CN114057788A - Preparation method of high-purity 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate) - Google Patents
Preparation method of high-purity 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate) Download PDFInfo
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- CN114057788A CN114057788A CN202111492294.0A CN202111492294A CN114057788A CN 114057788 A CN114057788 A CN 114057788A CN 202111492294 A CN202111492294 A CN 202111492294A CN 114057788 A CN114057788 A CN 114057788A
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- biphenol
- phosphate
- dimethylphenyl
- phosphorus oxychloride
- bis
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- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 78
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000004821 distillation Methods 0.000 claims abstract description 28
- 239000012043 crude product Substances 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 4,4 ' -biphenol phosphoryl chloride Chemical compound 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000007711 solidification Methods 0.000 claims abstract description 3
- 230000008023 solidification Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 49
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 32
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 16
- 239000002841 Lewis acid Substances 0.000 claims description 12
- 150000007517 lewis acids Chemical class 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- MMGGLJRTCOAXHD-UHFFFAOYSA-N bis(2,6-dimethylphenyl) [4-(4-hydroxyphenyl)phenyl] phosphate Chemical compound Cc1cccc(C)c1OP(=O)(Oc1ccc(cc1)-c1ccc(O)cc1)Oc1c(C)cccc1C MMGGLJRTCOAXHD-UHFFFAOYSA-N 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000000539 dimer Substances 0.000 abstract description 4
- VXZJUYUVOQZBNU-UHFFFAOYSA-N phosphoric acid 1,2-xylene Chemical compound P(=O)(O)(O)O.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C VXZJUYUVOQZBNU-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 5
- 229940117389 dichlorobenzene Drugs 0.000 description 5
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
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-
- 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
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
-
- 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
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
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- 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 preparation method of high-purity 4,4 ' -biphenol bis (di (2, 6-dimethylphenyl) phosphate), which is characterized in that 4,4 ' -biphenol reacts with phosphorus oxychloride under the action of a catalyst to generate a mixture of 4,4 ' -biphenol phosphoryl chloride and phosphorus oxychloride; removing phosphorus oxychloride by reduced pressure distillation under high vacuum to obtain 4, 4' -biphenol phosphorus oxychloride; under the action of a catalyst, 4,4 '-biphenol phosphoryl chloride reacts with 2, 6-xylenol to generate a crude product of 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate); adding toluene and the like into the crude product as a solvent, and carrying out acid washing, alkali washing, water washing, reduced pressure distillation, solidification and crushing to obtain a finished product of the 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate). The method has simple process, and the prepared finished product has low content of the tri (xylene) phosphate TXP, low content of the dimer and high purity; and can be mass-produced by using the existing equipment.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of high-purity 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate).
Background
4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) is a solid halogen-free phosphate flame retardant, and has high melting point, good thermal stability and hydrolysis resistance. The flame retardant can be used as a flame retardant for most types of engineering plastic products, and particularly can be used as a flame retardant for high polymer materials such as PC, PC/ABS, PPO/HIPS/ABS/PET/PBT/PA 6/phenolic resin, epoxy resin and the like; can also be used in combination with other environment-friendly flame retardants, flame-retardant resins, flame-retardant synergists and the like;
the engineering plastic flame retardant existing in the market at present, such as: the melting points of BDP, PX-200 and other flame retardants are far less than that of 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate).
Currently, Daba chemical industries, Japan, Inc. discloses a process (CN 102985430A) for preparing 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) in two steps, the first step: reacting phosphorus oxychloride with xylenol to obtain phosphorus oxychloride; the second step is that: the phosphorus oxychloride reacts with the diphenol to obtain a product, and the method easily generates trixylenyl phosphate (TXP) in the first step; dichlorobenzene is used as a solvent, so that solvent residue is easily caused, the product quality and the using effect are influenced, and in the aspect of environmental protection treatment, greater pressure is caused, and the molecular formula of TXP is as follows:
disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of high-purity 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate).
The invention discloses a preparation method of high-purity 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate), which is characterized by comprising the following steps:
step 1) reacting 4,4 '-biphenol with excessive phosphorus oxychloride under the catalytic action of Lewis acid to generate a mixture of 4, 4' -biphenol phosphorus oxychloride intermediate and phosphorus oxychloride,
the intermediate comprises a monomeric intermediate and a dimeric intermediate, wherein the structural formula of the monomeric intermediate is as follows:
the structural formula of the dimeric intermediate is as follows:
step 2) carrying out reduced pressure distillation on the product obtained in the step 1) under high vacuum to remove phosphorus oxychloride and obtain an intermediate 4, 4' -biphenol phosphorus oxychloride;
step 3) reacting the 4,4 '-biphenol phosphoryl chloride obtained in the step 2) with 2, 6-xylenol under the action of a catalyst to generate a crude product of 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate);
step 4) adding a toluene solvent into the crude product obtained in the step 3), and obtaining a target product 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate) after acid washing, alkali washing, water washing, reduced pressure distillation, solidification and crushing,
the molecular formula of 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) is as follows:
further, the invention also defines that the Lewis acid in the step 1) comprises anhydrous magnesium chloride, anhydrous aluminum chloride, zinc chloride, titanium tetrachloride or butyl titanate, and is preferably anhydrous magnesium chloride; the charging amount of the Lewis acid is 0.3-2 percent of the 4, 4' -biphenol, and the preferred charging amount is 0.5 percent.
Further, the invention also defines the feeding molar ratio of the phosphorus oxychloride and the 4, 4' -biphenol in the step 1) to be 2-10:1, preferably 2-6:1, and optimally 4: 1.
Further, the present invention also defines the reaction temperature in step 1) to be 90-150 ℃, preferably 120 ℃.
Further, the invention also defines the distillation temperature of the step 2) as 120-200 ℃, preferably 140 ℃.
Further, the invention also defines that the catalyst in the step 3) is Lewis acid, and the Lewis acid is anhydrous magnesium chloride, anhydrous aluminum chloride, anhydrous zinc chloride, titanium tetrachloride or butyl titanate, and is preferably anhydrous aluminum chloride; the charging amount of the Lewis acid is 0.3-2%, preferably 0.5% of the 4, 4' -biphenol.
Further, the invention also limits the reaction temperature of the step 3) to be 120-200 ℃, and preferably 180 ℃.
By adopting the limited technology, compared with the prior art, the invention has the following beneficial effects:
1) in the preparation method, 4 '-biphenol and phosphorus oxychloride react to generate 4, 4' -biphenol phosphoryl chloride, so that in the phosphorus oxychloride removal process, although the temperature is raised, a byproduct dimer is only generated, and in the subsequent reaction, the TXP content is lower;
2) the synthesis process of the invention is carried out under the condition of no solvent, namely no solvent is required to be added, thus not only reducing the production cost, but also greatly reducing the environmental protection pressure and reducing the cost of three-waste treatment; the invention only adds toluene in the post-treatment, and is easier to remove compared with high boiling point solvents such as dichlorobenzene and the like used in the prior art, thereby not only improving the product purity, but also being easy for environmental protection treatment.
Drawings
FIG. 1 is a HPLC chart of the final product of example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
A detection instrument: high performance liquid chromatograph, model: shimadzu LC-2030Plus (ultraviolet detector);
a chromatographic column: shimadzu VP-ODS
Detection conditions are as follows: mobile phase: acetonitrile: water 9: 1; temperature: 25 ℃; total flow rate: 1 ml/min; data acquisition time: 20 min; sample solution introduction amount: 10 ml; detection wavelength: 254 nm.
Example 1
1) Adding 10kg of 4, 4' -biphenol and 50g of anhydrous magnesium chloride into a reaction kettle, slowly heating to 100 ℃, starting to dropwise add 33kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, keeping the temperature for 2 hours after the dropwise adding is finished, heating to 120 ℃, and keeping the temperature until the reaction is finished;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 140 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, slowly heating to 180 ℃, and keeping the temperature for 4 h;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to obtain 38.16kg of finished product with yield 93.16% and HPLC content 98.656%, and the chromatogram is shown in FIG. 1.
Example 2
The same operation as in example 1 was carried out except that the amount of phosphorus oxychloride charged in the first reaction step was changed from 33Kg to 16.5 Kg;
1) adding 10kg of 4, 4' -biphenol and 50g of anhydrous magnesium chloride into a reaction kettle, slowly heating to 100 ℃, starting to dropwise add 16.5kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, keeping the temperature for 2 hours after the dropwise adding is finished, heating to 120 ℃, and keeping the temperature until the reaction is finished;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 140 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, slowly heating to 180 ℃, and keeping the temperature for 4 h;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to obtain 30.11kg of finished product with yield 73.51%.
Example 3
The same operation as in example 1 was carried out except that the maximum temperature in the first reaction step was changed to 120 ℃ and 140 ℃;
1) adding 10kg of 4, 4' -biphenol and 50g of anhydrous magnesium chloride into a reaction kettle, slowly heating to 100 ℃, starting to dropwise add 33kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, keeping the temperature for 2 hours after the dropwise adding is finished, heating to 140 ℃, and keeping the temperature until the reaction is finished;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 140 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, slowly heating to 180 ℃, and keeping the temperature for 4 h;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to obtain 36.32kg of finished product with a yield of 88.67%.
Example 4
The same operation as in example 1 was carried out except that the vacuum distillation temperature was changed from 140 ℃ to 160 ℃ after the second reaction;
1) adding 10kg of 4, 4' -biphenol and 50g of anhydrous magnesium chloride into a reaction kettle, slowly heating to 100 ℃, starting to dropwise add 33kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, keeping the temperature for 2 hours after the dropwise adding is finished, heating to 120 ℃, and keeping the temperature until the reaction is finished;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 160 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, slowly heating to 180 ℃, and keeping the temperature for 4 h;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to obtain 37.58kg of finished product with a yield of 91.75%.
Example 5
The same operation as in example 1 was carried out except that the temperature in the third reaction step was changed from 180 ℃ to 170 ℃;
1) adding 10kg of 4, 4' -biphenol and 50g of anhydrous magnesium chloride into a reaction kettle, slowly heating to 100 ℃, starting to dropwise add 33kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, keeping the temperature for 2 hours after the dropwise adding is finished, heating to 120 ℃, and keeping the temperature until the reaction is finished;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 140 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, slowly heating to 170 ℃, and keeping the temperature for 4 h;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to yield a finished product of 34.52kg with a yield of 84.28%.
Example 6
1) Adding 10kg of 4, 4' -biphenol and 50g of anhydrous magnesium chloride into a reaction kettle, slowly heating to 90 ℃, starting to dropwise add 16.5kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, and keeping the temperature until the reaction is finished after the dropwise adding;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 120 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, and preserving heat for 4 hours after the addition is finished;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degaussing treatment to obtain 21.72kg of finished product with a yield of 53.08%.
Example 7
1) Adding 10kg of 4, 4' -biphenol and 30g of anhydrous aluminum chloride into a reaction kettle, slowly heating to 90 ℃, starting to dropwise add 82.43kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, and keeping the temperature until the reaction is finished after the dropwise adding is finished;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 150 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, and slowly heating to 180 ℃;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to obtain 36.91kg of finished product with a yield of 90.2%.
Example 8
1) Adding 10kg of 4, 4' -biphenol and 200g of butyl titanate into a reaction kettle, slowly heating to 150 ℃, starting to dropwise add 49.46kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, and keeping the temperature until the reaction is finished after the dropwise adding;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 200 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous aluminum chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, and slowly heating to 200 ℃;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to yield 31.73kg of finished product with 77.54% yield.
Example 9
1) Adding 10kg of 4, 4' -biphenol and 50g of magnesium chloride into a reaction kettle, slowly heating to 120 ℃, starting to dropwise add 33kg of phosphorus oxychloride, controlling the dropwise adding speed according to the reflux size, and keeping the temperature until the reaction is finished after the dropwise adding;
2) slowly introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 200 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 50g of anhydrous zinc chloride, gradually adding 26.2kg of 2, 6-xylenol, keeping the temperature for 4h after the addition is finished, and slowly heating to 190 ℃;
4) slowly introducing into vacuum to perform reduced pressure reaction, wherein the maximum vacuum degree reaches 0.096MPa, and obtaining a crude product after the reaction is finished; 2, 6-xylenol is recycled;
5) adding 80kg of toluene into the crude product, heating to 65-70 ℃, washing once with 20kg of hydrochloric acid with the concentration of 7 percent, washing 2 times with 20kg of NaOH solution with the concentration of 7 percent, and washing 2 times with 20kg of deionized water; the solution was subjected to degustation to obtain 34.69kg of finished product with a yield of 84.78%.
Comparative example
1) Adding 25kg of 2, 6-xylenol, 50g of magnesium chloride and 2kg of dichlorobenzene into a reaction kettle, heating to 120 ℃, dropwise adding 15.73kg of phosphorus oxychloride, and slowly heating to 180 ℃ after dropwise adding till the reaction is complete.
2) Introducing vacuum, distilling phosphorus oxychloride, gradually increasing the distillation temperature and the vacuum degree, wherein the distillation temperature is 180 ℃ at most, and the vacuum degree reaches 0.096MPa until no fraction is distilled off, thus obtaining an intermediate;
3) cooling to 120 ℃, adding 9.54kg of 4, 4' -biphenol, 2kg of dichlorobenzene and 45g of aluminum chloride, slowly heating to 180 ℃, preserving heat for 4 hours, then reducing pressure to 20KPa, and reacting until the reaction is finished to obtain a crude product;
4) adding 90kg of dichlorobenzene into the crude product, heating to 85 ℃, washing once with 150kg of hydrochloric acid with the concentration of 2.5 percent and washing 2 times with 150kg of NaOH solution with the concentration of 2 percent respectively, and then washing 2 times with 50kg of deionized water; the solution was subjected to degustation to obtain 25kg of finished product with a yield of 64.02%.
The HPLC analysis results of the products of examples 1 to 9 of the present invention and the products of comparative examples are shown in Table 1:
TABLE 1 HPLC analysis of the products obtained in the inventive and comparative examples
As can be seen from Table 1, by the method defined in the present invention, 4 '-biphenol is firstly reacted with phosphorus oxychloride to generate 4, 4' -biphenol phosphoryl chloride, so that during the phosphorus oxychloride removal process, although the temperature is increased, only by-product dimer is generated, and in the subsequent reaction, the TXP content is lower, so that the dimer content is greatly reduced, and the product content is increased.
Claims (7)
1. A preparation method of high-purity 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate) is characterized by comprising the following steps:
step 1) reacting 4,4 '-biphenol with excessive phosphorus oxychloride under the catalytic action of Lewis acid to generate a mixture of 4, 4' -biphenol phosphorus oxychloride and phosphorus oxychloride;
step 2) carrying out reduced pressure distillation on the product obtained in the step 1) under high vacuum to remove phosphorus oxychloride and obtain an intermediate 4, 4' -biphenol phosphorus oxychloride;
step 3) reacting the 4,4 '-biphenol phosphoryl chloride obtained in the step 2) with 2, 6-xylenol under the action of a catalyst to generate a crude product of 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate);
step 4) adding a toluene solvent into the crude product obtained in the step 3), and obtaining a target product 4, 4' -biphenol bis (di (2, 6-dimethylphenyl) phosphate) after acid washing, alkali washing, water washing, reduced pressure distillation, solidification and crushing,
the molecular formula of 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) is as follows:
2. the method for preparing 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) according to claim 1, wherein the Lewis acid used in the step 1) comprises anhydrous magnesium chloride, anhydrous aluminum chloride, anhydrous zinc chloride, titanium tetrachloride or butyl titanate, preferably anhydrous magnesium chloride; the charging amount of the Lewis acid is 0.3 to 2 percent of the 4, 4' -biphenol.
3. The method for preparing high-purity 4,4 '-biphenol bis (2, 6-dimethylphenyl) phosphate) according to claim 1, wherein the feeding molar ratio of the phosphorus oxychloride to the 4, 4' -biphenol in step 1) is 2-10: 1.
4. The method for preparing high-purity 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) according to claim 1, wherein the reaction temperature in step 1) is 90-150 ℃.
5. The process according to claim 1, wherein the distillation temperature in step 2) is 120-200 ℃.
6. The method for preparing high purity 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) according to claim 1, wherein the catalyst in the step 3) is a lewis acid, and the lewis acid is anhydrous magnesium chloride, anhydrous aluminum chloride, anhydrous zinc chloride, titanium tetrachloride or butyl titanate, preferably anhydrous aluminum chloride; the charging amount of the Lewis acid is 0.3-2% of the 4, 4' -biphenol.
7. The method for preparing high purity 4, 4' -biphenol bis (2, 6-dimethylphenyl) phosphate) according to claim 1, wherein the reaction temperature in step 3) is 120-200 ℃.
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| CN102985430A (en) * | 2010-07-06 | 2013-03-20 | 大八化学工业株式会社 | Method for producing aromatic diphosphates |
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| CN102985430A (en) * | 2010-07-06 | 2013-03-20 | 大八化学工业株式会社 | Method for producing aromatic diphosphates |
| CN110317228A (en) * | 2019-07-09 | 2019-10-11 | 浙江万盛股份有限公司 | A kind of preparation method of bisphenol-A-bis- (diphenyl phosphoesters) |
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