Al2O3, zeolite molecular sieve and one kind in atlapulgite or
It is several；
The activated centre of the loaded catalyst is DMF, hexamethylene, triphenyl phosphorus, n,N-Dimethylaniline, DMAP and pyrrole
One or more of pyridine.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798325A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Preparation method of antioxidant product with stable performance |
| CN104387417A (en) * | 2014-11-20 | 2015-03-04 | 茂名市科达化工有限公司 | Preparation method of environment-friendly antioxidant triphosphite |
| CN104744506A (en) * | 2014-05-22 | 2015-07-01 | 安徽时联特种溶剂股份有限公司 | Method for preparing tri-(2, 4-di-tertiary butyl phenyl) phosphite ester antioxidant |
| CN106220681A (en) * | 2016-07-22 | 2016-12-14 | 上海石化西尼尔化工科技有限公司 | A kind of preparation method of phosphite antioxidant |
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2018
- 2018-04-04 CN CN201810298321.2A patent/CN108467406A/en active Pending
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|---|---|---|---|---|
| CN101798325A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Preparation method of antioxidant product with stable performance |
| CN104744506A (en) * | 2014-05-22 | 2015-07-01 | 安徽时联特种溶剂股份有限公司 | Method for preparing tri-(2, 4-di-tertiary butyl phenyl) phosphite ester antioxidant |
| CN104387417A (en) * | 2014-11-20 | 2015-03-04 | 茂名市科达化工有限公司 | Preparation method of environment-friendly antioxidant triphosphite |
| CN106220681A (en) * | 2016-07-22 | 2016-12-14 | 上海石化西尼尔化工科技有限公司 | A kind of preparation method of phosphite antioxidant |
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