CN115304638A - 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite synthesis method - Google Patents
4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite synthesis method Download PDFInfo
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- -1 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) Chemical group 0.000 title claims abstract description 23
- PDNNNTTZJOPATP-UHFFFAOYSA-N dihydroxyphosphanyl tridecyl hydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)OP(O)O PDNNNTTZJOPATP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 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 49
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 230000005496 eutectics Effects 0.000 claims abstract description 35
- 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 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012467 final product Substances 0.000 claims abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 52
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 40
- 235000019743 Choline chloride Nutrition 0.000 claims description 40
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 40
- 229960003178 choline chloride Drugs 0.000 claims description 40
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 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 26
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment 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 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 9
- 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
- 238000009835 boiling Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 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
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RLKFNDFGXOQHQN-UHFFFAOYSA-N 2-nonylphenol;phosphorous acid Chemical compound OP(O)O.CCCCCCCCCC1=CC=CC=C1O.CCCCCCCCCC1=CC=CC=C1O.CCCCCCCCCC1=CC=CC=C1O RLKFNDFGXOQHQN-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 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
- 238000006053 organic reaction Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920000642 polymer Polymers 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
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- QUTZUATVZPXUJR-UHFFFAOYSA-N trinonyl phosphite Chemical compound CCCCCCCCCOP(OCCCCCCCCC)OCCCCCCCCC QUTZUATVZPXUJR-UHFFFAOYSA-N 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' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite. According to the method, a eutectic solvent [ ChCl ] [ TsOH ] or [ ChCl ] [ MA ] is used as a solvent and a catalyst at the same time, an intermediate 4,4 '-butylidene bis (3-methyl-6-tert-butylphenol) is prepared by a microwave synthesis method, and 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite is synthesized from the intermediate. The method has high yield of the intermediate and high purity of the product, so the quality of the final product is good. The synthetic method is green and environment-friendly, and the eutectic solvent can be recycled and is suitable for being applied in industry.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for synthesizing 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite.
Background
The phosphite ester antioxidant has a structural formula of
(R 1 、R 3 Is alkyl, aryl or substituted aryl, which can be the same or different, and can also form a ring), is an auxiliary antioxidant and is used as hydroperoxyThe compound decomposer and the radical scavenger play an antioxidant role in the polymer, are often used together with hindered phenol, and are not generally used independently. Phosphite antioxidants include: triphenyl phosphite, trinonyl phosphite, monobutyldiphenyl phosphite, tris (nonylphenol) phosphite, tris (2,4-di-tert-butyl) phenyl phosphite, trioctyl phosphite, bis (2-methyl-4,6-bis (1,3-dimethylethyl) phenyl) ethyl phosphite, dioctadecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite, and the like.
Among them, 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite is excellent in properties and has strong market demand. It is generally prepared by the following method: 3-methyl-6-tert-butylphenol and n-butyl aldehyde are synthesized into an intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol) in the presence of alkali and a catalyst, the intermediate is further reacted with triphenyl phosphite and tridecanol in the presence of alkali to obtain the compound, and low-boiling-point impurities and phenol are removed by distillation. The purity of the intermediate 4,4 '-butylidenebis (3-methyl-6-tert-butylphenol) is, among others, a concern with respect to the quality of 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite. The intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol) (BBM) is an antioxidant, and U.S. Pat. No. 4, 2970151, U.S. Pat. No. 4, 28318974, U.S. Pat. No. 3, 2822404, JP2007269711A, JP2012136548A, CN108586206A, CN104591972A and the like disclose that hydrochloric acid, sulfuric acid, p-toluenesulfonic acid and the like are used as catalysts, but the problems of low product yield and purity, troublesome post-treatment, more three wastes and the like exist.
Therefore, there is a need to develop more efficient methods for the synthesis of 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetrakis (tridecyl) diphosphite.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite, which comprises the steps of synthesizing an intermediate 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite under microwave radiation by using 3-methyl-6-tert-butylphenol and n-butyl aldehyde as raw materials and a eutectic solvent containing p-toluenesulfonic acid or malonic acid as a solvent and a catalyst at the same time, and then synthesizing 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite.
The eutectic solvent (DES) is a eutectic mixture with melting point below 100 deg.C formed by Hydrogen Bond Donor (HBD) and Hydrogen Bond Acceptor (HBA) via intermolecular hydrogen bonding. HBA includes quaternary ammonium salt, quaternary phosphonium salt, etc., and HBD includes amides, alcohols, carboxylic acids, sulfonic acids, etc. DES can be used both as an extractant and as a solvent in organic reactions, and as a catalyst when HBD or HBA contains specific functional groups. The DES has the advantages of simple preparation, cheap raw materials and the like, and can be repeatedly utilized.
The invention provides a 4,4' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite synthesis method, which comprises the following steps:
step 1: adding 3-methyl-6-tert-butylphenol, 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 the extract liquor, and recrystallizing the residue to obtain an intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol);
step 2: intermediate 4,4 '-butylidenebis (3-methyl-6-tert-butylphenol) was reacted with triphenyl phosphite, tridecyl alcohol in the presence of a base to give 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetrakis (tridecyl) diphosphite.
In a preferred embodiment, the eutectic solvent consisting of choline chloride (ChCl) and p-toluenesulfonic acid (TsOH) or Malonic Acid (MA) comprises a mixture of two or more of the following components in a molar ratio of 1:1 choline chloride (ChCl) and p-toluenesulfonic acid (TsOH), and a eutectic solvent [ ChCl ] [ TsOH ] consisting of 1:1 choline chloride (ChCl) 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-toluenesulfonic acid or malonic acid is 1:1.
preferably, the stirring temperature is 100 to 110 ℃.
In the invention, the amount of the eutectic solvent is such that the ratio of the molar weight of p-toluenesulfonic acid or malonic acid to the molar weight of 3-methyl-6-tert-butylphenol is 0.5-1.5: 1, preferably 0.8 to 1.2:1.
in a preferred embodiment, the organic base is selected from at least one of triethylamine, pyridine, tetramethylethylenediamine, and preferably tetramethylethylenediamine. The amount of the organic base is 0.5 to 5% by mass, preferably 1 to 2.5% by mass, based on the mass of 3-methyl-6-tert-butylphenol.
In a preferred embodiment, the molar ratio of 3-methyl-6-tert-butylphenol to n-butyraldehyde is between 2 and 2.2:1, preferably, from 2 to 2.1:1.
in a preferred embodiment, the microwave power is from 200 to 600W, preferably from 300 to 400W.
In a preferred embodiment, the temperature of the reaction is between 55 and 65 ℃; the reaction time is 1-30 min, preferably 10-15 min.
In a preferred embodiment, the organic solvent is selected from at least one of ethyl ether, methyl tert-butyl ether, ethyl acetate; preferably, it is selected from methyl tert-butyl ether.
In a preferred embodiment, the washing comprises washing with a saturated aqueous sodium bicarbonate solution, water, 1 to 3 times, respectively.
In a preferred embodiment, the recrystallization comprises heating and dissolving the residue after desolventizing in methanol of 1.5 to 2.5 times by mass, and then back-dropping water of 0.4 to 0.6 times by mass of methanol, 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 residual substance; 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 the intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol), tridecanol and triphenyl phosphite into a reactor, heating to 45-60 ℃ under stirring to form turbid solution, then adding inorganic base, and heating the reaction mixture to 140-170 ℃ for reaction for 1.5h; the low boilers and phenol were removed by vacuum distillation and the remaining mixture was cooled to 50-60 ℃ and filtered to give 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite.
In a preferred embodiment, the intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol), tridecanol, triphenyl phosphite are present in a molar ratio of: 1:4 to 5:2 to 2.5, preferably it is 1: 4-4.2: 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 dosage of the inorganic base is 4,4' -butylidene bis (3-methyl-6-tert-butylphenol) 0.1-1% of the mass.
The eutectic solvent has the advantages of regeneration and recycling, and can be continuously used for the synthesis process of an intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol) after regeneration. Therefore, the method of the present invention may further include the step of regenerating the eutectic solvent, and further, the step of recycling the regenerated eutectic solvent.
In a preferred embodiment, the step of regenerating the eutectic solvent: collecting the used eutectic solvent, washing with at least one organic solvent selected from diethyl ether, methyl tert-butyl ether and ethyl acetate, and drying at 80-120 deg.C to obtain the final product.
In a preferred embodiment, the regenerated eutectic solvent may be used in step 1. Under the condition of recycling, the eutectic solvent can still keep better catalytic property after being recycled for 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' -butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite. According to the method, in the synthesis process of the intermediate 4,4 '-butylidene bis (3-methyl-6-tert-butylphenol), the intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol) is prepared by a microwave synthesis method by using a eutectic solvent [ ChCl ] [ TsOH ] or [ ChCl ] [ MA ] as a solvent and a catalyst, 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 multiple times, the product purity can still reach more than 99.0 percent after 6 times of recycling, and the synthesis method is green and environment-friendly. The 4,4 '-butylidene bis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite product prepared by using the high-purity intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol) as a raw material has high content and good quality. Therefore, the method of the present invention is suitable for industrial applications.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
Hereinafter, preferred examples of the invention will be described in detail. The examples are given for the purpose of better understanding of the inventive content and are not intended to be limiting only. Insubstantial modifications and adaptations of the embodiments in accordance with the present disclosure remain within the scope of the invention.
The experimental procedures in the following examples are conventional unless otherwise specified. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.
Example 1:
under the protection of nitrogen, adding a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of p-toluenesulfonic acid (TsOH) into a reactor of a magnetic device, heating to 100 ℃, stirring for 1h until the solution is completely transparent, and absorbing a small amount of released HCl with alkali liquor; slowly cooling to room temperature to obtain eutectic solvent [ ChCl][TsOH]. 0.2mol of 3-methyl-6-tert-butylphenol and 0.5g of tetramethylethylenediamine were added thereto, and 0.1mol of n-butyraldehyde was slowly added dropwise thereto, followed by reaction at 60 ℃ for 10 minutes under 300W microwave irradiation. 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 bicarbonate solution and water, dried over anhydrous sodium sulfate and desolventized to obtain 37.1g of a residue, which was put into 60g of methanol and heated to boiling to dissolve, after heating, 30g of water was stopped and slowly added dropwise, followed by natural cooling to room temperature to precipitate crystals, to obtain 34.9g of a crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol), with 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 tridecanol and 100mmol of triphenyl phosphite are added to a reactor under nitrogen, heated to 55 ℃ with stirring to form a turbid solution, 0.1g of KOH is added, and the reaction mixture is heated to 150 ℃ for 1.5h; thereafter, the nitrogen feed was stopped and the vacuum distillation was carried out at a pressure of 1mmHg and a temperature of 180 to 185 ℃ until low boiling substances and phenol were distilled off completely. The remaining mixture was cooled to 55 ℃ and filtered to give 61.8g of colorless clear 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite with a content of 98.41%. ESI-MS:1240.1[ 2 ] M + H] + 。
Example 2: recycling of eutectic solvent [ ChCl ] [ TsOH ]
The eutectic solvent [ ChCl ] [ TsOH ] extracted from the methyl tert-butyl ether in example 1 was washed with methyl tert-butyl ether 1-2 times, and then warmed to 95 ℃ and dried for 1 hour. After cooling, the subsequent reaction and treatment steps were carried out in a similar manner to example 1. This step is repeated a number of times. The intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) obtained is shown in the table below:
| number of repetitions | 1 | 2 | 3 | 4 | 5 | 6 |
| Yield of the product | 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:
adding a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of p-toluenesulfonic acid (TsOH) into a reactor of a magnetic device under the protection of nitrogen, heating to 100 ℃, stirring for 1h until the solution is completely transparent, and absorbing a small amount of HCl released by alkali liquor; slowly cooling to room temperature to obtain a eutectic solvent [ ChCl ] [ TsOH ]. 0.25mol of 3-methyl-6-tert-butylphenol and 0.625g of tetramethylethylenediamine were added thereto, 0.125mol of n-butyraldehyde was slowly added dropwise thereto, and the reaction was carried out for 10 minutes at 60 ℃ under 300W microwave irradiation. 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 bicarbonate solution and water, dried over anhydrous sodium sulfate and desolventized to obtain 45.2g of a residue, which was put into 75g of methanol and heated to boiling to dissolve, after stopping heating and slowly dropping 37.5g of water, followed by natural cooling to room temperature to precipitate crystals, to obtain a crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) 42.8g, with a yield of 89.49% and a purity of 99.5%.
Example 4:
adding a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of Malonic Acid (MA) into a reactor of a magnetic device under the protection of nitrogen, heating to 100 ℃, stirring for 1.5 hours until the solution is completely transparent, and absorbing a small amount of HCl released 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 tetramethylethylenediamine were added thereto, and 0.1mol of n-butyraldehyde was slowly added dropwise and reacted at 60 ℃ for 10min under 300W microwave irradiation. 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 bicarbonate solution and water, dried over anhydrous sodium sulfate and desolventized to give 37.8g of a residue, which was put into 60g of methanol, heated to boiling to dissolve, then heated and slowly added dropwise with 30g of water, followed by natural cooling to room temperature to precipitate crystals, to give 35.4g of a crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol), with 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 from example 2 with methyl tert-butyl ether was washed 1-2 times with methyl tert-butyl ether, and then dried at 95 ℃ for 1h. After cooling, the subsequent reaction and treatment steps were carried out in a similar manner to example 4. This step is repeated a number of times. The intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) obtained is shown in the table below:
| number of repetitions | 1 | 2 | 3 | 4 | 5 | 6 |
| Yield of the product | 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:
adding a mixture of 0.2mol of choline chloride (ChCl) and 0.2mol of p-toluenesulfonic acid (TsOH) into a reactor of a magnetic device under the protection of nitrogen, heating to 100 ℃, stirring for 1h until the solution is completely transparent, and absorbing a small amount of HCl released by alkali liquor; slowly cooling to room temperature to obtain a eutectic solvent [ ChCl ] [ TsOH ]. 0.2mol of 3-methyl-6-tert-butylphenol and 0.5g of tetramethylethylenediamine were added thereto, 0.1mol of n-butyraldehyde was slowly added dropwise thereto, and the mixture was heated in an oil bath to 60 ℃ for reaction for 3 hours. After cooling, slowly adding 300ml of methyl tert-butyl ether to extract a product, carefully separating a methyl tert-butyl ether layer, respectively washing twice with saturated sodium bicarbonate aqueous solution and water, drying with anhydrous sodium sulfate, desolventizing to obtain 36.2g of residue, adding the residue into 60g of methanol, heating until boiling to dissolve, stopping heating, slowly adding 30g of water dropwise, and naturally cooling to room temperature to precipitate crystals, thereby obtaining a crystalline intermediate 4,4' -butylidenebis (3-methyl-6-tert-butylphenol) 32.3g, wherein the yield is 84.42%, and the purity is 98.76%.
The above description is of the preferred embodiment of the present invention, but it is not intended to limit the present invention. Modifications and variations of the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (10)
1. A method of 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetrakis (tridecyl) diphosphite synthesis comprising:
step 1: adding 3-methyl-6-tert-butylphenol, organic base and n-butyl aldehyde 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 the extract liquor, and recrystallizing the residue to obtain an intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol);
step 2: intermediate 4,4 '-butylidenebis (3-methyl-6-tert-butylphenol) was reacted with triphenyl phosphite, tridecyl alcohol in the presence of a base to give 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetrakis (tridecyl) diphosphite.
2. The synthesis method according to claim 1, wherein the eutectic solvent consisting of choline chloride (ChCl) and p-toluenesulfonic acid (TsOH) or Malonic Acid (MA) comprises a mixture of two or more of the following compounds in a molar ratio of 1:1 of choline chloride (ChCl) and p-toluenesulfonic acid (TsOH), and a mixture of 1:1 choline chloride (ChCl) and Malonic Acid (MA) [ ChCl ] [ MA ].
3. A synthesis method according to claim 1 or 2, characterized in that the eutectic solvent can be 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.
4. The synthesis method according to claim 1, characterized in that the amount of the eutectic solvent is such that the ratio of the molar amount of p-toluenesulfonic acid or malonic acid to the molar amount of 3-methyl-6-tert-butylphenol is 0.5 to 1.5:1, preferably 0.8 to 1.2:1.
5. the synthesis method according to claim 1, wherein the organic base is at least one selected from triethylamine, pyridine and tetramethylethylenediamine, and is preferably tetramethylethylenediamine; the dosage of the organic alkali is 0.5-5% of the mass of the 3-methyl-6-tert-butylphenol.
6. The synthesis method according to claim 1, wherein the organic solvent is at least one selected from diethyl ether, methyl tert-butyl ether and ethyl acetate; preferably, it is selected from methyl tert-butyl ether.
7. The synthesis method of claim 1, wherein the recrystallization comprises heating and dissolving the residue after desolventizing in methanol of 1.5 to 2.5 times by mass, and then back-dropping water of 0.4 to 0.6 times by mass of methanol, and naturally cooling to room temperature to precipitate crystals.
8. The synthesis method according to claim 1, characterized in that said step 2 comprises:
under the protection of inert gas, adding the intermediate 4,4' -butylidene bis (3-methyl-6-tert-butylphenol), tridecanol and triphenyl phosphite into a reactor, heating to 45-60 ℃ under stirring to form turbid solution, then adding inorganic base, and heating the reaction mixture to 140-170 ℃ for reaction for 1.5h; the low boilers and phenol were removed by vacuum distillation and the remaining mixture was cooled to 50-60 ℃ and filtered to give 4,4' -butylidenebis- (3-methyl-6-tert-butylphenyl) -tetra (tridecyl) diphosphite.
9. The method of synthesis according to claim 1, further comprising the step of regenerating the eutectic solvent, and the step of recycling the regenerated eutectic solvent.
10. The synthesis method according to claim 9, characterized in that the regeneration step of the eutectic solvent: collecting the used eutectic solvent, washing with at least one organic solvent selected from diethyl ether, methyl tert-butyl ether and ethyl acetate, and drying at 80-120 deg.C to obtain the final product.
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