CN115304638B - Synthesis method of 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite - Google Patents
Synthesis method of 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite Download PDFInfo
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- -1 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite Chemical compound 0.000 title claims abstract description 18
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 230000005496 eutectics Effects 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 19
- PDNNNTTZJOPATP-UHFFFAOYSA-N dihydroxyphosphanyl tridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OP(O)O PDNNNTTZJOPATP-UHFFFAOYSA-N 0.000 claims abstract description 14
- DGQFNPWGWSSTMN-UHFFFAOYSA-N 2-tert-butyl-4-[4-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1CCCCC1=CC(C(C)(C)C)=C(O)C=C1C DGQFNPWGWSSTMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 54
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 39
- 235000019743 Choline chloride Nutrition 0.000 claims description 39
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 39
- 229960003178 choline chloride Drugs 0.000 claims description 39
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 claims description 20
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 7
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- 239000000047 product Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000012467 final product Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical group CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 1
- GIATZHZBSIMOEE-UHFFFAOYSA-N P(O)(O)O.P(O)(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 Chemical compound P(O)(O)O.P(O)(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 GIATZHZBSIMOEE-UHFFFAOYSA-N 0.000 description 1
- RRFWWSOELBTKEK-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC Chemical compound P(O)(O)O.P(O)(O)O.C(CCCCCCCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCCCCCCC RRFWWSOELBTKEK-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ZWRWUGGYDBHANL-UHFFFAOYSA-N butyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCC)OC1=CC=CC=C1 ZWRWUGGYDBHANL-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 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
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-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
- C07F9/06—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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite. The method adopts a eutectic solvent [ ChCl ] [ TsOH ] or [ ChCl ] [ MA ] as a solvent and a catalyst, and prepares an intermediate 4,4 '-butylene bis (3-methyl-6-tertiary butyl phenol) by a microwave synthesis method, and synthesizes 4,4' -butylene bis- (3-methyl-6-tertiary butyl phenyl) -tetra (tridecyl) diphosphite from the intermediate. The method provided by the invention has the advantages of high intermediate yield and high product purity, so that the quality of the final product is good. The synthesis method is environment-friendly, and the eutectic solvent can be recycled and is suitable for industrial application.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for synthesizing 4,4' -butylene-bis- (3-methyl-6-tertiary butylbenzene) -tetra (tridecyl) diphosphite.
Background
Phosphite antioxidant is represented by structural formula(R 1 、R 3 Alkyl, aryl, substituted aryl, which may be the same or different, or may be cyclic), is an auxiliary antioxidant that acts as a hydroperoxide decomposer and a radical scavenger in the polymer to exert an antioxidant effect, and is often used in combination with hindered phenols, generally not alone. Phosphite antioxidants include: triphenyl phosphite, trisnonyl phosphite, monobutyl diphenyl phosphite, tris (nonyl)Alkylphenol) phosphite, phenyl tris (2, 4-di-tert-butyl) phosphite, trioctyl phosphite, ethyl bis (2-methyl-4, 6-bis (1, 3-dimethylethyl) phenyl) phosphite, dioctadecyl pentaerythritol bisphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol bisphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol bisphosphite, 4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) bisphosphite, and the like.
Among them, 4' -butylene bis- (3-methyl-6-tertiary butylbenzene group) -tetra (tridecyl) diphosphite has excellent property and strong market demand. It is generally prepared by the following method: 3-methyl-6-tertiary butyl phenol and n-butyl aldehyde are synthesized into an intermediate 4,4' -butylene bis (3-methyl-6-tertiary butyl phenol) in the presence of alkali and a catalyst, and the intermediate is obtained by reacting the intermediate with triphenyl phosphite and tridecyl alcohol in the presence of alkali, and removing low-boiling impurities and phenol through distillation. Wherein the purity of the intermediate 4,4 '-butylidenebis (3-methyl-6-tert-butylphenol) is related to the quality of 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite. Intermediate 4,4' -butylene bis (3-methyl-6-tert-butylphenol) (BBM) is also an antioxidant, and as such, US2970151, US28318974, US2822404, JP2007269711A, JP2012136548A, CN108586206A, CN104591972A and the like disclose the use of hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like as catalysts, but the yield and purity of the product are not high, and the post-treatment is troublesome and the amount of three wastes is large.
Thus, there is a need to develop more methods capable of efficiently synthesizing 4,4' -butylidenebis- (3-methyl-6-t-butylphenyl) -tetra (tridecyl) diphosphite.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a method for preparing 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite, which uses 3-methyl-6-tert-butylphenol and n-butyraldehyde as raw materials, uses eutectic solvent containing p-toluenesulfonic acid or malonic acid as solvent and catalyst, synthesizes intermediate 4,4' -butylidenebis- (3-methyl-6-tert-butylphenol) under microwave radiation, and then synthesizes 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite.
The eutectic solvent (DES) is a eutectic mixture formed by intermolecular hydrogen bonds from a Hydrogen Bond Donor (HBD) and a Hydrogen Bond Acceptor (HBA) with a melting point below 100 ℃. The HBA includes quaternary ammonium salts, quaternary phosphonium salts, etc., and the HBD includes amides, alcohols, carboxylic acids, sulfonic acids, etc. DES can be used as both extractant and solvent in organic reactions, and can also be used as catalyst when HBD or HBA contains specific functional groups. The DES has the advantages of simple preparation, cheap raw materials, repeated use and the like.
The invention provides a method for synthesizing 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene base) -tetra (tridecyl) diphosphite, which comprises the following steps:
step 1: adding 3-methyl-6-tertiary butyl phenol, organic base and n-butyraldehyde into a eutectic solvent consisting of choline chloride (ChCl) and p-toluenesulfonic acid (TsOH) or Malonic Acid (MA), and reacting at 40-70 ℃ under microwave radiation; then adding an organic solvent for extraction, washing, drying and desolventizing an extract, and recrystallizing residues to obtain an intermediate 4,4' -butylene bis (3-methyl-6-tertiary butyl phenol);
step 2: intermediate 4,4 '-butylene bis (3-methyl-6-tertiary butyl phenol) and triphenyl phosphite are reacted with tridecyl alcohol in the presence of alkali to obtain 4,4' -butylene bis- (3-methyl-6-tertiary butyl phenyl) -tetra (tridecyl) diphosphite.
In a preferred embodiment, the eutectic solvent consisting of choline chloride (ChCl) and p-toluene sulfonic acid (TsOH) or Malonic Acid (MA) comprises a mixture of a molar ratio of 1:1 choline chloride (ChCl) and p-toluene sulfonic acid (TsOH), and a eutectic solvent [ ChCl ] [ TsOH ], consisting of a molar ratio of 1:1 and Malonic Acid (MA) [ ChCl ] [ MA ].
The eutectic solvent may be prepared by the following method:
under the protection of inert gas, the mixture of choline chloride and p-toluenesulfonic acid or malonic acid is heated to 90-120 ℃ and stirred until the solution is completely transparent.
Preferably, the molar ratio of choline chloride to p-toluene sulfonic acid or malonic acid is 1:1.
preferably, the stirring temperature is 100 to 110 ℃.
In the present invention, the eutectic solvent is used in an amount such that the ratio of the molar amount of p-toluene sulfonic acid or malonic acid to the molar amount of 3-methyl-6-t-butylphenol is 0.5 to 1.5:1, preferably 0.8 to 1.2:1.
in a preferred embodiment, the organic base is selected from at least one of triethylamine, pyridine, tetramethyl ethylenediamine, and preferably tetramethyl ethylenediamine. The amount of the organic base to be used is 0.5 to 5% by mass, preferably 1 to 2.5% by mass, based on 3-methyl-6-t-butylphenol.
In a preferred embodiment, the molar ratio of 3-methyl-6-tert-butylphenol to n-butyraldehyde is from 2 to 2.2:1, preferably from 2 to 2.1:1.
in a preferred embodiment, the microwave power is 200 to 600W, preferably 300 to 400W.
In a preferred embodiment, the temperature of the reaction is from 55 to 65 ℃; the reaction time is 1min to 30min, preferably 10min to 15min.
In a preferred embodiment, the organic solvent is selected from at least one of diethyl ether, methyl tert-butyl ether, ethyl acetate; preferably, it is selected from methyl tert-butyl ether.
In a preferred embodiment, the washing comprises washing 1 to 3 times with saturated aqueous sodium bicarbonate, each separately.
In a preferred embodiment, the recrystallization comprises dissolving the desolventized residue in 1.5 to 2.5 times by mass of methanol under heating, and then reversely dripping 0.4 to 0.6 times by mass of water, and naturally cooling to room temperature to precipitate crystals.
Preferably, the heating comprises heating to a boiling state; the dosage of the methanol is preferably 1.8 to 2.2 times of the mass of the residue; the amount of water used is preferably 0.45 to 0.55 times the mass of methanol.
In the present invention, the step 2 includes:
under the protection of inert gas, adding an intermediate 4,4' -butylene bis (3-methyl-6-tertiary butyl phenol), tridecyl alcohol and triphenyl phosphite into a reactor, heating to 45-60 ℃ under stirring to form a turbid solution, adding inorganic base, and then heating the reaction mixture to 140-170 ℃ to react for 1.5h; the low-boiling substances and phenol are removed by vacuum distillation, the rest mixture is reduced to 50-60 ℃ and filtered, and 4,4' -butylidenebis- (3-methyl-6-tertiary butylphenyl) -tetra (tridecyl) diphosphite is obtained.
In a preferred embodiment, the molar ratio of the intermediates 4,4' -butylidenebis (3-methyl-6-tert-butylphenol), tridecyl alcohol, triphenyl phosphite is: 1:4 to 5:2 to 2.5, preferably 1:4 to 4.2:2 to 2.1.
In a preferred embodiment, the inorganic base is selected from at least one of sodium hydroxide, potassium hydroxide, cesium carbonate. The inorganic base is used in an amount of 0.1 to 1% by mass of 4,4' -butylidenebis (3-methyl-6-t-butylphenol).
The eutectic solvent has the advantages of being renewable and recyclable, and can be continuously used for the synthesis process of the intermediate 4,4' -butylene bis (3-methyl-6-tert-butylphenol) after being regenerated. Thus, the method of the present invention may further include a step of regenerating the eutectic solvent, and further, a step of recycling the regenerated eutectic solvent.
In a preferred embodiment, the regeneration step of the eutectic solvent: collecting the used eutectic solvent, washing with at least one organic solvent selected from diethyl ether, methyl tertiary butyl ether and ethyl acetate, and drying at 80-120 ℃.
In a preferred embodiment, the regenerated eutectic solvent may be used in step 1. Under the condition of recycling the eutectic solvent, the recycling times can still keep better catalytic property at 6 times.
In the present invention, the inert gas includes at least one of nitrogen or argon.
Advantageous effects
The invention provides a method for synthesizing 4,4' -butylene bis- (3-methyl-6-tertiary butylbenzene group) -tetra (tridecyl) diphosphite. In the method, in the synthesis process of the intermediate 4,4 '-butylene bis (3-methyl-6-tert-butylphenol), the eutectic solvent [ ChCl ] [ TsOH ] or [ ChCl ] [ MA ] is adopted as a solvent and a catalyst, and the intermediate 4,4' -butylene bis (3-methyl-6-tert-butylphenol) is prepared by a microwave synthesis method, so that the reaction yield is high, and the product purity can reach more than 99.5%. In the invention, under the condition of using the eutectic solvent, the microwave assistance not only greatly improves the reaction rate, but also obviously improves the reaction yield. The eutectic solvent can be recycled for a plurality of times, the purity of the product can still reach more than 99.0% after the eutectic solvent is recycled for 6 times, and the synthesis method is environment-friendly. The 4,4 '-butylene bis- (3-methyl-6-tertiary butylphenyl) -tetra (tridecyl) diphosphite product prepared by taking the high-purity intermediate 4,4' -butylene bis (3-methyl-6-tertiary butyl phenol) as a raw material has high content and good quality. Thus, the method of the present invention is suitable for industrial application.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
Hereinafter, preferred examples of the invention will be described in detail. The examples are presented for better understanding of the invention and are not intended to limit the invention to the examples. Insubstantial modifications and adaptations of the embodiments in accordance with the summary of the invention remain within the scope of the invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications.
Example 1:
under the protection of nitrogen, a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of p-toluenesulfonic acid (TsOH) is added to the magnetic deviceHeating to 100deg.C in a reactor, stirring for 1 hr until the solution is completely transparent, and absorbing small amount of released HCl with alkali solution; slowly cooling to room temperature to obtain eutectic solvent [ ChCl ]][TsOH]. 0.2mol of 3-methyl-6-tert-butylphenol and 0.5g of tetramethyl ethylenediamine are added thereto, 0.1mol of n-butyraldehyde is slowly added dropwise, and the mixture is reacted at 60℃for 10 minutes under 300W of microwave radiation. After cooling, 300ml of methyl tert-butyl ether was slowly added to extract the product, the methyl tert-butyl ether layer was carefully separated and washed twice with saturated aqueous sodium hydrogencarbonate, and water was separated, dried over anhydrous sodium sulfate, and after desolventizing, 37.1g of a residue was obtained, which was put into 60g of methanol, heated to boiling for dissolution, and after stopping heating and slowly dropping 30g of water, followed by natural cooling to room temperature to precipitate crystals, 34.9g of crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) was obtained in a yield of 91.22% and a purity of 99.73%. ESI-MS:383.3[ M+H ]] + 。
50mmol of intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol), 210mmol of tridecyl alcohol and 100mmol of triphenyl phosphite are added to a reactor under the protection of nitrogen, the mixture is heated to 55 ℃ under stirring to form a turbid solution, then 0.1g of KOH is added, and the reaction mixture is heated to 150 ℃ to react for 1.5h; thereafter, the supply of nitrogen was stopped and vacuum distillation was performed at a pressure of 1mmHg and a temperature of 180 to 185℃until all of the low boiling substances and phenol were distilled off. The remaining mixture was cooled to 55℃and filtered to give 61.8g of colorless transparent 4,4' -butylidenebis- (3-methyl-6-t-butylphenyl) -tetra (tridecyl) bisphosphite, content 98.41%. ESI-MS:1240.1[ M+H ]] + 。
Example 2: recycling of eutectic solvent [ ChCl ] [ TsOH ]
The eutectic solvent [ ChCl ] [ TsOH ] extracted with methyl tert-butyl ether in example 1 was washed 1-2 times with methyl tert-butyl ether, and then dried for 1h at 95 ℃. After cooling, the subsequent reaction and treatment steps were carried out in a similar manner to example 1. This step is repeated a plurality of times. The conditions for obtaining intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) are listed in the following table:
| number of repetitions | 1 | 2 | 3 | 4 | 5 | 6 |
| Yield is good | 90.83％ | 90.54％ | 90.11％ | 89.43％ | 88.34％ | 85.25％ |
| Purity of | 99.63％ | 99.61％ | 99.53％ | 99.40％ | 99.22％ | 99.04％ |
Example 3:
under the protection of nitrogen, a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of p-toluenesulfonic acid (TsOH) is added into a reactor of a magnetic device, heated to 100 ℃ and stirred for 1h until the solution is completely transparent, and a small amount of released HCl is absorbed by alkali liquor; slowly cooling to room temperature to obtain eutectic solvent [ ChCl ] [ TsOH ]. 0.25mol of 3-methyl-6-tert-butylphenol and 0.625g of tetramethyl ethylenediamine are added thereto, 0.125mol of n-butyraldehyde is slowly added dropwise, and the mixture is reacted at 60℃for 10 minutes under 300W of microwave radiation. After cooling, 370ml of methyl tert-butyl ether was slowly added to extract the product, the methyl tert-butyl ether layer was carefully separated and washed twice with saturated aqueous sodium hydrogencarbonate, and water was separated, dried over anhydrous sodium sulfate, and after desolventizing 45.2g of the residue was obtained, which was put into 75g of methanol, heated to boiling to dissolve, heating was stopped and 37.5g of water was slowly added dropwise, followed by natural cooling to room temperature to precipitate crystals, 42.8g of crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) was obtained in a yield of 89.49% and a purity of 99.5%.
Example 4:
under the protection of nitrogen, a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of Malonic Acid (MA) is added into a reactor of a magnetic device, heated to 100 ℃ and stirred for 1.5h until the solution is completely transparent, and a small amount of released HCl is absorbed by alkali liquor; slowly cooling to room temperature to obtain eutectic solvent [ ChCl ] [ MA ]. 0.2mol of 3-methyl-6-tert-butylphenol and 0.5g of tetramethyl ethylenediamine are added thereto, 0.1mol of n-butyraldehyde is slowly added dropwise, and the mixture is reacted at 60℃for 10 minutes under 300W of microwave radiation. After cooling, 330ml of methyl tert-butyl ether was slowly added to extract the product, the methyl tert-butyl ether layer was carefully separated and washed twice with saturated aqueous sodium hydrogencarbonate, and water was separated, dried over anhydrous sodium sulfate, and after desolventizing, 37.8g of a residue was obtained, which was put into 60g of methanol, heated to boiling for dissolution, and after stopping heating and slowly dropping 30g of water, followed by natural cooling to room temperature to precipitate crystals, 35.4g of crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) was obtained in a yield of 92.52% and a purity of 99.6%.
Example 5: recycling of eutectic solvent [ ChCl ] [ MA ]
The eutectic solvent [ ChCl ] [ MA ] extracted with methyl tert-butyl ether in example 2 was washed 1-2 times with methyl tert-butyl ether, and then dried for 1h at 95 ℃. After cooling, the subsequent reaction and treatment steps were carried out in a similar manner to example 4. This step is repeated a plurality of times. The conditions for obtaining intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) are listed in the following table:
| number of repetitions | 1 | 2 | 3 | 4 | 5 | 6 |
| Yield is good | 91.73％ | 91.50％ | 91.02％ | 90.54％ | 89.86％ | 86.45％ |
| Purity of | 99.63％ | 99.70％ | 99.45％ | 99.31％ | 99.15％ | 99.10％ |
Comparative example 1:
under the protection of nitrogen, a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of p-toluenesulfonic acid (TsOH) is added into a reactor of a magnetic device, heated to 100 ℃ and stirred for 1h until the solution is completely transparent, and a small amount of released HCl is absorbed by alkali liquor; slowly cooling to room temperature to obtain eutectic solvent [ ChCl ] [ TsOH ]. To this was added 0.2mol of 3-methyl-6-t-butylphenol and 0.5g of tetramethyl ethylenediamine, and 0.1mol of n-butyraldehyde was slowly added dropwise thereto, and the mixture was heated to 60℃in an oil bath to react for 3 hours. After cooling, 300ml of methyl tert-butyl ether was slowly added to extract the product, the methyl tert-butyl ether layer was carefully separated and washed twice with saturated aqueous sodium hydrogencarbonate, and water was separated, dried over anhydrous sodium sulfate, and after desolventizing, 36.2g of the residue was obtained, which was put into 60g of methanol, heated to boiling for dissolution, and after stopping heating and slowly dropping 30g of water, followed by natural cooling to room temperature to precipitate crystals, 32.3g of crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) was obtained in a yield of 84.42% and a purity of 98.76%.
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Modifications and variations to the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (9)
1. A method for synthesizing 4,4' -butylene bis- (3-methyl-6-tertiary butylphenyl) -tetra (tridecyl) diphosphite, comprising:
step 1: adding 3-methyl-6-tertiary butyl phenol, organic base and n-butyraldehyde into a eutectic solvent consisting of choline chloride (ChCl) and p-toluenesulfonic acid (TsOH) or Malonic Acid (MA), and reacting at 40-70 ℃ under microwave radiation; then adding an organic solvent for extraction, washing, drying and desolventizing an extract, and recrystallizing residues to obtain an intermediate 4,4' -butylene bis (3-methyl-6-tertiary butyl phenol); the microwave radiation and the microwave power are 200-600W; the eutectic solvents consisting of choline chloride (ChCl) and p-toluenesulfonic acid (TsOH) or Malonic Acid (MA) are respectively prepared from the following components in a molar ratio of 1:1 choline chloride (ChCl) and p-toluene sulfonic acid (TsOH), and a eutectic solvent [ ChCl ] [ TsOH ], consisting of a molar ratio of 1:1 (i) a eutectic solvent [ ChCl ] [ MA ] consisting of choline chloride (ChCl) and Malonic Acid (MA); the organic base is selected from tetramethyl ethylenediamine; the organic solvent is at least one selected from diethyl ether, methyl tertiary butyl ether and ethyl acetate; the recrystallization comprises heating and dissolving the residue after desolventizing in 1.5-2.5 times of methanol, then reversely dripping water 0.4-0.6 times of the methanol, naturally cooling to room temperature to precipitate crystals;
step 2: intermediate 4,4 '-butylene bis (3-methyl-6-tertiary butyl phenol) and triphenyl phosphite are reacted with tridecyl alcohol in the presence of inorganic base to obtain 4,4' -butylene bis- (3-methyl-6-tertiary butyl phenyl) -tetra (tridecyl) diphosphite.
2. The synthetic method of claim 1, wherein the eutectic solvent is prepared by:
under the protection of inert gas, the mixture of choline chloride and p-toluenesulfonic acid or malonic acid is heated to 90-120 ℃ and stirred until the solution is completely transparent.
3. The synthetic method according to claim 1, wherein the eutectic solvent is used in an amount such that a ratio of a molar amount of p-toluene sulfonic acid or malonic acid to a molar amount of 3-methyl-6-t-butylphenol is 0.5 to 1.5:1.
4. the synthetic method according to claim 1, wherein the eutectic solvent is used in an amount such that a ratio of a molar amount of p-toluene sulfonic acid or malonic acid to a molar amount of 3-methyl-6-t-butylphenol is 0.8 to 1.2:1.
5. the synthesis method according to claim 1, wherein the amount of the organic base is 0.5 to 5% by mass of the 3-methyl-6-tert-butylphenol.
6. The synthetic method of claim 1 wherein the organic solvent is selected from the group consisting of methyl tertiary butyl ether.
7. The synthesis method according to claim 1, wherein the step 2 comprises:
under the protection of inert gas, adding an intermediate 4,4' -butylene bis (3-methyl-6-tertiary butyl phenol), tridecyl alcohol and triphenyl phosphite into a reactor, heating to 45-60 ℃ under stirring to form a turbid solution, adding inorganic base, and then heating the reaction mixture to 140-170 ℃ to react for 1.5h; the low-boiling substances and phenol are removed by vacuum distillation, the rest mixture is reduced to 50-60 ℃ and filtered, and 4,4' -butylidenebis- (3-methyl-6-tertiary butylphenyl) -tetra (tridecyl) diphosphite is obtained.
8. The method of synthesizing according to claim 1, further comprising the step of regenerating the eutectic solvent, and the step of recycling the regenerated eutectic solvent.
9. The method of synthesizing according to claim 8, wherein the regenerating step of the eutectic solvent: collecting the used eutectic solvent, washing with at least one organic solvent selected from diethyl ether, methyl tertiary butyl ether and ethyl acetate, and drying at 80-120 ℃.
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