CN108250240A - A kind of 626 synthesis technology of antioxidant - Google Patents
A kind of 626 synthesis technology of antioxidant Download PDFInfo
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- CN108250240A CN108250240A CN201810217614.3A CN201810217614A CN108250240A CN 108250240 A CN108250240 A CN 108250240A CN 201810217614 A CN201810217614 A CN 201810217614A CN 108250240 A CN108250240 A CN 108250240A
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- butyl
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- 239000003963 antioxidant agent Substances 0.000 title abstract description 34
- 230000003078 antioxidant effect Effects 0.000 title abstract description 33
- 238000005516 engineering process Methods 0.000 title description 5
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 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 50
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000035484 reaction time Effects 0.000 claims abstract description 19
- 238000010189 synthetic method Methods 0.000 claims abstract description 17
- RGASRBUYZODJTG-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C RGASRBUYZODJTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 8
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 37
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 13
- -1 diphosphorous acid ester Chemical class 0.000 claims description 12
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 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 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 4
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 56
- 230000007062 hydrolysis Effects 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 32
- 238000002360 preparation method Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- 230000003301 hydrolyzing effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000008301 phosphite esters Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- GQJWRLJHGJGGIP-UHFFFAOYSA-N 1,1-dichloro-2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)C(O)(Cl)Cl GQJWRLJHGJGGIP-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004425 Makrolon Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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)
Abstract
The invention discloses a kind of antioxidant 626, i.e., the synthetic method of bis- (2,4 di-tert-butyl-phenyl) pentaerythritol diphosphites.The present invention includes the following steps：First, catalyst is added in selected solvent, starts stirring, then add in phosphorus trichloride, be passed through nitrogen, continue to start stirring, pentaerythrite is then added dropwise, the hydrogen chloride gas of generation is absorbed with sodium hydroxide solution；After reaction product purification, pentaerthiyldichlorodiphosphite solution is obtained；Then the solution is added drop-wise in 2,4 DI-tert-butylphenol compounds aqueous solutions, is passed through nitrogen gas stirring, the hydrogen chloride gas for reacting generation is absorbed with sodium hydroxide solution, and reaction product obtains product after purification.Low in raw material price employed in the present invention is reacted and is easily carried out, and side reaction is few, product purity is high, and the reaction time is short, and the storage time of product is long, and product has good hydrolysis resistance and stability, while the yield of product is also very high.
Description
Technical field
The present invention relates to a kind of synthetic methods of antioxidant, and in particular to a kind of antioxidant 626, i.e., bis- (2,4- bis- tertiary fourths
Base phenyl) pentaerythritol diphosphites methodology of organic synthesis.
Background technology
Phosphite ester kind antioxidant is a kind of important auxiliary antioxidant, as hydroperoxides distintegrant and dissociate
The agent for capturing of base, plays antioxidation in the polymer, and effectively prevents polymer discoloration, especially with Hinered phenols antioxygen
Agent is used in combination, and can generate fabulous synergistic effect.Therefore, volume of production and marketing rapid growth, global antioxidant increase every year in recent years
Long rate is about 5.5%, and the average growth rate per annum of the kind antioxidant is about 7.0%.
Antioxidant 626 is a kind of efficient pentaerythritol diphosphites class auxiliary antioxidant, and chemical name is bis- (2,4.
Di-tert-butyl-phenyl) pentaerythritol diphosphites, molecular formula C33H50O6P2, molecular weight 604, structural formula is：
The fusing point of bis- (2,4. di-tert-butyl-phenyl) pentaerythritol diphosphites is 170~180 DEG C, and appearance is tied for white
Brilliant particle or powder.Its phosphorus content is high and antioxygenic activity is big, and performance is better than other phosphite ester kind antioxidants, in production and processing
Dosage be only common phosphite kind antioxidant half.It can assign the excellent colour stability of plastic products and light is stablized
Property, the processing performance of plastics is made to significantly improve, and energy partial alternative top grade antioxidant and ultra-violet absorber are moulded to reduce
The cost of material of material.Polyethylene, polypropylene, polystyrene, polychlorostyrene are widely used in after antioxidant 626 and phenols primary antioxidant compounding
The high molecular materials such as ethylene, polyester, makrolon.Bis- (2,4. di-tert-butyl-phenyl) pentaerythritol diphosphites can decompose
The polymer hydroperoxides generated in high molecular material thermo-oxidative ageing chain reaction, so as to interrupt or weaken the heat of high molecular material
Oxygen aging process, while also be able to Hinered phenols primary antioxidant be made to obtain from thereon after free radical is captured as hydrogen atom donor
It obtains hydrogen atom and regenerates, generate significant heterogeneity synergistic effect, and therefore become the stabilizer of polyolefin processing.It is special
It is not the processing for polypropylene at high temperature, xanthochromia and control melt index can be inhibited to change in a certain range, so as to
The performance after processing is ensure that, with good development prospect.
At present, the synthetic route master of related bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites in the prior art
There are following a few classes：The first kind be using tris phosphite as starting material, under high temperature, high vacuum, tris phosphite and 2,4-
DI-tert-butylphenol compounds and pentaerythrite carry out ester exchange reaction, and by post-processing to obtain product, by-product is phenol in this method, secondary
Phenol product can recycle, however, phenol micro in product is difficult to remove, product easily turns to be yellow, limits it and eating
The application of product, field of medicaments；Second class be using phosphorus trichloride as starting material, it is anti-with pentaerythrite and 2,4-DTBP
Should, by post-processing to obtain product.Third class, it is anti-that irgasfos 168 carries out under high temperature, condition of high vacuum degree transesterification with pentaerythrite
It should, you can generation antioxidant 626, while by-product 2,4-DTBP, by-product can be as the raw materials for production of irgasfos 168
It recycles, in the production method, simple process, but reflect harshness, cost of material is higher.
There are side reaction is more, product purification process is complicated, the hydrolysis resistance of finished product is poor, and product yield for existing technique
The shortcomings of not high.Such as a kind of antioxidant 626 is disclosed in Chinese patent application 200810027160.X, i.e., bis- (2,4- bis- uncles
Butyl phenyl) pentaerythritol diphosphites synthetic method, although its low in raw material price, react easily carry out, its make
The product hydrolysis resistance obtained is very poor；For another example《Chemical Engineering Technology and exploitation》The 2nd phase of volume 40, " 626 new technique for synthesizing of antioxidant was ground
Study carefully " in refer to a kind of synthetic method of antioxidant 626, although avoiding the generation of side reaction in reaction process, its react
Time is long, and product hydrolysis resistance obtained is very poor, and yield is relatively low, and the purity of product is relatively low.
Invention content
It is an object of the invention to overcome shortcoming of the existing technology, propose a kind of antioxidant 626, i.e., bis- (2,4- bis-
Tert-butyl-phenyl) pentaerythritol diphosphites synthetic method, come reach the reaction time is short, product purity is high, high income and
Products obtained therefrom has the effect of good hydrolysis resistance.
To achieve these goals, the present invention provides following technical solutions：
A kind of synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, includes the following steps：
(1) catalyst is added in a solvent, using mixing speed as 600~900 revs/min, stirring 5~after ten minutes, it adds in
Phosphorus trichloride is passed through nitrogen, after being stirred for 20~30 minutes, is subsequently added into pentaerythrite, is reacted at a temperature of 50~100 DEG C
0.5~6h obtains solution A；The hydrogen chloride gas of generation is absorbed with sodium hydroxide solution；
(2) it is 60~85 DEG C in temperature by the solution A obtained by step (1), pressure is the condition of -0.003~0.009Mpa
Under be evaporated under reduced pressure, unreacted phosphorus trichloride is distilled out, after filtering out unreacted pentaerythrite, you can obtain dichloro
For pentaerythritol diphosphites solution；
(3) the product pentaerthiyldichlorodiphosphite solution of gained in step (2) is added drop-wise to 2,4-, bis- tertiary fourths
In base phenol solution, it being passed through nitrogen gas stirring, mixing speed is 600~900 revs/min, react 0.5 at a temperature of 40~85 DEG C~
3.5h, the hydrogen chloride gas for reacting generation are absorbed with sodium hydroxide solution；
(4) it is 90~140 DEG C in temperature, pressure is evaporated under reduced pressure out solvent under conditions of being -0.01~0.07Mpa, then
Suitable isopropanol is added in, stirred crystallization goes out product；
(5) product obtained by step (4) is filtered to obtain the solid powder of white, as bis- (2,4- di-t-butyls
Phenyl) pentaerythritol diphosphites.
The one kind of solvent in dimethylbenzene, toluene and hexamethylene in the step (1).
Further, the one kind of the solvent in the step (1) in toluene and hexamethylene.
Catalyst in the step (1) is selected from triethylamine, DMF (n,N-Dimethylformamide), tetraethylammonium bromide, ten
One or more of eight amine, tetramethyl ammonium chloride, tetra-n-butyl ammonium bromide and DMAP (4-dimethylaminopyridine).
Further, the catalyst in the step (1) is selected from triethylamine, tetraethylammonium bromide, octadecylamine, tetra-n-butyl
One or more of ammonium bromide and DMAP (4-dimethylaminopyridine).
Further, the catalyst in the step (1) is selected from tetraethylammonium bromide, tetra-n-butyl ammonium bromide and DMAP
One or more of (4-dimethylaminopyridine).
By weight, dosage is the 0.3%~3% of pentaerythrite to catalyst in the step (1).
Preferably, by weight, dosage is the 1%~2.5% of pentaerythrite to the catalyst in the step (1).
The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is 2.50~2.85:1.
Further, the molar ratio of the phosphorus trichloride in the step (1) and pentaerythrite is preferably 2.65~2.80:1.
Reaction temperature in the step (1) is preferably 60~90 DEG C.
Reaction time in the step (1) is preferably 2~4h.
The molar ratio of 2,4-DTBP and pentaerthiyldichlorodiphosphite in the step (3) is
2.20~2.45：1.
Further, the 2,4-DTBP in the step (3) and pentaerthiyldichlorodiphosphite
Molar ratio is preferably 2.25~2.35：1.
Reaction temperature in the step (3) is preferably 50~75 DEG C.
Reaction time in the step (3) is preferably 1~3h.
A concentration of 0.1~1.2mol/L of 2,4-DTBP aqueous solution in the step (3)；Preferably 0.3
~0.9mol/L；Further preferably 0.5~0.7mol/L.
Compared with prior art, beneficial effects of the present invention are：Low in raw material price employed in the present invention, reaction are held
It easily carries out, side reaction is few, product purity is high, and the reaction time is short, and the storage time of product is long, and product has good resistant to hydrolysis
Ability and stability, while the yield of product is also very high.
Specific embodiment
A kind of synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites of embodiment 1, including following
Step：
(1) tetraethylammonium bromide is added in toluene, by weight, the dosage of tetraethylammonium bromide is pentaerythrite
2%, using mixing speed as 800 revs/min, after stirring 8 minutes, phosphorus trichloride is added in, nitrogen is passed through, after being stirred for 25 minutes, connects
Addition pentaerythrite, the molar ratio of phosphorus trichloride and pentaerythrite is 2.75:1.3h is reacted at a temperature of 80 DEG C, obtains solution
A；The hydrogen chloride gas of generation is absorbed with sodium hydroxide solution；
(2) it is 70 DEG C in temperature by the solution A obtained by step (1), pressure carries out decompression steaming under conditions of being 0.006Mpa
It evaporates, distills out unreacted phosphorus trichloride, after filtering out unreacted pentaerythrite, you can obtain dichloro pentaerythritol two
Phosphite ester solution；
(3) the product pentaerthiyldichlorodiphosphite solution of gained in step (2) is added drop-wise to a concentration of
In the 2,4-DTBP aqueous solution of 0.6mol/L, 2,4-DTBP and pentaerthiyldichlorodiphosphite
Molar ratio be 2.30：1, nitrogen gas stirring is passed through, mixing speed is 800 revs/min, and 2h, reaction generation are reacted at a temperature of 60 DEG C
Hydrogen chloride gas absorbed with sodium hydroxide solution；
(4) it is 100 DEG C in temperature, pressure is evaporated under reduced pressure out solvent under conditions of being 0.06Mpa, then adds in suitable different
Propyl alcohol, stirred crystallization go out product；
(5) product obtained by step (4) is filtered to obtain the solid powder of white, as bis- (2,4- di-t-butyls
Phenyl) pentaerythritol diphosphites.
Embodiment 2
With embodiment 1 only difference is that：Solvent in the step (1) is hexamethylene.
Embodiment 3
With embodiment 1 only difference is that：Solvent in the step (1) is dimethylbenzene.
Embodiment 4
With embodiment 1 only difference is that：Catalyst in the step (1) is tetra-n-butyl ammonium bromide.
Embodiment 5
With embodiment 1 only difference is that：Catalyst in the step (1) is DMAP (4-dimethylaminopyridine).
Embodiment 6
With embodiment 1 only difference is that：Catalyst in the step (1) is tetramethyl ammonium chloride and tetra-n-butyl
Two kinds of ammonium bromide, mass ratio 1：1.
Embodiment 7
With embodiment 1 only difference is that：Catalyst in the step (1) is tetra-n-butyl ammonium bromide and DMAP
(4-dimethylaminopyridine), mass ratio 1：1.
Embodiment 8
With embodiment 1 only difference is that：Catalyst in the step (1) is triethylamine.
Embodiment 9
With embodiment 1 only difference is that：Catalyst in the step (1) is octadecylamine.
Embodiment 10
With embodiment 1 only difference is that：Catalyst in the step (1) is DMF (n,N-Dimethylformamide).
Embodiment 11
With embodiment 1 only difference is that：Catalyst tetraethylammonium bromide in the step (1), by weight,
Dosage is the 1% of pentaerythrite.
Embodiment 12
With embodiment 1 only difference is that：Catalyst tetraethylammonium bromide in the step (1), by weight,
Dosage is the 2.5% of pentaerythrite.
Embodiment 13
With embodiment 1 only difference is that：Catalyst tetraethylammonium bromide in the step (1), by weight,
Dosage is the 0.3% of pentaerythrite.
Embodiment 14
With embodiment 1 only difference is that：Catalyst tetraethylammonium bromide in the step (1), by weight,
Dosage is the 3% of pentaerythrite.
Embodiment 15
With embodiment 1 only difference is that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is
2.65:1。
Embodiment 16
With embodiment 1 only difference is that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is
2.80:1。
Embodiment 17
With embodiment 1 only difference is that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is
2.50:1。
Embodiment 18
With embodiment 1 only difference is that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is
2.85:1。
Embodiment 19
With embodiment 1 only difference is that：Reaction temperature in the step (1) is 60 DEG C.
Embodiment 20
With embodiment 1 only difference is that：Reaction temperature in the step (1) is 90 DEG C.
Embodiment 21
With embodiment 1 only difference is that：Reaction temperature in the step (1) is 50 DEG C.
Embodiment 22
With embodiment 1 only difference is that：Reaction temperature in the step (1) is 100 DEG C.
Embodiment 23
With embodiment 1 only difference is that：Reaction time in the step (1) is 2h.
Embodiment 24
With embodiment 1 only difference is that：Reaction time in the step (1) is 4h.
Embodiment 25
With embodiment 1 only difference is that：Reaction time in the step (1) is 0.5h.
Embodiment 26
With embodiment 1 only difference is that：Reaction time in the step (1) is 6h.
Embodiment 27
With embodiment 1 only difference is that：2,4-DTBP and dichloro- Ji Wusi in the step (3)
The molar ratio of alcohol diphosphites is 2.25：1.
Embodiment 28
With embodiment 1 only difference is that：2,4-DTBP and dichloro- Ji Wusi in the step (3)
The molar ratio of alcohol diphosphites is 2.35：1.
Embodiment 29
With embodiment 1 only difference is that：2,4-DTBP and dichloro- Ji Wusi in the step (3)
The molar ratio of alcohol diphosphites is 2.20：1.
Embodiment 30
With embodiment 1 only difference is that：2,4-DTBP and dichloro- Ji Wusi in the step (3)
The molar ratio of alcohol diphosphites is 2.45：1.
Embodiment 31
With embodiment 1 only difference is that：2,4-DTBP aqueous solution in the step (3) it is a concentration of
0.3mol/L。
Embodiment 32
With embodiment 1 only difference is that：2,4-DTBP aqueous solution in the step (3) it is a concentration of
0.9mol/L。
Embodiment 33
With embodiment 1 only difference is that：2,4-DTBP aqueous solution in the step (3) it is a concentration of
0.1mol/L。
Embodiment 34
With embodiment 1 only difference is that：2,4-DTBP aqueous solution in the step (3) it is a concentration of
1.2mol/L。
Embodiment 35
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 50 DEG C.
Embodiment 36
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 75 DEG C.
Embodiment 37
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 40 DEG C.
Embodiment 38
With embodiment 1 only difference is that：Reaction time in the step (3) is 85 DEG C.
Embodiment 39
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 1h.
Embodiment 40
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 3h.
Embodiment 41
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 0.5h.
Embodiment 42
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 3.5h.
Comparative example 1
With embodiment 1 only difference is that：Catalyst tetraethylammonium bromide in the step (1), by weight,
Dosage is the 0.1% of pentaerythrite.
Comparative example 2
With embodiment 1 only difference is that：Catalyst tetraethylammonium bromide in the step (1), by weight,
Dosage is the 5% of pentaerythrite.
Comparative example 3
With embodiment 1 only difference is that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is
2.35:1。
Comparative example 4
With embodiment 1 only difference is that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is
2.95:1。
Comparative example 5
With embodiment 1 only difference is that：Reaction temperature in the step (1) is 45 DEG C.
Comparative example 6
With embodiment 1 only difference is that：Reaction temperature in the step (1) is 110 DEG C.
Comparative example 7
With embodiment 1 only difference is that：Reaction time in the step (1) is 0.3h.
Comparative example 8
With embodiment 1 only difference is that：Reaction time in the step (1) is 7h.
Comparative example 9
With embodiment 1 only difference is that：2,4-DTBP and dichloro- Ji Wusi in the step (3)
The molar ratio of alcohol diphosphites is 2.05：1.
Comparative example 10
With embodiment 1 only difference is that：2,4-DTBP and dichloro- Ji Wusi in the step (3)
The molar ratio of alcohol diphosphites is 2.55：1.
Comparative example 11
With embodiment 1 only difference is that：2,4-DTBP aqueous solution in the step (3) it is a concentration of
0.05mol/L。
Comparative example 12
With embodiment 1 only difference is that：2,4-DTBP aqueous solution in the step (3) it is a concentration of
1.5mol/L。
Comparative example 13
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 35 DEG C.
Comparative example 14
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 95 DEG C.
Comparative example 15
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 0.3h.
Comparative example 16
With embodiment 1 only difference is that：Reaction temperature in the step (3) is 4.5h.
As a result it tests
If antioxidant 626 is exposed in wet environment, will absorb moisture causes to hydrolyze, and acid value increases, while weight
Increase.It is typically to increase along with the increase of the acid value of antioxidant 626 that weight, which increases,.The increased size of acid value, can evaluate
The hydrolytic stability effect of antioxidant 626.Under identical environmental condition, with the extension of exposure duration, acid value variation is got over
Small, hydrolytic stability is higher；Conversely, acid value variation is bigger, hydrolytic stability is lower.
(1) test result of embodiment 1-3 is listed in the table below：
As seen from the above table, using the preparation method provided by the invention for preparing antioxidant 626, in the step (1)
One kind in dimethylbenzene, toluene and hexamethylene of solvent, product yield obtained is up to more than 99%, and purity is also up to
99%；If antioxidant 626 is exposed in wet environment, under identical environmental condition, with the extension of exposure duration, production
The acid value variation of product is smaller, and it is good to illustrate that product made from the preparation method using antioxidant 626 of the present invention has
Hydrolytic stability, equally can it can be seen from the table, when solvent is toluene, the yield highest of product obtained, purity highest,
Hydrolytic stability is also best simultaneously.
(2) test result of embodiment 1 and embodiment 4-10 is listed in the table below：
As shown above, during the preparation method of antioxidant 626 of the present invention, in the step (1)
Catalyst is being selected from triethylamine, DMF (n,N-Dimethylformamide), tetraethylammonium bromide, octadecylamine, tetramethyl ammonium chloride, four just
When one or more of butylammonium bromide and DMAP (4-dimethylaminopyridine), product yield obtained can reach 95% with
On, the purity of product can reach more than 96%, and product has good hydrolytic stability, wherein, embodiment 1, reality
A 4-7 is applied as preferred embodiment.
(3) test result of embodiment 1, embodiment 11-14 and comparative example 1-2 is listed in the table below：
As can be seen from the above table, in the preparation method of antioxidant 626 of the present invention, in the step (1)
By weight, when its dosage is the 0.3%~3% of pentaerythrite, product obtained not only high income, purity is big for catalyst,
The hydrolysis resistance of product is also very strong, and when beyond the range, yield and purity are substantially reduced, while hydrolysis resistance is apparent
It reduces.
(4) test result of embodiment 1, embodiment 15-18 and comparative example 3-4 is listed in the table below：
In preparation method described in embodiment 1 and embodiment 15-18, phosphorus trichloride and season penta in the step (1)
The molar ratio of tetrol is 2.50~2.85:1；In preparation method described in comparative example 3, the phosphorus trichloride in the step (1)
Molar ratio with pentaerythrite is 2.35:1, in the preparation method described in comparative example 4, the phosphorus trichloride in the step (1)
Molar ratio with pentaerythrite is 2.95:1；It can be found that when the molar ratio of phosphorus trichloride and pentaerythrite is 2.50~2.85:
When between 1, the yield and purity of product are very high, reach more than 90%, and the hydrolysis resistance of product is very strong.
(5) test result of embodiment 1, embodiment 19-22 and comparative example 5-6 is listed in the table below：
In preparation method described in embodiment 1 and embodiment 19-22, in the step (1) in the step (1)
Reaction temperature is 50~100 DEG C；In preparation method described in comparative example 5, the reaction temperature in the step (1) is 45 DEG C,
In preparation method described in comparative example 6, the reaction temperature in the step (1) is 110 DEG C, carries out reaction system at this temperature
The yield and purity of the product obtained will significantly be less than embodiment 1 and embodiment 19-22；Therefore, reaction temperature it is unsuitable excessively high or
It is too low, reaction temperature only when between 50~100 DEG C of the present invention, the yield and purity of product reach 90% with
On, and the hydrolysis resistance of product is very strong.
(6) test result of embodiment 1, embodiment 23-26 and comparative example 7-8 is listed in the table below：
In preparation method described in embodiment 1 and embodiment 23-26, reaction time in the step (1) for 0.5~
6h；In preparation method described in comparative example 7, reaction time in the step (1) is 0.3h, the system described in comparative example 8
In Preparation Method, reaction time in the step (1) is 7h, it is found that the reaction time is unsuitable long or too short, during reaction
Between only between 0.5~6h of the present invention when, the high income and purity of product are high, and product has good water resistant
Solve performance.
(7) test result of embodiment 1, embodiment 27-30 and comparative example 9-10 is listed in the table below：
In preparation method described in embodiment 1 and embodiment 27-30,2, the 4- di-tert-butyls in the step (3)
The molar ratio of phenol and pentaerthiyldichlorodiphosphite is 2.20~2.45：1；The high income of product obtained and pure at this time
Degree is high, and product has good hydrolytic Resistance.In embodiment 9 and embodiment 10,2, the 4- bis- in the step (3)
The molar ratio of tert-butyl phenol and pentaerthiyldichlorodiphosphite is respectively 2.05：1 and 2.55：1, product obtained
Performance be not so good as 1 He of embodiment
Embodiment 27-30.
(8) test result of embodiment 1, embodiment 31-34 and comparative example 11-12 is listed in the table below：
In preparation method described in embodiment 1, embodiment 31-34, the 2,4-DTBP in the step (3)
A concentration of 0.1~1.2mol/L of aqueous solution, no matter product purity obtained or yield are greater than comparative example 11- at this time
12, while its hydrolytic Resistance is also fine.
(9) test result of embodiment 1, embodiment 35-38 and comparative example 13-14 is listed in the table below：
In the preparation method of antioxidant 626 in embodiment 1 and embodiment 35-38, the reaction temperature in the step (3)
It is 40~85 DEG C to spend, as can be seen from the above table, in this temperature range the yield of product obtained and purity reach 90% with
On, and the hydrolytic Resistance of product is very strong, as can be seen from the data in the table, further, temperature is preferably 50~75 DEG C.It is and right
The performance of product is relatively poor made from ratio 13-14, illustrates in the method for the present invention for preparing antioxidant 626, institute
The reaction temperature stated in step (3) is unsuitable too high or too low.
(10) test result of embodiment 1, embodiment 39-42 and comparative example 15-16 is listed in the table below：
In the preparation method of antioxidant 626 in embodiment 1 and embodiment 39-42, during reaction in the step (3)
Between for 0.5~3.5h, as can be seen from the above table, in the range of this time the yield of product obtained and purity reach 93% with
On, and the hydrolytic Resistance of product is very strong, and the performance of product made from comparative example 15-16 is relatively poor, illustrates this hair
In the bright method for preparing antioxidant 626, the reaction time in the step (3) is unsuitable too high or too low.
Only as described above, only the preferred embodiments of the invention, when the model that implementation of the invention cannot be limited with this
It encloses, i.e., generally according to equivalent changes and modifications simple 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, be not used for limiting the interest field of the present invention.
Claims (10)
1. a kind of synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, it is characterised in that：Including with
Lower step：
(1) catalyst is added in a solvent, using mixing speed as 600~900 revs/min, stirring 5~after ten minutes, add in trichlorine
Change phosphorus, be passed through nitrogen, after being stirred for 20~30 minutes, be subsequently added into pentaerythrite, at a temperature of 50~100 DEG C react 0.5~
6h obtains solution A；The hydrogen chloride gas of generation is absorbed with sodium hydroxide solution；
(2) by the solution A obtained by step (1) temperature be 60~85 DEG C, pressure be -0.003~0.009Mpa under conditions of into
Row vacuum distillation, distills out unreacted phosphorus trichloride, after filtering out unreacted pentaerythrite, you can obtain dichloro- season
Penta tetrol diphosphorous acid ester solution；
(3) the product pentaerthiyldichlorodiphosphite solution of gained in step (2) is added drop-wise to a concentration of 0.3mol/L
2,4-DTBP solution in, be passed through nitrogen gas stirring, mixing speed is 600~900 revs/min, in 40~85 DEG C of temperature
0.5~3.5h of lower reaction, the hydrogen chloride gas for reacting generation are absorbed with sodium hydroxide solution；
(4) it is 90~140 DEG C in temperature, pressure is evaporated under reduced pressure out solvent under conditions of being -0.01~0.07Mpa, then adds in
Suitable isopropanol, stirred crystallization go out product；
(5) product obtained by step (4) is filtered to obtain the solid powder of white, as bis- (2,4- di-tert-butyl-phenyls)
Pentaerythritol diphosphites.
2. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：The one kind of solvent in dimethylbenzene, toluene and hexamethylene in the step (1).
3. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：Catalyst in the step (1) be selected from triethylamine, DMF (n,N-Dimethylformamide), tetraethylammonium bromide,
One or more of octadecylamine, tetramethyl ammonium chloride, tetra-n-butyl ammonium bromide and DMAP (4-dimethylaminopyridine).
4. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：By weight, dosage is the 0.3%~3% of pentaerythrite to catalyst in the step (1).
5. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：The molar ratio of phosphorus trichloride and pentaerythrite in the step (1) is 2.50~2.85:1.
6. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：Reaction temperature in the step (1) is 60~90 DEG C；Reaction time is 2~4h.
7. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：The molar ratio of 2,4-DTBP and pentaerthiyldichlorodiphosphite in the step (3) is
2.20~2.45：1.
8. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：Reaction temperature in the step (3) is 50~75 DEG C；Reaction time is 1~3h.
9. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：A concentration of 0.1~1.2mol/L of 2,4-DTBP aqueous solution in the step (3).
10. the synthetic method of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites according to claim 1,
It is characterized in that：A concentration of 0.3~0.9mol/L of 2,4-DTBP aqueous solution in the step (3).
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| CN109232652A (en) * | 2018-11-16 | 2019-01-18 | 锦州英诺威科技服务有限公司 | A kind of preparation method of bis- (2,4- dicumylphenyl) pentaerythritol diphosphites |
| CN110563556A (en) * | 2019-09-26 | 2019-12-13 | 黄河三角洲京博化工研究院有限公司 | method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor |
| CN112898916A (en) * | 2021-01-28 | 2021-06-04 | 江苏极易新材料有限公司 | Preparation method of composite antioxidant |
| CN113004331A (en) * | 2021-03-08 | 2021-06-22 | 江苏极易新材料有限公司 | Synthetic method of antioxidant |
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Application publication date: 20180706 |